CN1110249A - High effective desoxydation dehydrogenation catalyst and its preparation and application - Google Patents
High effective desoxydation dehydrogenation catalyst and its preparation and application Download PDFInfo
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- CN1110249A CN1110249A CN 94103686 CN94103686A CN1110249A CN 1110249 A CN1110249 A CN 1110249A CN 94103686 CN94103686 CN 94103686 CN 94103686 A CN94103686 A CN 94103686A CN 1110249 A CN1110249 A CN 1110249A
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- desoxydation
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Abstract
The present invention relates to a deoxidation and dehydrogenation catalyst and its application and preparation method. For deoxidation catalyst non-matching hydrogen, the weight ratio of NiO and Al2O3 is 5.0-35.0%, and the weight of MnO2 and Al2O3 is 10-40%, and the weight ratio of one or several oxides of alkaline-earth metals and Al2O3 is 0.3-3.0%, and for dehydrogenation catalyst non-matching oxygen, the weight ratio of NiO and Al2O3 is 10.0-40.0%, and the weight ratio of CuO and Al2O3 is 4.0-24.0%, and the weight ratio of one or several oxides of alkaline-earth metals and Al2O3 is 0.5-5.0%. The above-mentioned catalysts have low activating temp. and lower catalyst bed height-radius ratio, so that they can be used for deoxidation and dehydrogenation treatment for preparing high-pure nitrogen by using pure nitrogen or general nitrogen.
Description
The present invention relates to desoxydation dehydrogenation catalyst and preparation and application, often need to use high pure nitrogen (nitrogen content reaches more than 99.999%) in departments such as petrochemical industry, metallurgy, electronics, building materials, machineries.At present at the dehydrogenation catalyst of industrial widely used platiniferous or palladium, needing could be with oxygen removal in the nitrogen after the hydrogen make-up, and this uses as reducing gas atmosphere is feasible, but many Industrial products have strict demand to the content of hydrogen in the nitrogen.There are two kinds of methods can obtain high-purity N industrial at present
2: the one, directly by pure N
2(oxygen level is 20～100ppm) through being unworthy of the hydrogen dehydrogenation catalyst, oxygen in the nitrogen is taken off to 1ppm, present domestic usefulness mainly be with MnO
2It is main dehydrogenation catalyst, this catalyzer exist granularity little (≤1mm), require beds aspect ratio big (reaching 20:1) during use, reduction activation temperature height shortcomings such as (～350 ℃), in the laboratory, use all rightly, and can have certain difficulty in industrial use; Consult Lab.Pract.1975,24(12), 808(Eng) and J.Phy.E 1973.6(12) 1208-10(Eng) the 2nd, by general nitrogen (oxygen level is 1～3%(V)) after palladium-aluminium oxide catalyst is joined the hydrogen deoxidation, also do not reach the purpose of removing remaining hydrogen (≤0.2%(V)), must be again through be unworthy of the oxygen catalyst for removing hydrogen with nitrogen in hydrogen be removed to below the 5ppm.
One of purpose of the present invention is to overcome above-mentioned prior art deficiency, and a class desoxydation dehydrogenation catalyst is provided, to satisfy industrial requirement of producing high purity nitrogen by purity nitrogen or general nitrogen.
Another purpose of the present invention is the application that is unworthy of the hydrogen dehydrogenation catalyst and is unworthy of the oxygen catalyst for removing hydrogen.
Desoxydation dehydrogenation catalyst adopts nickel, manganese or nickel, copper to be active ingredient, and to add at least a alkali earth metal as auxiliary agent, with Al
2O
3Be carrier, being unworthy of the hydrogen dehydrogenation catalyst or being unworthy of the oxygen catalyst for removing hydrogen of formation.
The active ingredient Ni of desoxydation dehydrogenation catalyst, Mn, the Cu element can improve the deoxidation capacity of catalyzer, reduces the catalyst reduction temperature, and alkali earth metal adds as auxiliary agent, and it is better that active ingredient is distributed, and helps the rugged catalyst structure.
The active ingredient that is unworthy of the hydrogen dehydrogenation catalyst, the proportion relation of auxiliary agent and carrier is as follows: NiO and Al
2O
3Weight ratio be 5.0～35.0%, MnO
2With Al
2O
3Weight ratio be 10.0～40.0%, one or more oxide compounds and Al in the alkaline-earth metal
2O
3Weight ratio be 0.3～3.0%.
The active ingredient that is unworthy of the hydrogen dehydrogenation catalyst, the best proportion relation of auxiliary agent and carrier: NiO and Al
2O
3Weight ratio be 7.5～20.0%, MnO
2With Al
2O
3Weight ratio be 15.0～30.0%, one or more oxide compounds and Al in the alkaline-earth metal
2O
3Weight ratio be 0.5～1.5%.
The proportion relation that is unworthy of active ingredient, auxiliary agent and the carrier of oxygen catalyst for removing hydrogen: NiO and Al
2O
3Weight ratio be 10～40%, CuO and Al
2O
3Weight ratio be 4.0-24.0%, the oxide compound of one or more in the alkaline-earth metal and Al
2O
3Weight ratio be 0.5～5.0%.
Be unworthy of oxygen catalyst for removing hydrogen NiO and Al
2O
3Weight ratio be preferably 15.0-25.0, CuO and Al
2O
3Weight ratio be preferably 7.0-16.0%, one or more oxide compounds and Al in the alkaline-earth metal
2O
3Weight ratio be preferably 1.0～2.0%.
The preparation method of desoxydation dehydrogenation catalyst generally can adopt pickling process or coprecipitation method.The preparation process of pickling process is as follows: will contain the salt dissolving of Ni and Mn or Cu element, and add the alkaline earth salt mixed preparing again, employing is soaked altogether or the method for step impregnation is immersed in Al
2O
3On the carrier, the salts solution of active ingredient and the volume ratio of carrier are 0.6-1.2, dipping at room temperature, leave standstill 15～20 minutes after, 80～110 ℃ dry 10-16 hour down, then 400～500 ℃ of following roastings 6 hours, obtain being the catalyzer of black.
The catalyst particles granularity is generally 2～3mm, 2.5～3.2mm or 3～4mm.
Active ingredient Ni, Mn, Cu element can come the various Ni(NO of self-contained this component
3)
26H
2O, Ni(CH
3COO)
2, NiCl
2, Mn(NO
3)
2, Mn(CH
3COO)
2, MnCl
2, Cu(NO
3)
23H
2O, CuCl
2, Cu(CH
3COO)
2
Auxiliary element can be an alkaline earth salt, nitrate or oxide compound etc.
Carrier adopts spherical or column, strip r-Al
2O
3Or with r-Al
2O
3It is main mixture.
Desoxydation dehydrogenation catalyst can be used for being produced by purity nitrogen or general nitrogen the desoxydation dehydrogenation processing of high purity nitrogen.
Be unworthy of hydrogen dehydrogenation catalyst optimum as the deoxidation treatment of producing high purity nitrogen by purity nitrogen.
Being unworthy of oxygen catalyst for removing hydrogen optimum handles as the dehydrogenation of being produced high purity nitrogen by general nitrogen.
Being determined in the fixed-bed reactor of catalyzer deoxy activity carried out.Reactor inside diameter is φ 18mm, and the catalyzer loading amount is 40ml.The reaction procatalyst is used H earlier under 250～300 ℃
2Reduced 3 hours, and fed pure N then
2Carry out deoxygenation, gas space velocity was generally 2000～4000 hours
-1After oxygen in the nitrogen is greater than 1ppm, get final product stopped reaction.By the whole weight that meets the total nitrogen volume, nitrogen oxygen level and the 40ml catalyzer that feed in the reaction times of deoxidation requirement, can calculate the deoxidation capacity (mlO of this catalyzer
2/ g) be generally (13～15) mlO
2/ g.The catalyst life test adopts the method for quickening to carry out, promptly at pure N
2In allocate a small amount of general N into
2, make and mix that oxygen level reaches about 1000ppm in the nitrogen, can shorten dramatically reaction time like this.Catalyzer work-ing life is more than 2 years.
The reaction that is unworthy of the catalyst for removing hydrogen of oxygen is two reaction tubess to be together in series carry out, earlier with general N
2Allocate certain amount of H into
2After palladium-aluminium oxide catalyst makes its remaining oxygen≤1ppm, residual hydrogen amount≤1500ppm, being unworthy of in the oxygen catalyst for removing hydrogen under then this gas mixture being fed 250～300 ℃ is 2000 hours in air speed generally
-1Under the condition, residual hydrogen amount≤5ppm.After residual hydrogen amount is greater than 5ppm, get final product bubbling air, be 300～500 hours in air speed
-1Under regenerated 3～4 hours.Catalyzer work-ing life is more than 2 years.Industrially generally remove in parallel switching of hydrogen reactor and use two.Hydrogen adopts gas chromatograph to analyze in the nitrogen, and micro amount of oxygen adopts homemade trace oxygen analyzer to analyze in the nitrogen, and constant oxygen is analyzed with chromatographic process in the nitrogen.
This shows that the desoxydation dehydrogenation catalyst that the present invention makes has activation temperature low (250 ℃-300 ℃), granularity is big (Φ 2-4mm), and the beds aspect ratio is lower, and (6:1～8:1), physical strength is than characteristics such as height.This catalyzer can make the work simplification by purity nitrogen or the high purity nitrogen of general nitrogen system, easily-controlled reaction conditions, and, the remaining oxygen≤1ppm of high purity nitrogen, residual hydrogen amount≤5ppm, catalyzer long service life.
In order to illustrate in greater detail the present invention, enumerate the following examples:
Example one:
Take by weighing spherical γ-Al of the Φ 2.5～3.2mm of Jiangsu factory production
2O
31000g is measured 770ml Mn(NO
3)
2The aqueous solution (contains 50% Mn(NO
3)
2) placing enamelled cup, slowly heating takes by weighing 555.5g Ni(NO on electric furnace
3)
26H
2O divides and adds in this solution for several times, stirs, and it is dissolved fully.Add a spot of Ca(NO again
3)
2Auxiliary agent to this mixed solution, dissolve it.With Al
2O
3Pour in the solution and flood it.Placed under the room temperature 15 minutes then, can place in the loft drier in 80～100 ℃ dry 10 hours down, place in the High Temperature Furnaces Heating Apparatus earlier 250 ℃ of following roastings 1 hour again, again in 350 ℃ of following roastings 1 hour, at last in 450 ℃ of following roastings 5 hours.The toxic gas that discharges during roasting emptying after treatment.Cooled catalyzer finished product is black.
40ml is 2000 hours through this catalyzer of reduction activation in room temperature, air speed
-1(gas volume that per hour enters reactor is 100 liters) feeds pure N
2Nitrogen oxygen level after (oxygen level is 100ppm) purified in 61 hours is less than 1ppm, and the deoxidation capacity of this catalyzer is 15.1mlO
2/ g.
Example two:
Take by weighing 518.3g Ni(NO earlier
3)
26H
2The O heating is dissolved in the 150ml distilled water, and the spherical alumina example of 400g Φ 2-3mm is gone in this solution to flood it, leaves standstill then 20 minutes, puts into 90～110 ℃ of loft drier inner dryings 12 hours.Measure the Mn(NO of 359ml
3)
2Solution takes by weighing a certain amount of Mg(NO
3)
2Pour in this solution and dissolve it, above-mentioned work in-process are poured in this mixing solutions, left standstill 15 minutes, put into 80～100 ℃ loft drier inner drying 10 hours, put into High Temperature Furnaces Heating Apparatus at last, 450 ℃ of following roastings 6 hours in 350 ℃ of following roastings 2 hours.Obtain the catalyst prod of black.
(reduction temperature is 250 ℃, H through this catalyzer of reduction activation
2Air speed 500 hours
-1, the recovery time is 3 hours) under the condition identical, to estimate with example one, remaining oxygen is less than 1ppm.The mixing nitrogen that employing contains 1000ppm oxygen is 1000 hours in air speed
-1Carry out deoxygenation, remaining oxygen is less than 1ppm, and the deoxidation capacity can reach 16.2mlO
2/ g.Accumulative total has been carried out 300 hours longevity tests, and the catalyzer deoxy activity is very stable.
Example three:
Take by weighing the spherical alumina of 400g Φ 2.5-3.2mm, take by weighing 444.2g Ni(NO
3)
26H
2O, 173.5g Cu(NO
3)
23H
2O and a spot of Sr(NO
3)
2Heating is dissolved in the 200ml distilled water, this mixing solutions is poured in the aluminum oxide flooded it, leaves standstill 25 minutes, put into 90～110 ℃ loft drier 12 hours, 350 ℃ of following roastings 2 hours in High Temperature Furnaces Heating Apparatus at last, 450 ℃ of following roastings 6 hours obtain being the catalyst prod of black.
This catalyzer is 2000 hours for being unworthy of the oxygen catalyst for removing hydrogen in air speed
-1, under 250～300 ℃, N
2Middle hydrogen is 1500ppm, in 5 hours, hydrogen in the nitrogen can be removed to below the 5ppm.In 250～300 ℃, air speed is 300～500 hours with air
-1Under regenerated 3 hours, can make it recover remove hydrogen activity.As be used general N with palladium-aluminium oxide catalyst
2In oxygen level be 3%, allocate deoxidation on palladium-aluminium oxide catalyst behind the hydrogen into, remaining oxygen≤1ppm, residual hydrogen amount≤1500ppm through this routine catalyst for removing hydrogen dehydrogenation, makes N again
2Middle hydrogen≤5ppm can be by general N
2Make purity and reach high-purity N more than 99.999%
2
Claims (8)
1, a kind of desoxydation dehydrogenation catalyst is characterized in that with NIi, Mn element be active ingredient, and alkali earth metal is as auxiliary agent, Al
2O
3Be carrier, NiO and Al
2O
3Weight ratio be 5-35%, MnO
2With Al
2O
3Weight ratio be 10-40%, one or more oxide compounds and Al in the alkali earth metal
2O
3Weight ratio 0.3%-3%.
2, catalyzer as claimed in claim 1 is characterized in that NiO and Al
2O
3Weight ratio be 7.5-20%, MnO
2With Al
2O
3Weight ratio be 15-30%, one or more oxide compounds and Al in the alkaline-earth metal
2O
3Weight ratio is 0.5-1.5%.
3, a kind of desoxydation dehydrogenation catalyst is characterized in that with Ni, Cu element be active ingredient, and alkali earth metal is as auxiliary agent, Al
2O
3Be carrier, NiO and Al
2O
3Weight ratio be 10-40%, CuO and Al
2O
3Weight ratio be 4-24%, one or more oxide compounds and Al in the alkali earth metal
2O
3Weight ratio be 0.5-5%.
4, catalyzer as claimed in claim 3 is characterized in that NiO and Al
2O
3Weight ratio 15-25%, CuO and Al
2O
3Weight ratio 7-16%, one or more oxide compounds and Al in the alkali earth metal
2O
3Weight ratio 1-2%.
5, a kind of method for preparing claim 1 or 3 described desoxydation dehydrogenation catalysts, it is characterized in that to contain the salt dissolving of Ni and Mn or Cu element, prepare with alkaline earth salt again, at room temperature adopt to soak altogether or divide and be immersed on the alumina supporter, the solution of active ingredient and the volume ratio of carrier are 0.6-1.2, descended dry 10-16 hour at 80-110 ℃, then 400-500 ℃ of following roasting 6 hours.
6, the desoxydation dehydrogenation that is used for being produced by purity nitrogen or general nitrogen high purity nitrogen as claim 1 or 3 described desoxydation dehydrogenation catalysts is handled.
7, desoxydation dehydrogenation catalyst as claimed in claim 1 is unworthy of the hydrogen dehydrogenation catalyst as what produced high purity nitrogen by purity nitrogen.
8, desoxydation dehydrogenation catalyst as claimed in claim is unworthy of the oxygen catalyst for removing hydrogen as what produced high purity nitrogen by general nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94103686 CN1053843C (en) | 1994-04-05 | 1994-04-05 | High effective desoxydation dehydrogenation catalyst and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94103686 CN1053843C (en) | 1994-04-05 | 1994-04-05 | High effective desoxydation dehydrogenation catalyst and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110249A true CN1110249A (en) | 1995-10-18 |
| CN1053843C CN1053843C (en) | 2000-06-28 |
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ID=5031213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94103686 Expired - Fee Related CN1053843C (en) | 1994-04-05 | 1994-04-05 | High effective desoxydation dehydrogenation catalyst and its preparation and application |
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| Country | Link |
|---|---|
| CN (1) | CN1053843C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088622C (en) * | 1998-11-26 | 2002-08-07 | 北京大学 | Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application |
| CN102266768A (en) * | 2010-07-29 | 2011-12-07 | 西南化工研究设计院 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
| CN102850159A (en) * | 2011-06-29 | 2013-01-02 | 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 |
| CN102850163A (en) * | 2011-06-29 | 2013-01-02 | 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 |
| CN111068712A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Bifunctional catalyst for simultaneously removing oxygen and nitrogen oxide, preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087655C (en) * | 1996-09-04 | 2002-07-17 | 中国科学院大连化学物理研究所 | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst |
-
1994
- 1994-04-05 CN CN 94103686 patent/CN1053843C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088622C (en) * | 1998-11-26 | 2002-08-07 | 北京大学 | Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application |
| CN102266768A (en) * | 2010-07-29 | 2011-12-07 | 西南化工研究设计院 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
| CN102266768B (en) * | 2010-07-29 | 2012-12-26 | 西南化工研究设计院有限公司 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
| CN102850159A (en) * | 2011-06-29 | 2013-01-02 | 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 |
| CN102850163A (en) * | 2011-06-29 | 2013-01-02 | 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 |
| 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 |
| CN111068712A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Bifunctional catalyst for simultaneously removing oxygen and nitrogen oxide, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1053843C (en) | 2000-06-28 |
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