CN100513367C - Manganese deoxidier and its preparation method and application - Google Patents
Manganese deoxidier and its preparation method and application Download PDFInfo
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- CN100513367C CN100513367C CNB2005101167101A CN200510116710A CN100513367C CN 100513367 C CN100513367 C CN 100513367C CN B2005101167101 A CNB2005101167101 A CN B2005101167101A CN 200510116710 A CN200510116710 A CN 200510116710A CN 100513367 C CN100513367 C CN 100513367C
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Abstract
This invention discloses a deoxidizer of manganese system and its preparation and application. The deoxidizer of this invention is using MnO/Mn3O4 as active constituent. Add alkali metal oxide and aluminium oxide that are active accelerators. This invention provides two preparations, which adopt precurosor compound of Mn3O4 or active Mn3O4 that is produced by calcining precurosor compound of Mn3O4 to mix with alkali metal oxide or hydroxide oxide and aluminium, kneading, forming, open-air drying, at last drying or then producing deoxidizer of this invention by calcining after drying. The deoxidizer of this invention can eliminate 1- 2000ppm oxygen which is in the aethylenum or propylene, at the same time it possesses fairly high mechanical strength.
Description
Technical field
The present invention relates to a kind of manganese deoxidier and its production and application, more particularly, the present invention relates to a kind of with MnO/Mn
3O
4Be heavy body high-activity deoxidant of active ingredient and its production and application.
Background technology
Ethene and propylene are important basic Organic Chemicals, wherein generally contain micro amount of oxygen.According to ethylene raw standard GB 7715-87 and propylene feedstocks standard GB 7716-87, oxygen level is≤5ppm (5 * 10 in qualified polymer grade ethylene, the propylene
-6V/V, below identical).Along with developing rapidly of polyethylene and polypropylene technology, various new and effective polyethylene and polypropylene catalyst, for example: sequential use such as BCG, BCH, DQ, PZ, metallocene catalyst are in industrial production.For avoiding the efficient polyolefin catalyst poisoning and deactivation of this class, in production technique, micro-oxygen content in ethene and the propylene there are more strict requirement for restriction, oxygen level≤0.1ppm.Therefore, to be applied to the degree of depth high efficiency deoxidiser of ethene and propylene gas phase or liquid phase be necessary in research and development.
At present, the reductor of using in relevant patent documentation and the industrial production is divided into and is unworthy of the hydrogen deoxidation and joins hydrogen deoxidation two big classes.Be unworthy of the hydrogen deoxidation and be utilizing the principle of oxygen and reductor generation oxidizing reaction to reach the decontamination effect improving of deoxidation.Such reductor for preventing frequent reducing/regenerating, influences normal production because the deoxidation finite capacity, mainly is applicable in the gas oxygen level less than 500ppm, particularly less than the deoxidization technique of 200ppm.The present invention just belongs to this hydrogen reductor type that is unworthy of.
It is 24%～44% that Chinese patent CN1077446 discloses a kind of Mn content, and the support monomer is high-alumina cement, diatomite, Al
2O
3Reductor.Utilize the reductor of this invention preparation to be used for the ethene deoxidation, its deoxidation capacity only is 5.3ml/g, as the data of example among the CN1077446 6, is used for propylene deoxidation activating and regenerating temperature up to 350 ℃.
Chinese patent CN1110249 discloses a kind of loading type reductor, utilizes pickling process at Al
2O
3Load Mn (NO on the carrier
3)
2, Ni (NO
3)
2And Ca (NO
3)
2(example 1 of this patent) or Mg (NO
3)
2(example 2 of this patent) and preparation is unworthy of the hydrogen reductor.Utilize the reductor of this invention preparation when high-temperature roasting, to discharge a large amount of poisonous NO because nitrate decomposes
x, and can be with Al
2O
3Burst.This reductor is applicable to removing of micro amount of oxygen in the nitrogen.
Chinese patent CN1342516 discloses a kind of bimetallic oxide MnO and CuO is the reductor of active constituent, and adds Al
2O
3Carrier machine-shaping can be used for the alkene deoxidation.
The analysis-by-synthesis prior art, activating and regenerating temperature height not only when being used for the alkene deoxidation, and under comparatively high temps, use, make alkene generation polymerization produce green oil easily and bring new contaminating impurity.In addition, existing reductor uses a large amount of carriers, has reduced the content of active constituent manganese in the reductor, thereby has influenced the deoxidation capacity.
People wish to invent a kind of high deoxidation capacity, highly selective and high strength that is used for the alkene medium, and reducing/regenerating and all lower reductor of use temperature.
Summary of the invention
The present invention exists activation, regeneration and use temperature height and the low defective of deoxidation capacity in order to overcome existing reductor, provides a kind of with MnO/Mn
3O
4Being active constituent, is alkene reductor of accelerative activator and its production and application with alkaline earth metal oxide and aluminum oxide.
Concrete technical scheme is as follows:
Manganese deoxidier of the present invention comprises following components in weight percentage: Mn
3O
436%～90%, alkaline earth metal oxide 1%～30%, aluminum oxide 5%～35%.
Reductor of the present invention can also comprise tackiness agent, and the weight percent content of described tackiness agent in manganese deoxidier of the present invention is 1%～10%.The adding tackiness agent can further improve the intensity of reductor.
Described tackiness agent is preferably cement or water glass.
Described alkaline earth metal oxide is preferably calcium oxide, magnesium oxide or barium oxide.The present invention can directly use alkaline earth metal oxide, also can be with alkaline earth metal oxide Ca (OH) for example
2, Mg (OH)
2, Ba (OH)
2Be starting raw material, the high temperature on-site preparation.Alkaline-earth metal not only has the alkalescence that increases reductor and improves deoxy performance, and can improve the physical strength of reductor significantly.
Described aluminum oxide is precursor with the pseudo-boehmite preferably, at the γ-Al of 400～500 ℃ of following roastings
2O
3, the bulk density of described pseudo-boehmite is preferably 0.2～0.8g/ml, 0.2～0.3g/ml more preferably, and loss of weight 20～40% after the roasting, more preferably loss of weight 20～30% after the roasting.Described γ-Al
2O
3Specific surface area be 200～300m
2/ g, more preferably 250～300m
2/ g.
Deoxidation principle of the present invention is the oxide M n that the reaction of the micro amount of oxygen in MnO and the alkene generates high price manganese in the reductor
3O
4And reach the deoxidation purpose.
Because Mn (OH)
2As easy as rolling off a log by dioxygen oxidation, even water-soluble trace oxygen also can be oxidized to it brown MnO (OH)
2So in reductor of the present invention, add stability that II A family alkaline earth metal oxide just is being based on divalence Mn under alkaline environment than much lower under sour environment, easier of the principle of dioxygen oxidation, thus reductor of the present invention deoxy activity and capacity at room temperature improved.In addition, add the dispersity that aluminum oxide can also increase Mn, further improve reductor of the present invention deoxy activity and capacity at room temperature.
Manganese deoxidier of the present invention can use following preparation method's preparation, and described preparation method may further comprise the steps:
(1) composition according to reductor weighs Mn
3O
4Precursor compound, alkaline earth metal oxide or oxyhydroxide and aluminum oxide mix;
(2) adding entry or weight percent in the mixture that step (1) obtains is rare nitric acid of 0.5%～1.5%, mediates moulding;
(3) with the airtight placement of reductor of step (2) moulding 6～48 hours, dry, 80～150 ℃ dry 3～12 hours down, then 200～800 ℃ of following roastings 2～10 hours.
In this a kind of preparation method, maturing temperature is preferably 300～600 ℃ described in the step (3).Roasting can be carried out under air or oxygen-free atmosphere.Those skilled in the art can easily determine suitable airtight placement, drying and roasting condition.
Manganese deoxidier of the present invention can also use following preparation method's preparation, and described preparation method may further comprise the steps:
(1) with Mn
3O
4Precursor compound obtained active Mn in 2～10 hours 200～800 ℃ of following roastings
3O
4Oxide compound;
(2) composition according to reductor weighs the active Mn that step (1) obtains
3O
4Oxide compound, alkaline earth metal oxide or oxyhydroxide and aluminum oxide mix;
(3) adding entry or weight percent in the mixture that step (2) obtains is rare nitric acid of 0.5%～1.5%, mediates moulding;
(4) reductor with step (3) moulding dries, and drying is 3～12 hours under 80～150 ℃.
In this a kind of preparation method, maturing temperature is preferably 300～600 ℃ described in the step (1).Identical with preceding a kind of preparation method, roasting can be carried out under air or oxygen-free atmosphere.Those skilled in the art can easily determine suitable airtight placement, drying and roasting condition.
In these two kinds of preparation methods, described Mn
3O
4Precursor compound is preferably manganous carbonate or manganous oxalate, and more preferably triangle is the rhombus manganous carbonate.
In these two kinds of preparation methods, described alkaline earth metal oxide has Ca (OH) for example
2, Mg (OH)
2, Ba (OH)
2
In two kinds of preparation methods provided by the invention, when adding entry or rare nitric acid and mediating, there is no particular limitation for the add-on of water or rare nitric acid and adding method, add-on and adding method are very common general knowledge in the preparation process of many solid catalysts, those skilled in the art can continue to add and mediate fully according to scene kneading situation, reductor can be processed into different shapes such as bar shaped, sphere or sheet, the size of reductor, shape do not have the influence of essence to the activity of reductor of the present invention.
Reductor by above-mentioned two kinds of methods preparation is analyzed through XRD (X-ray diffraction method), and the main form of manganese is Mn
3O
4
The reductor of above-mentioned two kinds of methods preparation needs before use at 150～350 ℃, under preferred 180-280 ℃, and logical hydrogen or hydrogen and N
2The on-the-spot reduction of mixed gas, the volume space velocity of reducing gas is 50-1000h
-1, be preferably 100-500h
-1, with the high oxide Mn of Mn
3O
4Be reduced into active constituent MnO.
Water-content shows that the oxide compound reduction of Mn is complete in the reducing gas when the no change of reduction front and back.Concrete recovery time and reduction temperature, reductor loadings are relevant.Those skilled in the art can be easy to determine suitable reductive condition according to general knowledge, does not here limit.
The present invention proposes the method for using manganese deoxidier of the present invention to carry out deoxidation, at first with described manganese deoxidier reduction, the raw material that will contain 1～2000ppm oxygen again carries out gas phase or liquid phase deoxidation by the bed of described manganese deoxidier, described raw material is rare gas element, contain the alkane of 1～5 carbon atom or contain the alkene of 2～5 carbon atoms, in gas phase, the gaseous phase volume air speed that needs the logistics of deoxidation is 100～10000h
-1, bed temperature is 20～200 ℃, pressure is 0.1～10Mpa.
Described rare gas element can be nitrogen, argon gas or helium, and described alkane is methane, ethane or propane for example, and described alkene for example is ethene or propylene.
The reductor deoxidation degree of depth of the present invention can reach＜0.05ppm (the lower limit sensitivity of little oxygen analyzer).
Reductor of the present invention is 1000ppm in the inlet oxygen level, air speed 1500h
-1, under the deoxidation degree of depth＜1ppm condition, when temperature was room temperature and 150 ℃, deoxidation capacity maximum can reach 6.8 and 31ml/g respectively.
Reductor of the present invention can on-the-spot reducing/regenerating after oxygen penetrates, and reuses.
Reductor of the present invention compared with prior art has following advantage:
(1) reductor of the present invention only adds small amount of alkali earth metals and IIIA family oxide compound as accelerative activator owing to be not the loading type reductor, has improved active constituent MnO/Mn in the reductor significantly
3O
4Content, therefore the theoretical deoxidation capacity of reductor of the present invention is big, the deoxidation capacity under room temperature and high temperature is higher than the prior art level naturally, has prolonged the reductor reprocessing cycle cycle, has reduced energy expenditure, has reduced production cost.
(2) therefore reductor of the present invention is specially adapted to the deoxidization technique of alkene media such as ethene, propylene owing to improved under the room temperature or the oxygen capacity under the low temperature, has avoided MnO/Mn
3O
4Reductor at high temperature uses, and the polyreaction that alkene media such as ethene, propylene produce has stoped the generation of impurity such as green oil.
(3) reductor of the present invention is active high, allows to surpass the inlet oxygen concn of 1000ppm.Can effective elimination in start-stop car process, thereby the elevated oxygen level that cause former because of operation fluctuation, raw material sources switching etc.
(4) reductor of the present invention has added alkaline-earth metal and IIIA family oxide compound, has improved the physical strength of reductor greatly, can not produce dust thereby have when the reductor filling is used, and repeatedly reprocessing cycle is used the advantage that does not run off.
Embodiment
Embodiment 1～4
Taking by weighing the 420g triangle is rhombus MnCO
3(bulk density is that specific surface area is 280m after 0.28g/ml, the 450 ℃ of roastings for fine powder, 60g pseudo-boehmite powder
2/ g, loss of weight 25%), 60g CaO fine powder, three's thorough mixing is even.Add an amount of distilled water, fully mediate.Be prepared into the strip of Φ 5 then with banded extruder; Placement is spent the night, and dries; Dried 3 hours for 120 ℃; Be cut into the segment of long 3～5mm after the cooling.Sample evenly is divided into 4 parts, respectively 350,400, roasting 4 hours (embodiment 1～4) under 450,500 ℃ of air atmosphere.The sample that takes a morsel is analyzed the Mn of four kinds of reductors with the X-gamma spectrometer
3O
4, Al
2O
3, CaO content.Get the 50ml reductor respectively and pack in the stainless steel reactor of Φ 25, at 280 ℃ of down logical H
2Reduction 12h, H
2Air speed is 10h
-1After the cooling, under pressure 0.4Mpa, under temperature 20 and 150 ℃, feed ethene respectively, ethene gas phase air speed is 1500h
-1, inlet oxygen level 1000ppm measures the deoxidation capacity under the deoxidation degree of depth≤1ppm condition, the results are shown in Table 1.
The reductor of table 1 embodiment 1～4 is formed and the reductor performance
Embodiment 5～8
According to triangle is rhombus MnCO
3: (bulk density is that specific surface area is 260m after 0.28g/ml, the 450 ℃ of roastings to pseudo-boehmite
2/ g, loss of weight 24%): CaO prepares four duplicate samples with weight ratio 7:2:0.5 (embodiment 5), 7:3:0.25 (embodiment 6), 7:1:2 (embodiment 7), 7:3:0.5 (embodiment 8) respectively, thorough mixing is even, each adds an amount of 1.0% rare nitric acid mediates, and is prepared into the strip of Φ 5 then with banded extruder; Placement is spent the night, and dries; Dried 3 hours for 120 ℃; Be cut into the segment of long 3～5mm after the cooling.Roasting 4 hours under 450 ℃ of air atmosphere then.Reductor to preparation activates and estimates, and operational condition is identical with embodiment 1, and evaluation result sees Table 2.
The chemical constitution of table 2 embodiment 5～8 and reductor performance
Embodiment 9
With the 10 10 gram CaO powder that restrain among the MgO replacement embodiment 3, prepare, activate and the evaluation reductor by the same terms with embodiment 3, the results are shown in Table 3.
Embodiment 10
With 13.2g Ca (OH)
2(being equivalent to 10g CaO) replaces the 10g CaO powder among the embodiment 3, prepares, activates and the evaluation reductor by the same terms with embodiment 3, the results are shown in Table 3.
Table 3 embodiment 9,10 reductor evaluation results
See from the test-results of embodiment 9 and 10, with Ca (OH)
2Have the close deoxidation capacity and the deoxidation degree of depth with MgO replaced C aO.
Embodiment 11
Getting 200 gram triangles is rhombus MnCO
3Prepared active Mn in 4 hours 450 ℃ of following roastings
3O
4Oxide compound 134 grams.(bulk density is that specific surface area is 260m after 0.28g/ml, the 450 ℃ of roastings to add pseudo-boehmite
2/ g, loss of weight 25%), CaO and each 28 gram of cement, thorough mixing is even, adds rare nitric acid of an amount of 1.0% and mediates.Then, be prepared into the strip of Φ 5 with banded extruder; Placement is spent the night, and dries; Dried 3 hours for 120 ℃; Be cut into the segment of long 3～5mm after the cooling.Roasting 8 hours under 450 ℃ of air atmosphere at last.Press the condition activation of embodiment 1 and estimate reductor, the deoxidation capacity under room temperature and 150 ℃ is respectively 5.8 and 27.4ml/g.
Embodiment 12
According to triangle is rhombus MnCO
3: (bulk density is that specific surface area is 260m after 0.28g/ml, the 450 ℃ of roastings to pseudo-boehmite
2/ g, loss of weight 24%): CaO: cement is 100 kilograms of samples of weight ratio preparation of 7:1:1:1, and thorough mixing is even, is processed into the spheroid of diameter 4-5mm with coater; Placement is spent the night, and dries; Dried 6 hours for 120 ℃.Roasting 4 hours under 450 ℃ of air atmosphere then.Press the condition activation of embodiment 1 and estimate reductor, the deoxidation capacity under room temperature and 150 ℃ is respectively 6.8 and 31.0ml/g.Oxygen level is 10ppm in ethene, air speed 3000～8000h
-1Under the condition, its deoxidation degree of depth still can reach≤0.1ppm when room temperature.Ethene is formed after utilizing the gas chromatographic detection deoxidation, and ethene is not found to generate new trace impurity after room temperature to 150 ℃ following deoxidation, illustrates that this reductor has good selectivity.
Embodiment 13 and 14
The reductor of getting 50ml embodiment 12 preparation is packed in the stainless steel reactor of Φ 25, at 280 ℃ of down logical H
2Reduction 12h.After the cooling, when pressure was 0.4Mpa, under temperature 20 and 150 ℃, using propylene (embodiment 13) and nitrogen (embodiment 14) respectively was raw material respectively, and the gas phase air speed is 1500h
-1, at inlet oxygen level 1000ppm, under the deoxidation degree of depth≤1ppm condition, measure the deoxidation capacity, the results are shown in Table 4.
Table 4 embodiment 13,14 reductor evaluation results
See that from the result of embodiment 13 and 14 reductor of the present invention has the deoxidation capacity close with ethene and the deoxidation degree of depth for propylene and nitrogen.
Comparative Examples 1
Get the commercially available MnO of 70g respectively
2Add the common Al of 10 grams
2O
3, 10 gram CaO and 10 gram cement, mediate with suitable quantity of water, be prepared into the strip of Φ 5 with banded extruder.All the other preparations, activation and appreciation condition are identical with embodiment 3.The deoxidation capacity of this reductor under room temperature and 150 ℃ has only 2.5 and 9.8ml/g.Illustrate and utilize MnCO
3The Mn that decomposes preparation
3O
4For its deoxy activity of active constituent and deoxidation capacity much larger than common MnO
2And Al
2O
3The reductor of preparation.
Claims (14)
1. a manganese deoxidier is characterized in that, it comprises following components in weight percentage:
Mn
3O
436%～90%, alkaline earth metal oxide 1%～30%, aluminum oxide 5%～35%.
2. manganese deoxidier according to claim 1 is characterized in that it also comprises tackiness agent, and the weight percent content of described tackiness agent in described manganese deoxidier is 1%～10%.
3. manganese deoxidier according to claim 1 and 2 is characterized in that, described alkaline earth metal oxide is calcium oxide, magnesium oxide or barium oxide.
4. manganese deoxidier according to claim 3 is characterized in that, described aluminum oxide is to be precursor with the pseudo-boehmite, at the γ-Al of 400～500 ℃ of following roastings
2O
3The bulk density of described pseudo-boehmite is 0.2～0.8g/ml, and loss of weight 20～40% after the roasting, described γ-Al
2O
3Specific surface area be 200～300m
2/ g.
5. manganese deoxidier according to claim 4 is characterized in that the bulk density of described pseudo-boehmite is 0.2～0.3g/ml, and loss of weight 20～30% after the roasting, described γ-Al
2O
3Specific surface area be 250～300m
2/ g.
6. manganese deoxidier according to claim 2 is characterized in that, described tackiness agent is cement or water glass.
7. preparation method as any described manganese deoxidier in the claim 1～6 is characterized in that it may further comprise the steps:
(1) composition according to reductor weighs Mn
3O
4Precursor compound, alkaline earth metal oxide or oxyhydroxide and aluminum oxide mix;
(2) adding entry or weight percent in the mixture that step (1) obtains is rare nitric acid of 0.5%～1.5%, mediates moulding;
(3) with the airtight placement of reductor of step (2) moulding 6～48 hours, dry, 80～150 ℃ dry 3～12 hours down, then 200～800 ℃ of following roastings 2～10 hours.
8. preparation method according to claim 7 is characterized in that, described Mn
3O
4Precursor compound is manganous carbonate or manganous oxalate.
9. preparation method according to claim 7 is characterized in that, the maturing temperature in the step (3) is 300～600 ℃.
10. preparation method as any described manganese deoxidier in the claim 1～6 is characterized in that it may further comprise the steps:
(1) with Mn
3O
4Precursor compound obtained active Mn in 2～10 hours 200～800 ℃ of following roastings
3O
4Oxide compound;
(2) weigh the active Mn that alkaline earth metal oxide or oxyhydroxide, aluminum oxide and step (1) obtain according to the composition of reductor
3O
4Oxide compound mixes;
(3) adding entry or weight percent in the mixture that step (2) obtains is rare nitric acid of 0.5%～1.5%, mediates moulding;
(4) reductor with step (3) moulding dries, and drying is 3～12 hours under 80～150 ℃.
11. preparation method according to claim 10 is characterized in that, described Mn
3O
4Precursor compound is manganous carbonate or manganous oxalate.
12. preparation method according to claim 10 is characterized in that, the maturing temperature in the described step (1) is 300～600 ℃.
13. method of using the described manganese deoxidier of one of claim 1～6 to carry out gas phase or liquid phase deoxidation, it is characterized in that, after described manganese deoxidier reduction, the raw material that will contain 1～2000ppm oxygen again carries out gas phase or liquid phase deoxidation by the bed of described manganese deoxidier, described raw material is rare gas element, contain the alkane of 1～5 carbon atom or contain the alkene of 2～5 carbon atoms, and the gaseous phase volume air speed is 100～10000h
-1, bed temperature is 20～200 ℃, pressure is 0.1～10Mpa.
14. the method for deoxidation according to claim 13 is characterized in that, described rare gas element is nitrogen, argon gas or helium, and described alkane is methane, ethane or propane, and described alkene is ethene or propylene.
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|---|---|---|---|
| CNB2005101167101A CN100513367C (en) | 2005-10-28 | 2005-10-28 | Manganese deoxidier and its preparation method and application |
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|---|---|---|---|
| CNB2005101167101A CN100513367C (en) | 2005-10-28 | 2005-10-28 | Manganese deoxidier and its preparation method and application |
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| CN100513367C true CN100513367C (en) | 2009-07-15 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102850162B (en) * | 2011-06-29 | 2014-11-05 | 中国石油化工股份有限公司 | Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same |
| CN102850159B (en) * | 2011-06-29 | 2014-11-05 | 中国石油化工股份有限公司 | Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same |
| CN102850163B (en) * | 2011-06-29 | 2014-11-05 | 中国石油化工股份有限公司 | Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same |
| CN102850165B (en) * | 2011-06-29 | 2014-08-27 | 中国石油化工股份有限公司 | Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same |
| CN102850160B (en) * | 2011-06-29 | 2014-11-05 | 中国石油化工股份有限公司 | Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same |
| CN102850164B (en) * | 2011-06-29 | 2014-08-27 | 中国石油化工股份有限公司 | Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same |
| CN102302931A (en) * | 2011-07-11 | 2012-01-04 | 大连瑞克科技有限公司 | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof |
| CN105363406A (en) * | 2014-08-18 | 2016-03-02 | 王雅坤 | Multifunctional deoxidizer, preparation and applications thereof |
| CN107029684B (en) * | 2017-06-20 | 2020-02-21 | 柳州豪祥特科技有限公司 | Slow-release type long-acting gas deoxidizer and preparation method thereof |
| CN108620063A (en) * | 2018-05-29 | 2018-10-09 | 湖北浚然新材料有限公司 | A kind of oil refinery dry gas dehydrogenation catalyst and its preparation method and application |
| WO2023020044A1 (en) | 2021-08-19 | 2023-02-23 | 中国石油化工股份有限公司 | Method for reducing risk of burning and explosion in deoxygenation process of oxygen-containing gas |
| CN115707516A (en) * | 2021-08-19 | 2023-02-21 | 中国石油化工股份有限公司 | Catalyst with deoxidation function and method for deoxidizing gas containing oxygen |
-
2005
- 2005-10-28 CN CNB2005101167101A patent/CN100513367C/en not_active Ceased
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| 气体纯化用脱氧剂和催化剂. 张俊香等.低温与特气，第1期. 1994 |
| 气体纯化用脱氧剂和催化剂. 张俊香等.低温与特气，第1期. 1994 * |
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| CN1955150A (en) | 2007-05-02 |
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