CN105037064A - Processing method of catalytic hydrogenation of olefin-containing exhaust gas - Google Patents
Processing method of catalytic hydrogenation of olefin-containing exhaust gas Download PDFInfo
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- CN105037064A CN105037064A CN201510400396.3A CN201510400396A CN105037064A CN 105037064 A CN105037064 A CN 105037064A CN 201510400396 A CN201510400396 A CN 201510400396A CN 105037064 A CN105037064 A CN 105037064A
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Abstract
The invention relates to a processing method of catalytic hydrogenation of olefin-containing exhaust gas, and mainly solves problems of a low unstaturated hydrocarbons conversion rate and a low alkane yield. The invention employs the processing method of catalytic hydrogenation of the olefin-containing exhaust gas. The processing method of catalytic hydrogenation of the olefin-containing exhaust gas comprises: exhaust gas with a volume concentration of olefin being 0.05%-50% entering a reactor and coming into contact with a catalyst; and performing catalytic hydrogenation with a reaction pressure being 0-4.0 MPaG, a reaction temperature being the room temperature-200 DEG C and a space velocity being 500-20000h-1, wherein the catalyst comprises an active component, an auxiliary agent and a carrier, the active component is copper or copper oxide and the auxiliary agent is at least one of La2O3, ZrO2, CeO2, Fe2O3, NiO, MgO, MnO, Al2O3 and K2O. The technical scheme with the carrier being zinc oxide solves the above problems and can be applied in the process of the catalytic hydrogenation of the olefin-containing exhaust gas.
Description
Technical field
The present invention relates to a kind for the treatment of process containing the tail gas catalyzed hydrogenation of alkene.
Background technology
Hydrogenation reaction tool in Chemical Manufacture has been widely used.In some reaction process, (as toluene and methanol alkylation reaction, methane aromatization) raw material or product constantly carries out dealkylation and generates olefin component, these alkene are main carbon distribution presomas, very easily polymerization forms superpolymer blocking reaction duct, causes catalyst deactivation.Under hydro condition, utilizing the characteristic of double-bond hydrogenation, is alkane by conversion of olefines, reduces the ratio of alkene, suppresses the generation of carbon distribution presoma, has delayed the carbon distribution process of catalyzer, improve the stability of catalyzer.Simultaneously along with development and the technical progress of oil refining, chemical industry, the by product of cracking of ethylene and the deep processing of refinery gas are more and more subject to people's attention.Their utilization has number of ways, the method of C4 and C 5 fraction hydrogenation reaction preparation feedback raw material is utilized to be exactly the alkene in its cut and diene hydrogenation are refined, make it to become alkane, products therefrom can be used as the cracking stock producing light olefins of high-quality, namely improve the added value of C4 and C 5 fraction, alleviate again the problem that low-carbon alkene raw material is in short supply.
The catalyzer that current hydrogenation of olefins is suitable for mainly is carried on precious metal and the nickel catalyzator of alumina supporter, and preferred metal is palladium and platinum.
CN102989477A discloses reduction, the renovation process of a kind of nickel-base hydrogenation catalyst, preparation method and catalyzer.Saturated hydrogenation catalyzer, comprises main active ingredient Ni, helps active ingredient Mg, Mo, Sn etc., the mass percentage in catalyzer composition: containing NiO40 ~ 50%, MgO0.02 ~ 2%, MoO
31 ~ 5%, SnO
22 ~ 5%.Disclosed nickel-base hydrogenation catalyst has higher hydrogenation activity, and can carry out hydrogenation reaction at a lower temperature, adapt to the saturated hydrogenation of undersaturated hydrocarbon raw material, particularly in C4, C5, C9 cut, alkynes, diolefine, monoolefin hydrogenation become corresponding alkane.
CN200810222182.1 discloses one and supports precious metals pd selective hydrogenation catalyst and preparation method thereof.This selective hydrogenation catalyst, is carrier with aluminum oxide, comprises active component palladium, Cu additives, auxiliary agent X
1with auxiliary agent X
2, in total catalyst weight 100%: containing palladium 0.1 ~ 0.5%, copper 0.1 ~ 6%, X
10.5 ~ 15%, X
20.5 ~ 5%, 0 ~ 2% is selected from one or more promoter metal in cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium, neodymium; Wherein X
1be selected from IVA element, X
2be selected from basic metal, alkaline-earth metal or its mixture.This catalyzer is rich in the selec-tive hydrogenation of alkynes salvage stores except alkynes after being specially adapted to Butadiene Extraction.CN200710179443.1 reports a kind of selective hydrogenation catalyst supporting precious metals pd, take aluminum oxide as carrier, take palladium as active ingredient, active ingredient is the distribution in eggshell type on carrier surface, it is characterized in that described catalyzer is in weight 100%, active ingredient Pd0.2 ~ 0.5wt%, auxiliary agent lanthanum and/or cerium 2 ~ 8wt%, alkali earth metal 2 ~ 8wt%, catalyst specific surface 70 ~ 150m
2/ g, pore volume 0.3 ~ 0.6ml/g, the crystal formation of carrier is Θ type or based on Θ, Α mixing crystal formation of Θ type.Catalyzer of the present invention is applicable to the selec-tive hydrogenation of medium-low distillate oil, be specially adapted to one-stage selective hydrogenation of gasoline splitting, this catalyzer has good Hydrogenation, especially in hydrogenating materials, minor amount of water is with, colloid, arsenic content, under the operating mode that diene content is higher, still there is good hydrogenation activity and stability.
The defect of above-mentioned prior art is: adopt active ingredient to be the catalyzer of nickel, and reaction conditions requires higher, and in product, olefin(e) centent is higher, there is carbon deposition phenomenon; Adopt active ingredient to be the catalyzer of precious metal, catalyzer cost is high, and require harsh to raw material impurity, working cost is higher.
The present invention solves this problem targetedly.
Summary of the invention
The problem that technical problem to be solved by this invention is unsaturated hydrocarbons low conversion rate in prior art, alkane yield is low, provides a kind for the treatment of process containing the tail gas catalyzed hydrogenation of alkene newly.The method is used for, in the process containing the tail gas catalyzed hydrogenation of alkene, having the advantage that unsaturated hydrocarbons transformation efficiency is high, alkane yield is high.
For solving the problem, the technical solution used in the present invention is as follows: a kind for the treatment of process containing the tail gas catalyzed hydrogenation of alkene, alkene volumetric concentration is that the tail gas of 0.05-50% enters reactor and catalyst exposure, be 0-4.0MPaG in reaction pressure, temperature of reaction is room temperature-200 DEG C, and volume space velocity is 500-20000h
-1under carry out shortening; Described catalyzer comprises active ingredient, auxiliary agent and carrier, and described active ingredient is the oxide compound of copper or copper, and content is 30-75wt%, and described auxiliary agent is La
2o
3, ZrO
2, CeO
2, Fe
2o
3, NiO, MgO, MnO, Al
2o
3, K
2at least one in O, content is 1-40wt%, and described carrier is zinc oxide, content 20-65wt%; Described catalyzer adopts the method preparation comprised the following steps:
1) preparing metal salts solution I, the metal ion containing cupric ion, zine ion, at least one auxiliary agent in solution;
2) prepare precipitant solution, be designated as solution II;
3) by solution I, solution II successively or add in container simultaneously, at 35-85 DEG C, carry out precipitin reaction, reaction end pH=6-8, aging 0-6 hour, obtain catalyst precursor slurry;
4) by catalyst precursor slurry washing, filtration, the ion of free state is removed, dry 6-48 hour at 60-200 DEG C;
5) by dried catalyst precursor slurry roasting 1-24 hour at 300-700 DEG C, obtained described catalyzer.。
In technique scheme, preferably, described metal salt solution I is the nitrate of metal, acetate, oxalate or muriate.
In technique scheme, preferably, described precipitant solution is selected from sodium carbonate, sodium hydroxide, volatile salt, bicarbonate of ammonia, sodium bicarbonate, urea or ammonia soln.
In technique scheme, preferably, the temperature 40-70 DEG C of described precipitin reaction.
In technique scheme, preferably, described maturing temperature 350-500 DEG C.
In technique scheme, preferably, described alkene comprises monoolefine and diolefine.
In technique scheme, preferably, described alkene volumetric concentration is that the tail gas of 0.05-20% enters reactor and catalyst exposure, and be 0-3.0MPaG in reaction pressure, temperature of reaction is room temperature-150 DEG C, and volume space velocity is 1000-10000h
-1.
In technique scheme, preferably, described catalyzer needs first activation treatment, and activation temperature is 150-350 DEG C, and activation phenomenon is H
2or H
2with N
2, Ar, He rare gas element mixed gas, wherein the volumn concentration of hydrogen is 0.1-99.9%, soak time 1-72 hour.
The invention provides a kind for the treatment of process containing the tail gas catalyzed hydrogenation of alkene, described catalyzer is under lesser temps, larger air speed, and ethylenic unsaturation hydrocarbon conversion rate is close to 100%, and alkane yield is close to 100%.And the preparation method of described catalyzer is simple, the raw material sources of catalyzer are extensive, significantly can reduce costs, obtain higher Production Gain, the preparation process environmental friendliness of catalyzer, are applicable to suitability for industrialized production, achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
By the Cu (NO of 60.4g
3)
2, the Fe (NO of 10.0g
3)
2, the Zn (NO of 74.4g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution II is added drop-wise in solution I, keeps temperature to be 50 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 350 DEG C, obtains target product catalyzer.
Above-mentioned obtained catalyzer is made the particle of 20-30 order size, loading diameter is in the tubular reactor of 12mm, under 250 DEG C of hydrogen atmospheres, activate 10 hours.With the ethene of volumetric concentration 6% for raw material, temperature of reaction 30 DEG C, volume space velocity 8000h
-1, reaction pressure normal pressure, reaction result is in table 1.
[embodiment 2]
By the Cu (NO of 60.4g
3)
2, the Ni (NO of 10.0g
3)
2with the Zn (NO of 74.4g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, keep pH=7.0, under temperature 70 C aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 500 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 3]
By the Cu (NO of 60.4g
3)
2, the Ce (NO of 10.0g
3)
3, the Zn (NO of 74.4g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution I is added drop-wise in solution II, keeps temperature to be 40 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 120 DEG C of dryings 8 hours, and roasting 6 hours at 400 DEG C, obtains target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 4]
By the Cu (NO of 36.2g
3)
2, the La (NO of 12.0g
3)
3, the Zn (NO of 104.1g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the precipitation agent Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 70 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 350 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 5]
By the Cu (CH of 48.3g
3cOO)
2, the Mn (CH of 20.0g
3cOO)
2zn (the CH of solution and 89.3g
3cOO)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the precipitation agent Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 60 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 500 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 6]
By the Cu (NO of 72.5g
3)
2, the ZrOCl of 20.0g
2with the Zn (NO of 59.5g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the precipitation agent Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution 1 I and solution II are added simultaneously and precipitate, temperature is kept to be 70 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 450 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 7]
By the Cu (NO of 84.6g
3)
2, the Mg (NO of 15.0g
3)
2with the Zn (NO of 44.6g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; By the precipitation agent Na of 53.7g
2cO
3be placed in another beaker, add 500g distilled water and make it dissolve completely, be denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 70 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 100 DEG C of dryings 12 hours, and roasting 6 hours at 400 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 8]
By the CuC of 60.4g
2o
4, the K of 10.0g
2c
2o
4with the ZnC of 74.4g
2o
4be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as normal solution I; The precipitation agent NaOH of 20g is placed in another beaker, adds 500g distilled water and make it dissolve completely, be denoted as normal solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 80 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 350 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 9]
By the Cu (NO of 60.4g
3)
2, the Al (NO of 10.0g
3)
3with the Zn (NO of 74.4g
3)
2be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; Preparation 10wt% ammoniacal liquor 350g is denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 70 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 400 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 10]
By 60.4gCu (NO
3)
2, 10.0gAl (NO
3)
3, 74.4gZn (NO
3)
2with 12.0gMn (NO
3)
2solution is placed in beaker, adds 500g distilled water and makes it dissolve completely, be denoted as solution I; Preparation 10wt% ammoniacal liquor 350g is denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 70 DEG C, control reaction end pH=6.5, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 6 hours at 450 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 11]
By the Cu (NO of 60.4g
3)
2, the Al (NO of 10.0g
3)
3, the Zn (NO of 74.4g
3)
2with the La (NO of 3.0g
3)
4, be placed in beaker, add 500g distilled water and make it dissolve completely, be denoted as solution I; Preparation 10wt% ammoniacal liquor 350g is denoted as solution II; Under condition of heating and stirring, solution I and solution II are added simultaneously and precipitate, temperature is kept to be 65 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry through washing, filter after 80 DEG C of dryings 15 hours, and roasting 3 hours at 500 DEG C, obtain target product catalyzer.
Evaluate processing condition with embodiment 1.
[embodiment 12]
It is in the tubular reactor of 12mm that catalyzer obtained for embodiment 2 is loaded diameter, and activates 6 hours under 300 DEG C of hydrogen atmospheres.With the iso-butylene of volumetric concentration 2% for raw material, temperature of reaction 40 DEG C, air speed 8000h
-1, reaction pressure normal pressure, reaction result is in table 1.
[embodiment 13]
It is in the tubular reactor of 12mm that catalyzer obtained for embodiment 2 is loaded diameter, under 250 DEG C of hydrogen atmospheres, activate 24 hours.With the divinyl of concentration 5% for raw material, temperature of reaction 30 DEG C, air speed 6000h
-1, reaction pressure 0.1Mpa, reaction result is in table 1.
[embodiment 14]
It is in the tubular reactor of 12mm that catalyzer obtained for embodiment 2 is loaded diameter, under 250 DEG C of hydrogen atmospheres, activate 6 hours.With the 1-amylene of volumetric concentration 10% for raw material, temperature of reaction room temperature (30 DEG C), air speed 6000h
-1, reaction pressure 0.5Mpa, reaction result is in table 1.
[embodiment 15]
It is in the tubular reactor of 12mm that catalyzer obtained for embodiment 6 is loaded diameter, under 240 DEG C of hydrogen atmospheres, activate 24 hours.With the propylene of volumetric concentration 6% for raw material, temperature of reaction 100 DEG C, air speed 10000h
-1, reaction pressure 0.5Mpa, reaction result is in table 1.
[embodiment 16]
It is in the tubular reactor of 12mm that catalyzer obtained for embodiment 11 is loaded diameter, under 250 DEG C of hydrogen atmospheres, activate 6 hours.With the propylene of volumetric concentration 15% for raw material, temperature of reaction 30 DEG C, air speed 8000h
-1, reaction pressure 2.5Mpa, reaction result is in table 1.
[embodiment 17]
It is in the tubular reactor of 12mm that catalyzer obtained for embodiment 11 is loaded diameter, activation phenomenon H
2/ N
2(H
2content is 15%, v/v), 250 DEG C of activation 8 hours.With the propylene of volumetric concentration 30% for raw material, temperature of reaction 100 DEG C, air speed 8000h
-1, reaction pressure 3.0Mpa, reaction result is in table 1.
[embodiment 18]
The catalyzer 100g taking embodiment 11 obtained carries out stability experiment.6 hours are activated under 250 DEG C of hydrogen atmospheres.With the ethene of volumetric concentration 10% for raw material, temperature of reaction 30 DEG C, air speed 8000h
-1, reaction pressure 0.1MPa, reaction result is listed in table 2.
Catalyzer was through the successive reaction of 1000 hours, and conversion of ethylene is greater than 99.5%, and ethane recovery is greater than 99.5%, shows satisfactory stability.
Table 1
| Alkene | Volumetric concentration | Ethylenic unsaturation hydrocarbon conversion rate/% | Saturated alkane yield/% | |
| Embodiment 1 | Ethene | 5％ | 100 | 100 |
| Embodiment 2 | Ethene | 5％ | 99.5 | 99.5 |
| Embodiment 3 | Ethene | 5％ | 100 | 100 |
| Embodiment 4 | Ethene | 5％ | 100 | 100 |
| Embodiment 5 | Ethene | 5％ | 100 | 100 |
| Embodiment 6 | Ethene | 5％ | 100 | 100 |
| Embodiment 7 | Ethene | 5％ | 100 | 100 |
| Embodiment 8 | Ethene | 5％ | 100 | 100 |
| Embodiment 9 | Ethene | 5％ | 100 | 100 |
| Embodiment 10 | Ethene | 5％ | 100 | 100 |
| Embodiment 11 | Ethene | 5％ | 100 | 100 |
| Embodiment 12 | Iso-butylene | 2％ | 100 | 100 |
| Embodiment 13 | Divinyl | 5％ | 100 | 100 |
| Embodiment 14 | 1-amylene | 10％ | 99.8 | 99.9 |
| Embodiment 15 | Propylene | 6％ | 100 | 100 |
| Embodiment 16 | Propylene | 15％ | 99.8 | 99.8 |
| Embodiment 17 | Propylene | 20％ | 100 | 100 |
Table 2
As can be seen from the above Table 1, under selected processing condition, the present invention is containing the transformation efficiency in the tail gas catalyzed reaction of alkene close to 100%, and alkane yield is close to 100%.As can be seen from Table 2, the catalyzer of the application has good stability.
Claims (8)
1., containing a treatment process for the tail gas catalyzed hydrogenation of alkene, alkene volumetric concentration is that the tail gas of 0.05-50% enters reactor and catalyst exposure, and be 0-4.0MPaG in reaction pressure, temperature of reaction is room temperature-200 DEG C, and volume space velocity is 500-20000h
-1under carry out shortening; Described catalyzer comprises active ingredient, auxiliary agent and carrier, and described active ingredient is the oxide compound of copper or copper, and content is 30-75wt%, and described auxiliary agent is La
2o
3, ZrO
2, CeO
2, Fe
2o
3, NiO, MgO, MnO, Al
2o
3, K
2at least one in O, content is 1-40wt%, and described carrier is zinc oxide, content 20-65wt%; Described catalyzer adopts the method preparation comprised the following steps:
1) preparing metal salts solution I, the metal ion containing cupric ion, zine ion, at least one auxiliary agent in solution;
2) prepare precipitant solution, be designated as solution II;
3) by solution I, solution II successively or add in container simultaneously, at 35-85 DEG C, carry out precipitin reaction, reaction end pH=6-8, aging 0-6 hour, obtain catalyst precursor slurry;
4) by catalyst precursor slurry washing, filtration, the ion of free state is removed, dry 6-48 hour at 60-200 DEG C;
5) by dried catalyst precursor slurry roasting 1-24 hour at 300-700 DEG C, obtained described catalyzer.
2., according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that described metal salt solution I is the nitrate of metal, acetate, oxalate or muriate.
3., according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that described precipitant solution is selected from sodium carbonate, sodium hydroxide, volatile salt, bicarbonate of ammonia, sodium bicarbonate, urea or ammonia soln.
4., according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that the temperature 40-70 DEG C of described precipitin reaction.
5., according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that described maturing temperature 350-500 DEG C.
6., according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that described alkene comprises monoolefine and diolefine.
7. according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that described alkene volumetric concentration is that the tail gas of 0.05-20% enters reactor and catalyst exposure, be 0-3.0MPaG in reaction pressure, temperature of reaction is room temperature-150 DEG C, and volume space velocity is 1000-10000h
-1.
8., according to claim 1 containing the treatment process of the tail gas catalyzed hydrogenation of alkene, it is characterized in that described catalyzer needs first activation treatment, activation temperature is 150-350 DEG C, and activation phenomenon is H
2or H
2with N
2, Ar, He rare gas element mixed gas, wherein the volumn concentration of hydrogen is 0.1-99.9%, soak time 1-72 hour.
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|---|---|---|---|---|
| CN108130127A (en) * | 2017-12-26 | 2018-06-08 | 中国科学院长春应用化学研究所 | A kind of processing method of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas |
| CN115254130A (en) * | 2022-08-23 | 2022-11-01 | 辽宁大学 | Rare earth element Sm modified Ni-based water-resistant catalyst and preparation method and application thereof |
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| CN102872878A (en) * | 2012-10-11 | 2013-01-16 | 上海华谊（集团）公司 | Catalyst for preparing ethanol from acetic ester hydrogenation, preparation method and application thereof |
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