CN105037064B - 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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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 the processing method of the tail gas catalyzed hydrogenation of a kind of olefin-containing.
Background technology
Hydrogenation reaction has having been widely used in Chemical Manufacture.(such as toluene and methanol alkylation in some course of reaction
Reaction, methane aromatization) raw material or product constantly carry out dealkylation and generate olefin component, and these alkene are main
Carbon distribution presoma, easily polymerization form high polymer blocking reaction duct, cause catalysqt deactivation.Under hydro condition, utilize double
The characteristic of key hydrogenation, is converted into alkane by alkene, reduces the ratio of alkene, the generation of suppression carbon distribution presoma, has delayed catalysis
The carbon distribution process of agent, improves the stability of catalyst.Simultaneously along with oil refining, the development of chemical industry and technological progress, ethylene
The by-product of cracking and the deep processing of refinery gas are increasingly subject to people's attention.Their utilization has number of ways, utilizes C4
The method preparing reaction raw materials with C 5 fraction hydrogenation reaction is exactly the alkene in its fraction and diene hydrogenation to be refined, and is allowed to into
For alkane, products therefrom can i.e. improve the added value of C4 and C 5 fraction as the cracking stock producing light olefins of high-quality, delay again
Solve the problem that low-carbon alkene raw material is in short supply.
The catalyst that hydrogenation of olefins is suitable at present is mainly carried on noble metal and the Raney nickel of alumina support, and excellent
The metal of choosing is palladium and platinum.
CN102989477A discloses the reduction of a kind of nickel-base hydrogenation catalyst, preparation method and catalyst, renovation process.
Saturated hydrogenation catalyst, including main active component Ni, helps active component Mg, Mo, Sn etc., contains with the percent mass of catalyst composition
Gauge: containing NiO 40～50%, MgO 0.02～2%, MoO31～5%, SnO22～5%.Disclosed nickel-base hydrogenation catalyst
There is higher hydrogenation activity, hydrogenation reaction can be carried out at a lower temperature, adapt to the saturated of undersaturated hydrocarbon raw material and add
In hydrogen, particularly C4, C5, C9 fraction, alkynes, alkadienes, monoolefin hydrogenation become corresponding alkane.
CN200810222182.1 discloses one and supports precious metals pd selective hydrocatalyst and preparation method thereof.Should
Selective hydrocatalyst, with aluminium oxide as carrier, comprises active component palladium, Cu additives, auxiliary agent X1With auxiliary agent X2, with catalyst
Gross weight 100% is counted: containing palladium 0.1～0.5%, copper 0.1～6%, X10.5～15%, X20.5～5%, 0～2% selected from cobalt,
One or more promoter metal in nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium, neodymium；Wherein X1Selected from IVA element, X2Selected from alkali metal,
Alkaline-earth metal or its mixture.This catalyst be particularly well-suited to Butadiene Extraction after rich in alkynes salvage stores selection be hydrogenated with remove
Alkynes.CN200710179443.1 reports a kind of selective hydrocatalyst supporting precious metals pd, with aluminium oxide as carrier,
With palladium as active component, active component is distributed in eggshell type on carrier surface, it is characterised in that described catalyst is with weight
100% meter, active component Pd 0.2～0.5wt%, auxiliary agent lanthanum and/or cerium 2～8wt%, alkali earth metal 2～8wt%, urge
Agent specific surface 70～150m2/ g, pore volume 0.3～0.6ml/g, the crystal formation of carrier is Θ type or mixes based on Θ, Α of Θ type
Synthetic type.Catalyst of the present invention is applicable to the selection hydrogenation of medium-low distillate oil, is particularly well-suited to drippolene one-stage selective and adds
Hydrogen, this catalyst has good Hydrogenation, especially band minor amount of water in hydrogenating materials, and colloid, arsenic content, diene content is relatively
Under high operating mode, still there is good hydrogenation activity and stability.
The defect of above-mentioned prior art is: using active component is the catalyst of nickel, and reaction condition requires higher, in product
Olefin(e) centent is higher, there is carbon deposition phenomenon；Using active component is the catalyst of noble metal, and catalyst cost is high, miscellaneous to raw material
Matter requires harshness, and operating cost is higher.
The present invention solves this problem targetedly.
Summary of the invention
The technical problem to be solved is that in prior art, unsaturated hydrocarbons conversion ratio is low, low the asking of alkane yield
Topic, it is provided that the processing method of a kind of tail gas catalyzed hydrogenation of new olefin-containing.The method is for the place of the tail gas catalyzed hydrogenation of olefin-containing
In reason, there is the advantage that unsaturated hydrocarbons conversion ratio is high, alkane yield is high.
For solving the problems referred to above, the technical solution used in the present invention is as follows: the process of the tail gas catalyzed hydrogenation of a kind of olefin-containing
Method, alkene volumetric concentration is that the tail gas entrance reactor of 0.05-50% contacts with catalyst, is 0-in reaction pressure
4.0MPaG, reaction temperature is room temperature-200 DEG C, and volume space velocity is 500-20000h-1Under carry out catalytic hydrogenation；Described catalyst bag
Including active component, auxiliary agent and carrier, described active component is the oxide of copper or copper, and content is 30-75wt%, described auxiliary agent
For La2O3、ZrO2、CeO2、Fe2O3、NiO、MgO、MnO、Al2O3、K2At least one in O, content is 1-40wt%, described load
Body is zinc oxide, content 20-65wt%；Described catalyst uses the method comprised the following steps to prepare:
1) preparing metal saline solution I, containing copper ion, zinc ion, the metal ion of at least one auxiliary agent in solution；
2) preparation precipitant solution, is designated as solution II；
3) solution I, solution II are simultaneously or successively added in container, at 35-85 DEG C, carry out precipitation, reaction end
PH=6-8, aging 0-6 hour, obtains catalyst precursor slurry；
4) by catalyst precursor slurry washing, filtration, the ion of removing free state, it is dried 6-48 at 60-200 DEG C little
Time；
5) by dried catalyst precursor slurry roasting 1-24 hour at 300-700 DEG C, described catalysis is prepared
Agent..
In technique scheme, it is preferable that described metal salt solution I is the nitrate of metal, acetate, oxalates or chlorine
Compound.
In technique scheme, it is preferable that described precipitant solution is selected from sodium carbonate, sodium hydroxide, ammonium carbonate, bicarbonate
Ammonium, sodium bicarbonate, carbamide or ammonia spirit.
In technique scheme, it is preferable that temperature 40-70 DEG C of described precipitation.
In technique scheme, it is preferable that described sintering temperature 350-500 DEG C.
In technique scheme, it is preferable that described alkene includes monoolefine and alkadienes.
In technique scheme, it is preferable that described alkene volumetric concentration is that the tail gas of 0.05-20% enters reactor and urges
Agent contacts, and is 0-3.0MPaG in reaction pressure, and reaction temperature is room temperature-150 DEG C, and volume space velocity is 1000-10000h-1。
In technique scheme, it is preferable that described catalyst needs first activation processing, and activation temperature is 150-350 DEG C, activation
Atmosphere is H2Or H2With N2, the mixed gas of Ar, He noble gas, wherein the volumn concentration of hydrogen is 0.1-99.9%, live
1-72 hour change time.
The present invention provides the processing method of the tail gas catalyzed hydrogenation of a kind of olefin-containing, and described catalyst is at lower temperature, bigger
Under air speed, ethylenic unsaturation hydrocarbon conversion rate is close to 100%, and alkane yield is close to 100%.And the preparation method letter of described catalyst
Single, the raw material sources of catalyst are extensive, cost can be greatly reduced, it is thus achieved that higher Production Gain, the preparation process of catalyst
Environmental friendliness, is suitable for industrialized production, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
By the Cu (NO of 60.4g3)2, the Fe (NO of 10.0g3)2, the Zn (NO of 74.4g3)2It is placed in beaker, adds 500g and steam
Distilled water makes it be completely dissolved, and is denoted as solution I；By the Na of 53.7g2CO3It is placed in another beaker, adds 500g distilled water and make it complete
CL, is denoted as solution II；Being added drop-wise in solution I by solution II under condition of heating and stirring, keeping temperature is 50 DEG C, controls reaction
Terminal pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after be dried 15 hours at 80 DEG C, and
Roasting 6 hours at 350 DEG C, obtain target product catalyst.
Above-mentioned prepared catalyst is made the granule of 20-30 mesh size, loads in the tubular reactor of a diameter of 12mm,
Activate 10 hours under 250 DEG C of hydrogen atmospheres.With the ethylene of volumetric concentration 6% as raw material, reaction temperature 30 DEG C, volume space velocity
8000h-1, reaction pressure normal pressure, reaction result is shown in Table 1.
[embodiment 2]
By the Cu (NO of 60.4g3)2, the Ni (NO of 10.0g3)2Zn (NO with 74.4g3)2It is placed in beaker, adds 500g and steam
Distilled water makes it be completely dissolved, and is denoted as solution I；By the Na of 53.7g2CO3It is placed in another beaker, adds 500g distilled water and make it complete
CL, is denoted as solution II；Under condition of heating and stirring, solution I is simultaneously introduced with solution II and precipitates, keep pH=7.0,
Under temperature 70 C aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after be dried 15 hours at 80 DEG C, and
Roasting 6 hours at 500 DEG C, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 3]
By the Cu (NO of 60.4g3)2, the Ce (NO of 10.0g3)3, the Zn (NO of 74.4g3)2It is placed in beaker, adds 500g and steam
Distilled water makes it be completely dissolved, and is denoted as solution I；By the Na of 53.7g2CO3It is placed in another beaker, adds 500g distilled water and make it complete
CL, is denoted as solution II；Being added drop-wise in solution II by solution I under condition of heating and stirring, keeping temperature is 40 DEG C, controls reaction
Terminal pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after be dried 8 hours at 120 DEG C, and
Roasting 6 hours at 400 DEG C, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 4]
By the Cu (NO of 36.2g3)2, the La (NO of 12.0g3)3, the Zn (NO of 104.1g3)2It is placed in beaker, adds 500g and steam
Distilled water makes it be completely dissolved, and is denoted as solution I；By the precipitant Na of 53.7g2CO3It is placed in another beaker, adds 500g distilled water
Make it be completely dissolved, be denoted as solution II；Under condition of heating and stirring, solution I is simultaneously introduced with solution II and precipitates, keep temperature
Degree is 70 DEG C, controls reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after 80
DEG C it is dried 15 hours, and roasting 6 hours at 350 DEG C, obtains target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 5]
By the Cu (CH of 48.3g3COO)2, the Mn (CH of 20.0g3COO)2Zn (the CH of solution and 89.3g3COO)2It is placed in beaker
In, add 500g distilled water and make it be completely dissolved, be denoted as solution I；By the precipitant Na of 53.7g2CO3It is placed in another beaker, adds
Entering 500g distilled water makes it be completely dissolved, and is denoted as solution II；Under condition of heating and stirring, solution I is simultaneously introduced with solution II and carries out
Precipitation, keeping temperature is 60 DEG C, controls reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed,
It is dried 15 hours at 80 DEG C after filtration, and roasting 6 hours at 500 DEG C, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 6]
By the Cu (NO of 72.5g3)2, the ZrOCl of 20.0g2Zn (NO with 59.5g3)2It is placed in beaker, adds 500g distillation
Water makes it be completely dissolved, and is denoted as solution I；By the precipitant Na of 53.7g2CO3It is placed in another beaker, adds 500g distilled water and make
It is completely dissolved, and is denoted as solution II；Under condition of heating and stirring, solution 1 I is simultaneously introduced with solution II and precipitates, keep temperature
Be 70 DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after at 80 DEG C
It is dried 15 hours, and roasting 6 hours at 450 DEG C, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 7]
By the Cu (NO of 84.6g3)2, the Mg (NO of 15.0g3)2Zn (NO with 44.6g3)2It is placed in beaker, adds 500g and steam
Distilled water makes it be completely dissolved, and is denoted as solution I；By the precipitant Na of 53.7g2CO3It is placed in another beaker, adds 500g distilled water
Make it be completely dissolved, be denoted as solution II；Under condition of heating and stirring, solution I is simultaneously introduced with solution II and precipitates, keep temperature
Degree is 70 DEG C, controls reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after 100
DEG C it is dried 12 hours, and roasting 6 hours at 400 DEG C, obtains target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 8]
By the CuC of 60.4g2O4, the K of 10.0g2C2O4ZnC with 74.4g2O4It is placed in beaker, adds 500g distilled water and make
It is completely dissolved, and is denoted as normal solution I；The precipitant NaOH of 20g is placed in another beaker, adds 500g distilled water and make it complete
Dissolve, be denoted as normal solution II；Being simultaneously introduced with solution II by solution I under condition of heating and stirring and precipitate, keeping temperature is 80
DEG C, control reaction end pH=7.0, aging 3 hours, gained catalyst precursor slurry is scrubbed, filter after be dried at 80 DEG C
15 hours, and roasting 6 hours at 350 DEG C, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 9]
By the Cu (NO of 60.4g3)2, the Al (NO of 10.0g3)3Zn (NO with 74.4g3)2It is placed in beaker, adds 500g and steam
Distilled water makes it be completely dissolved, and is denoted as solution I；Preparation 10wt% ammonia 350g is denoted as solution II；By solution I under condition of heating and stirring
Being simultaneously introduced with solution II and precipitate, keeping temperature is 70 DEG C, controls reaction end pH=7.0, and aging 3 hours, gained was urged
Agent precursor pulp is scrubbed, filter after be dried 15 hours at 80 DEG C, and roasting 6 hours at 400 DEG C, obtain target and produce
Thing catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 10]
By 60.4g Cu (NO3)2, 10.0g Al (NO3)3, 74.4g Zn (NO3)2With 12.0g Mn (NO3)2Solution is placed in burning
In Bei, add 500g distilled water and make it be completely dissolved, be denoted as solution I；Preparation 10wt% ammonia 350g is denoted as solution II；Heating is stirred
Being simultaneously introduced with solution II by solution I under the conditions of mixing and precipitate, keeping temperature is 70 DEG C, controls reaction end pH=6.5, always
Change 3 hours, gained catalyst precursor slurry is scrubbed, filter after be dried 15 hours at 80 DEG C, and roasting 6 at 450 DEG C
Hour, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 11]
By the Cu (NO of 60.4g3)2, the Al (NO of 10.0g3)3, the Zn (NO of 74.4g3)2La (NO with 3.0g3)4, it is placed in burning
In Bei, add 500g distilled water and make it be completely dissolved, be denoted as solution I；Preparation 10wt% ammonia 350g is denoted as solution II；Heating is stirred
Being simultaneously introduced with solution II by solution I under the conditions of mixing and precipitate, keeping temperature is 65 DEG C, controls reaction end pH=7.0, always
Change 3 hours, gained catalyst precursor slurry is scrubbed, filter after be dried 15 hours at 80 DEG C, and roasting 3 at 500 DEG C
Hour, obtain target product catalyst.
Evaluate process conditions with embodiment 1.
[embodiment 12]
The catalyst that embodiment 2 prepares is loaded in the tubular reactor of a diameter of 12mm, and under 300 DEG C of hydrogen atmospheres
Activate 6 hours.With the isobutene. of volumetric concentration 2% as raw material, reaction temperature 40 DEG C, air speed 8000h-1, reaction pressure normal pressure, instead
1 should be the results are shown in Table.
[embodiment 13]
The catalyst that embodiment 2 prepares is loaded in the tubular reactor of a diameter of 12mm, live under 250 DEG C of hydrogen atmospheres
Change 24 hours.With the butadiene of concentration 5% as raw material, reaction temperature 30 DEG C, air speed 6000h-1, reaction pressure 0.1Mpa, reaction
The results are shown in Table 1.
[embodiment 14]
The catalyst that embodiment 2 prepares is loaded in the tubular reactor of a diameter of 12mm, live under 250 DEG C of hydrogen atmospheres
Change 6 hours.With the 1-amylene of volumetric concentration 10% as raw material, reaction temperature room temperature (30 DEG C), air speed 6000h-1, reaction pressure
0.5Mpa, reaction result is shown in Table 1.
[embodiment 15]
The catalyst that embodiment 6 prepares is loaded in the tubular reactor of a diameter of 12mm, live under 240 DEG C of hydrogen atmospheres
Change 24 hours.With the propylene of volumetric concentration 6% as raw material, reaction temperature 100 DEG C, air speed 10000h-1, reaction pressure 0.5Mpa,
Reaction result is shown in Table 1.
[embodiment 16]
The catalyst that embodiment 11 prepares is loaded in the tubular reactor of a diameter of 12mm, under 250 DEG C of hydrogen atmospheres
Activate 6 hours.With the propylene of volumetric concentration 15% as raw material, reaction temperature 30 DEG C, air speed 8000h-1, reaction pressure 2.5Mpa,
Reaction result is shown in Table 1.
[embodiment 17]
The catalyst that embodiment 11 prepares is loaded in the tubular reactor of a diameter of 12mm, activation phenomenon H2/N2(H2Contain
Amount is 15%, v/v), activate 8 hours at 250 DEG C.With the propylene of volumetric concentration 30% as raw material, reaction temperature 100 DEG C, air speed
8000h-1, reaction pressure 3.0Mpa, reaction result is shown in Table 1.
[embodiment 18]
Weigh the prepared catalyst 100g of embodiment 11 and carry out stability experiment.6 are activated little under 250 DEG C of hydrogen atmospheres
Time.With the ethylene of volumetric concentration 10% as raw material, reaction temperature 30 DEG C, air speed 8000h-1, reaction pressure 0.1MPa, reaction result
It is shown in Table 2.
Catalyst is more than 99.5% through the successive reaction of 1000 hours, conversion of ethylene, and ethane recovery is more than 99.5%,
Show good stability.
Table 1
| Alkene | Volumetric concentration | Ethylenic unsaturation hydrocarbon conversion rate/% | Saturated alkane yield/% | |
| Embodiment 1 | Ethylene | 5% | 100 | 100 |
| Embodiment 2 | Ethylene | 5% | 99.5 | 99.5 |
| Embodiment 3 | Ethylene | 5% | 100 | 100 |
| Embodiment 4 | Ethylene | 5% | 100 | 100 |
| Embodiment 5 | Ethylene | 5% | 100 | 100 |
| Embodiment 6 | Ethylene | 5% | 100 | 100 |
| Embodiment 7 | Ethylene | 5% | 100 | 100 |
| Embodiment 8 | Ethylene | 5% | 100 | 100 |
| Embodiment 9 | Ethylene | 5% | 100 | 100 |
| Embodiment 10 | Ethylene | 5% | 100 | 100 |
| Embodiment 11 | Ethylene | 5% | 100 | 100 |
| Embodiment 12 | Isobutene. | 2% | 100 | 100 |
| Embodiment 13 | Butadiene | 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 process conditions, the present invention turning in the tail gas catalyzed reaction of olefin-containing
Rate is close to 100%, and alkane yield is close to 100%.From table 2 it can be seen that the catalyst of the application has good stability.
Claims (8)
1. a processing method for the tail gas catalyzed hydrogenation of olefin-containing, alkene volumetric concentration is that the tail gas of 0.05-50% enters reaction
Device contacts with catalyst, is 0-4.0MPaG in reaction pressure, and reaction temperature is room temperature-200 DEG C, and volume space velocity is 500-
20000h-1Under carry out catalytic hydrogenation；Described catalyst include active component, auxiliary agent and carrier, described active component be copper or
The oxide of copper, content is 30-75wt%, and described auxiliary agent is La2O3、ZrO2、CeO2、Fe2O3、NiO、MgO、MnO、Al2O3、K2O
In at least one, content is 1-40wt%, and described carrier is zinc oxide, content 20-65wt%；Described catalyst uses and includes
Prepared by the method for following steps:
1) preparing metal saline solution I, containing copper ion, zinc ion, the metal ion of at least one auxiliary agent in solution；
2) preparation precipitant solution, is designated as solution II；
3) solution I, solution II are simultaneously or successively added in container, at 35-85 DEG C, carry out precipitation, reaction end pH=
6-8, aging 0-6 hour, obtains catalyst precursor slurry；
4) by catalyst precursor slurry washing, filtration, the ion of removing free state, it is dried 6-48 hour at 60-200 DEG C；
5) by dried catalyst precursor slurry roasting 1-24 hour at 300-700 DEG C, described catalyst is prepared.
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described metal salt solution I
Nitrate, acetate, oxalates or chloride for metal.
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described precipitant solution
Selected from sodium carbonate, sodium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, sodium bicarbonate, carbamide or ammonia spirit.
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described precipitation
Temperature 40-70 DEG C.
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described sintering temperature
350-500℃。
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described alkene includes list
Alkene and alkadienes.
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described alkene volume is dense
The tail gas that degree is 0.05-20% enters reactor and contacts with catalyst, is 0-3.0MPaG in reaction pressure, and reaction temperature is room
Temperature-150 DEG C, volume space velocity is 1000-10000h-1。
The processing method of the tail gas catalyzed hydrogenation of olefin-containing the most according to claim 1, it is characterised in that described catalyst needs elder generation
Activation processing, activation temperature is 150-350 DEG C, and activation phenomenon is H2Or H2With N2, the mixed gas of Ar, He noble gas, wherein
The volumn concentration of hydrogen is 0.1-99.9%, soak time 1-72 hour.
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| US8680350B2 (en) * | 2006-07-17 | 2014-03-25 | Basf Se | Process for hydrogenating unsaturated hydrocarbons in the presence of catalysts containing copper and zinc |
| FR2909571B1 (en) * | 2006-12-11 | 2009-10-02 | Inst Francais Du Petrole | CATALYST PREPARED BY IMPREGNATION OF AQUEOUS SOLUTION CONTAINING OXY (HYDROXY) PARTICLES OF A CATION IN INTERACTION WITH A MOLECULAR SPECIES OF A GROUP VIII METAL |
| CN102327774B (en) * | 2011-07-06 | 2014-05-28 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
| CN102989477B (en) * | 2011-09-09 | 2015-02-25 | 中国石油天然气股份有限公司 | Nickel-based hydrogenation catalyst, preparation method and method for reducing and regenerating catalyst |
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