CN104174396A - Silver-containing light alkane dehydrogenation catalyst and preparation method thereof - Google Patents
Silver-containing light alkane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN104174396A CN104174396A CN201410392585.6A CN201410392585A CN104174396A CN 104174396 A CN104174396 A CN 104174396A CN 201410392585 A CN201410392585 A CN 201410392585A CN 104174396 A CN104174396 A CN 104174396A
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Abstract
The invention discloses a silver-containing light alkane dehydrogenation catalyst and a preparation method thereof. The catalyst is characterized by comprising three parts, namely, a main active component, additives and a carrier, wherein the main active component is oxide of chromium, and the content of the main active component is 1-30wt percent; the additives refer to one or more of Na, K, Ca, Mg, Cu, Zr, Ce and Ag, and the content of oxide of an additive element is 0.01-10wt percent; and the rest is the carrier aluminum oxide. The preparation method comprises the following steps: loading the active metal and the additives by using a dipping method or co-dipping method, and subsequently drying and roasting, thereby obtaining the silver-containing light alkane dehydrogenation catalyst.
Description
Technical field
The invention belongs to catalyst preparation field, relate to catalyst for dehydrogenation of low-carbon paraffin of a kind of argentiferous and preparation method thereof, particularly improve the method for preparing catalyst of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation activity and stability.
Background introduction
Propylene and isobutene are two kinds of important Organic Chemicals, and their consumption is only second to ethene.Propylene, except for the production of polypropylene, is still produced acrylonitrile, the primary raw material of the products such as butanols, octanol, expoxy propane, isopropyl alcohol, propyl benzene, acrylic acid, oxo-alcohols and nonyl phenol.Isobutene is widely used in multiple Organic Chemicals and the fine chemicals such as synthetic rubber, butyl rubber and polyisobutene.In traditional handicraft, these two kinds of low-carbon alkene main sources are by-product C of naphtha vapor cracking ethylene preparation device
3, C
4the byproduct of petrol and diesel oil is produced in cut and plant catalytic cracking, and isobutene also derives from the accessory substance tert-butyl alcohol (TAB) of Halcon method expoxy propane in synthetic.But naphtha cracking technique is mainly for the production of basic petrochemical material ethene, instead of the technique of being devoted to produce propylene and isobutene.In recent years, along with the rapid growth of the alkene downstream derivative market demand, the exploitation of propylene, butylene downstream product are day by day extensive, the low-carbon alkene that traditional handicraft is produced can not meet the demand it day by day being increased, the contradiction of global propylene, Butene shortage both at home and abroad at all.In order to meet the great demand of the world to low-carbon alkene, extensively carry out the research and development of low-carbon alkene generation new technology both at home and abroad.Wherein, the corresponding alkene of dehydrogenating low-carbon alkane system is the very competitive technology of one.
Dehydrogenating low-carbon alkane technology mainly contains catalytic dehydrogenation and oxidative dehydrogenation.Catalytic dehydrogenation is the endothermic reaction, and is the reversible reaction that molecular number increases, and high-temperature low-pressure is conducive to its reaction, but is subject to thermodynamics equilibrium limit.Have for the dehydrogenating technology of low-carbon alkanes at present: the Oleflex technique of (1) Uop Inc.; (2) the Catofin technique of Lummus; (3) the STAR technique of Phillips company; (4) the Linde technique of the FBD-4 technique of Snamprogetti SPA company and (5) German Linde company.The catalyst that these techniques are used is mainly chromium-based catalysts and the large class of precious metals pt series catalysts two.Oxidative dehydrogenation is exothermic reaction, is not subject to thermodynamic limitation, and reaction can be carried out at a lower temperature, has comparatively tempting development prospect, but may be due to more technical factors, at present and have no industrialization report.
For dehydrogenating low-carbon alkane technique, at present industrial is mainly Cr taking the Catofin technique of Lummus as representative
2o
3/ Al
2o
3catalyst and the precious metals pt-Sn/Al taking the Oleflex technique of Uop Inc. as representative
2o
3catalyst.Catofin process using fixed bed circulation multiple reactor system, is used Cr
2o
3/ Al
2o
3catalyst, for dehydrogenating propane, this reaction is carried out above at 550 DEG C, pressure (3～5) × 10
4pa, conversion per pass 48%～65%, selectivity ratios oleflex technique is high more than 2%.But the problem that this catalyst exists is that catalyst stability is not high, and inactivation is fast, only has 15～30min reaction time, need carry out coke-burning regeneration to catalyst every 7～15min, and complicated operation, has a strong impact on production efficiency.So people are actively developing the method that improves chromium-based catalysts activity and stability.
Patent CN 102019178A discloses a kind of catalyst of preparing propylene by dehydrogenating propane, and consisting of of this catalyst comprises Al
2o
3, the oxide of one or more Cr, one or more rare earth oxides, a kind of composition that one or more alkali metal oxides form, wherein
al2O3the oxide that accounts for 50～95%, Cr accounts for 3～40%, and rare earth oxide accounts for 0～20%, and alkaline-earth metal accounts for 0～10%.Be 30～40% for the conversion ratio of propane, Propylene Selectivity 80～90%.
Patent CN 1185994A discloses a kind of K
2o-CuO-La
2o
3-Cr
2o
3/ Al
2o
3catalyst, can carry out preparing isobutene through dehydrogenation of iso-butane, 500～800 DEG C of reaction temperatures, is greater than 50% for the conversion ratio of iso-butane, and selective isobutene is greater than 90%.This catalyst also can be for preparing propylene by dehydrogenating propane.
Patent CN 103044180A discloses and has a kind ofly prepared the Cr of isobutene containing auxiliary agent Ca and K for dehydrogenation of isobutane
2o
3-CaO-K
2o-Al
2o
3for catalyst, at 530～590 DEG C of reaction temperatures, reaction pressure 0.1～0.5MPa, iso-butane is carried out to catalytic dehydrogenating reaction, and after every reaction a period of time (5～30min), catalyst is regenerated with hydrogen, remain on more than 40% for iso-butane conversion ratio, selective isobutene is more than 95%.
Patent EP 0947247A1 discloses a kind of Cr containing auxiliary agent Zr and Ce
2o
3/ Al
2o
3catalyst, when conversion of propane keeps, has improved the selective of propylene, has reduced carbon deposition quantity.
Patent WO 2005040075A1 discloses a kind of catalyst Cr containing auxiliary agent Zr and Mg
2o
3/ Al
2o
3catalyst, than the catalyst that there is no zirconium and magnesium, this catalyst has higher selective and higher isobutene productive rate for the dehydrogenation of iso-butane.
Patent WO 2003106388A1, US 20060094914A1, US 7279611B2 and US 7012038B2 all disclose a kind of Cr containing Li and Na
2o
3/ Al
2o
3catalyst, the typical feature of this catalyst is high activity, high selectivity, and hydrothermal stability is high, and the life-span is long, and inactivation rate is low.
Existing catalyst is all that the method by adding auxiliary agent has been improved Cr to a certain extent
2o
3/ Al
2o
3the activity of catalyst and stability, and to add activity and the stability that auxiliary agent improves catalyst be a kind of simple method, and the auxiliary agent of interpolation mainly contains: the metallic elements such as Zr, Na, K, Mg, Li, Cu, Ca.But, improve for the example of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation stability and but rarely have report as auxiliary agent with Ag.High stability is an important performance of silver catalyst, and silver catalyst is widely used in the reaction of industrial ethylene epoxidizing production oxirane.We add in chromium-based catalysts silver as auxiliary agent, have significantly improved the stability of chromium-based catalysts, have solved well the fast problem of chromium-based catalysts inactivation.
Summary of the invention
For the Cr that is applied at present the Catofin of Lummus company technique
2o
3/ Al
2o
3catalyst stability is not high, and the shortcoming that inactivation is fast the invention provides a kind of Cr containing auxiliary agents such as Ag
2o
3/ Al
2o
3catalyst, this catalyst at conversion ratio with in selective maintenance, has the advantages such as stability is high, inactivation is slow, carbon accumulation resisting ability is strong for dehydrogenating low-carbon alkane and mixed alkanes dehydrogenation.
The present invention is catalyst for dehydrogenation of low-carbon paraffin of a kind of argentiferous and preparation method thereof, relates to:
A catalyst for dehydrogenation of low-carbon paraffin for argentiferous, is characterized in that:
Catalyst is made up of main active component, auxiliary agent and carrier three parts;
Wherein, the oxide that main active component is chromium, mass content is 1～30wt%;
Auxiliary agent is one or more in Na, K, Ca, Mg, Cu, Zr, Ce, Ag, and the oxide mass content of auxiliary element is 0.01～10wt%;
All the other are carrier, and carrier is Al
2o
3; Select ball-type, column type, star, trifolium-shaped, quatrefoil or the various shapes of sheet type;
Specific surface area of catalyst is 50～200m
2/ g, pore volume is 0.1～0.8ml/g.
The preparation method who the invention still further relates to a kind of catalyst for dehydrogenation of low-carbon paraffin of argentiferous, is characterized in that:
Comprise following concrete steps:
1) preparation of catalyst carrier: get aluminium hydroxide powder, add that to account for aluminium hydroxide powder mass content be that 1～10% sesbania powder mixes, adding mass concentration is that 1～10% citric acid and mass concentration are that 1～30% rare nitric acid carries out kneading again, the kneading time is 10min～2h, finally on forming machine, carry out again moulding, carrier after moulding dries in the air after 1～12h in room temperature, dry 1～12h in 80～150 DEG C again, finally 500～1000 DEG C of roasting 1～12h in Muffle furnace of carrier of drying, obtain final alumina catalyst support;
Preparing the aluminium hydroxide powder granularity that alumina catalyst support uses is between 50 microns to 300 microns, comprises amorphous hydroted alumina, false boehmite, boehmite, diaspore, gibbsite, surge aluminium stone, promise diaspore; The alumina catalyst support making is chosen as a kind of alumina powder jointed, or selects the one of two or more different grain size scopes alumina powder jointed, or selects the identical or different alumina powder jointed mixture of two or more granularities;
The machine of preparing the moulding that alumina catalyst support uses comprises tablet press machine, roll-type granulator, pellet processing machine, moulding machine, banded extruder; That the shape of moulding rear oxidation aluminium mixture comprises is spherical, sheet, cylinder, star, trilobal, quatrefoil;
2) catalyst preparation: adopt step impregnation method or co-impregnation to come load active component and auxiliary agent:
While wherein adopting step impregnation method, the dipping aqueous solution soaking of formulation aid or spray saturated impregnated carrier in advance, then after dry, roasting, prepare again the maceration extract aqueous solution of active metal, soak or spray saturated impregnated carrier, active component and adjuvant component metal are entered in carrier hole, and then dry, roasting makes catalyst for dehydrogenation of low-carbon paraffin;
Adopt while being total to dipping method, prepare the steep water solution of main active component and auxiliary agent, soak or spray saturated impregnated carrier, the catalyst for dehydrogenation of low-carbon paraffin be then dried, roasting making argentiferous.
According to catalyst of the present invention, it is characterized in that: the oxide of chromium mass content in catalyst is 5～28wt%; The auxiliary element adding in catalyst comprises in Na, K, Ca, Mg, Cu, Zr, Ce, Ag one or more, and its auxiliary element oxide mass content is 0.05～8.5wt%; All the other are alumina catalyst support.
According to catalyst of the present invention, it is characterized in that: in the combination of the auxiliary element that adds in catalyst, at least will comprise Ag, and in catalyst, the ratio of the oxide mass content of Ag and the oxide mass content of Cr is 0.001～0.5.
According to the preparation method of catalyst of the present invention, it is characterized in that: the steep water solution that contains chromium element and adjuvant component is soluble-salt solution, comprises nitrate, hydrochloride or acylate solution; The chromium element adding in catalyst preparation process is from the salt in water that is dissolvable in water of chromium, comprises one or more in chromic nitrate, chromate, chromic anhydride, chromium+oxalic acid, chromic tartrate;
According to the preparation method of catalyst of the present invention, it is characterized in that: dipping rear catalyst is dry at 120～220 DEG C, in the mist of 500～850 DEG C, carry out roasting, mist is by comprising that percent by volume is that the air that 0～10% steam and percent by volume are 90～100% forms.
In the preparation method of catalyst of the present invention, hydrothermal treatment consists generally has the effect of adjustment hole structure for catalyst and aluminium oxide, in the present invention, hydrothermal treatment consists under high temperature not only has certain regulating action to the pore structure of catalyst and carrier, also there is regulating action for the interaction between active component chromium oxide and alumina catalyst support, make on catalyst chromium oxide crystal grain more roomy, and present more crystal grain, improve the decentralization of active component crystal grain on catalyst, and then promote the stability of catalyst.
When catalyst of the present invention is used for dehydrogenating low-carbon alkane, generally under the reaction temperature higher than 500 DEG C, carry out dehydrogenation reaction, the general condition of reaction is reaction pressure: 0.01～1MPa, 500～680 DEG C of reaction temperatures, and low-carbon alkanes gas space velocity is 150～1000h
-1.
The applicable low-carbon alkanes raw material of catalyst of the present invention is the liquefied petroleum gas of low-carbon alkanes content more than 85%, and raw material low-carbon alkanes refers to alkane gaseous mixture, particularly propane below the C4 of arbitrary proportion and the mist of butane.During taking propane as raw material, at reaction pressure 0.03～0.5MPa, 570～600 DEG C of reaction temperatures, propane feed gas gas space velocity 200～500h
-1condition under, conversion of propane is greater than 60%, Propylene Selectivity is higher than 90%; During taking mixed alkanes as raw material, at reaction pressure 0.03～0.5MPa, 550～580 DEG C of reaction temperatures, mist air speed 200～500h
-1condition under, the conversion ratio of mixed alkanes more than 50%, generate alkene selectively also more than 90%, obtained gratifying result.
The remarkable advantage of technology of the present invention is: (1) adopts the distinguishing feature of catalyst of the present invention is, with auxiliary agents such as Ag, carrier is carried out to modification, make carrier there is stable structure, under maintenance applied at elevated temperature condition, pore passage structure, crystalline phase is stable, greatly improve catalyst stability, and then the extending catalyst life-span; (2) distinguishing feature is on the other hand to adopt the auxiliary combination effects such as Ag, the main active component of catalyst is carried out to modulation, make catalyst there is good carbon accumulation resisting ability, on microcosmic, regulate the interaction of chromium oxide crystal grain and carrier simultaneously, the change of inhibiting grain growth and structure, effectively improve the selective of low-carbon alkanes conversion ratio and low-carbon alkene, the service life of extending catalyst.(3) in addition, by catalyst is carried out to hydrothermal treatment consists, increase the dispersive property of catalyst activity component crystal grain and regulate grain size, playing the effect of stabilizing catalyst activity.
By the synergy of these aspects, ensure that the technology that the present invention proposes is different from the feature that has invention and technology: 1) simple catalyst preparation technology; 2) excellent dehydrogenating low-carbon alkane activity and olefine selective; 3) excellent catalyst activity and stability.
Detailed description of the invention
Below will by specific embodiment, the invention will be further described, but the present invention is not limited to these embodiment.
Embodiment 1
Carrier A l
2o
3preparation.By a certain amount of alumina powder jointed be that 8% sesbania powder mixes with accounting for alumina powder jointed mass fraction, adding mass concentration is that 6% citric acid and mass concentration are that 20% rare nitric acid carries out kneading again, the kneading time is 30min, finally on forming machine, carry out again moulding, carrier after moulding dries in the air after 8h in room temperature, then in 120 DEG C of oven dry 4h, the carrier of oven dry is 900 DEG C of roasting 6h in Muffle furnace finally, obtain final carrier, its water absorption rate is 62.3%.
Take chromium trioxide 18g, silver nitrate 0.45g, sodium nitrate 3.0g, zirconyl nitrate 2.4g, adds 30ml deionized water to be made into maceration extract, takes the carrier A l of above-mentioned preparation
2o
320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, at the room temperature 2h that dries in the air, then dries 2h in 120 DEG C, roasting 6h under 760 DEG C of air atmospheres, and the component that obtains catalyst finished product A is: Cr-Ag-Na-Zr/Al
2o
3, wherein each component is taking the quality percentage composition of oxide as Cr
2o
3: 20.5%, AgO:0.56%, Na
2o:1.9%, ZrO
2: 1.6%, Al
2o
3: 75.4%.
The dehydrogenating propane reactivity worth test of catalyst A: adopt 10ml fixed bed minisize reaction evaluation system, getting 10 milliliters, to pack internal diameter into be to carry out the test of dehydrogenating propane reactivity worth in the stainless steel reactor of 8 millimeters, and relevant reaction condition is: the mass space velocity of unstripped gas propane is 200h
-1, reaction pressure: 0.1MPa, 600 DEG C of reaction temperatures.
After reaction is carried out 10 minutes and 60 minutes, chromatography is carried out in sampling respectively, and analysis result shows that after this catalyst successive reaction 60min, selectively not significantly decreasing of the conversion ratio to propane and propylene, has shown good stability.The dehydrogenating propane reactivity worth of catalyst A the results are shown in Table 1.
Embodiment 2
Carrier A l
2o
3preparation with embodiment 1.
Take chromium trioxide 18g, silver nitrate 1.0g, potassium nitrate 2.8g, calcium nitrate 3.2g, adds 30ml deionized water to be made into maceration extract, takes the carrier A l of above-mentioned preparation
2o
320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, at the room temperature 2h that dries in the air, dry 2h in 120 DEG C again, roasting 6h under 760 DEG C of mixed atmospheres, mist is made up of 10% steam and 90% air, and the component that obtains catalyst finished product B is: Cr-Ag-K-Ca/Al
2o
3, wherein each component is taking the quality percentage composition of oxide as Cr
2o
3: 20.5%, AgO:1.2%, K
2o:2.2%, CaO:1.9%, Al
2o
3: 74.2%.
Evaluating catalyst condition is: in mixed alkanes, the mol ratio of propane and butane is 2:1, reaction pressure 0.1MPa, 550 DEG C of reaction temperatures, mist air speed 200h
-1, other conditions are identical with embodiment 1.Analysis result shows that after this catalyst successive reaction 60min, selectively not significantly decreasing of the conversion ratio to mixed alkanes and alkene, has shown good stability.The mixed alkanes dehydrogenation reaction results of property of catalyst B is in table 1.
Embodiment 3
Carrier A l
2o
3preparation with embodiment 1.
Take chromium trioxide 18g, silver nitrate 2.0g, magnesium nitrate 3.0g, copper nitrate 2.9g, adds 30ml deionized water to be made into maceration extract, takes the carrier A l of above-mentioned preparation
2o
320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, at the room temperature 2h that dries in the air, dry 2h in 120 DEG C again, roasting 6h under 760 DEG C of mixed atmospheres, mist is made up of 5% steam and 95% air, and the component that obtains catalyst finished product C is: Cr-Ag-Mg-Cu/Al
2o
3, wherein each component is taking the quality percentage composition of oxide as Cr
2o
3: 20.5%, AgO:2.5%, MgO:1.4%, CuO:2.1%, Al
2o
3: 73.5%.
Evaluating catalyst condition and chromatography are with embodiment 1.Analysis result shows that after this catalyst successive reaction 60min, selectively not significantly decreasing of the conversion ratio to propane and propylene, has shown good stability.The dehydrogenating propane reactivity worth of catalyst C the results are shown in Table 1.
Embodiment 4
Carrier A l
2o
3preparation with embodiment 1.
Take chromium trioxide 18g, silver nitrate 4.5g, calcium nitrate 3.2g, cerous nitrate 2.1g, adds 30ml deionized water to be made into maceration extract, takes the carrier A l of above-mentioned preparation
2o
320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, at the room temperature 2h that dries in the air, then dries 2h in 120 DEG C, roasting 6h under 760 DEG C of air atmospheres, and the component that obtains catalyst finished product D is: Cr-Ag-Ca-Ce/Al
2o
3, wherein each component is taking the quality percentage composition of oxide as Cr
2o
3: 20.5%, AgO:4.9%, CaO:1.9%, Ce
2o
3: 1.4%, Al
2o
3: 71.3%.
Evaluating catalyst condition and chromatography are with embodiment 1.Analysis result shows that after this catalyst successive reaction 60min, selectively not significantly decreasing of the conversion ratio to propane and propylene, has shown good stability.The dehydrogenating propane reactivity worth of catalyst D the results are shown in Table 1.
Comparative example 1
Carrier A l
2o
3preparation with embodiment 1.
Take chromium trioxide 18g, sodium nitrate 3.0g, zirconyl nitrate 2.4g, adds 30ml deionized water to be made into maceration extract, takes the carrier A l of above-mentioned preparation
2o
320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, at the room temperature 2h that dries in the air, then dries 2h in 120 DEG C, roasting 6h under 760 DEG C of air atmospheres, and the component that obtains catalyst finished product a is: C-Na-Zr/Al
2o
3, wherein each component is taking the quality percentage composition of oxide as Cr
2o
3: 20.5%, Na2O:1.9%, ZrO
2: 1.6%, Al
2o
3: 76.0%.
Evaluating catalyst condition and chromatography are with embodiment 1.Analysis result shows, this is the catalyst of the argentiferous conversion ratio to propane and propylene selective suitable with catalyst A in the time of reaction 10min not, but after successive reaction 60min, very obvious to the conversion ratio decline of propane, illustrate that stability is very poor.The dehydrogenating propane reactivity worth of catalyst a the results are shown in Table 1.
Comparative example 2
Carrier A l
2o
3preparation with embodiment 1.
Take chromium trioxide 18g, potassium nitrate 2.8g, calcium nitrate 3.2g, adds 30ml deionized water to be made into maceration extract, takes the carrier A l of above-mentioned preparation
2o
320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, at the room temperature 2h that dries in the air, dry 2h in 120 DEG C again, roasting 6h under 760 DEG C of mixed atmospheres, mist is made up of 10% steam and 90% air, and the component that obtains catalyst finished product b is: Cr-K-Fe/Al
2o
3, wherein each component is taking the quality percentage composition of oxide as Cr
2o
3: 20.5%, K
2o:2.2%, CaO:1.9%, Al
2o
3: 75.4%.
Evaluating catalyst condition and chromatography are with embodiment 2.Analysis result shows, this not the catalyst of argentiferous the reaction conversion ratio to mixed alkanes and alkene selective suitable with catalyst B when 10min, but after successive reaction 60min, the conversion ratio of mixed alkanes is declined obviously, less stable is described, but activity decreased amplitude is less than the catalyst a of comparative example 1.The mixed alkanes dehydrogenation reaction results of property of catalyst b is in table 1.
The dehydrating alkanes performance of table 1 different catalysts
Claims (6)
1. a catalyst for dehydrogenation of low-carbon paraffin for argentiferous, is characterized in that:
Catalyst is made up of main active component, auxiliary agent and carrier three parts;
Wherein, the oxide that main active component is chromium, mass content is 1～30wt%;
Auxiliary agent is one or more in Na, K, Ca, Mg, Cu, Zr, Ce, Ag, and the oxide mass content of auxiliary element is 0.01～10wt%;
All the other are carrier, and carrier is Al
2o
3; Select ball-type, column type, star, trifolium-shaped, quatrefoil or the various shapes of sheet type;
Specific surface area of catalyst is 50～200m
2/ g, pore volume is 0.1～0.8ml/g.
2. a preparation method for the catalyst for dehydrogenation of low-carbon paraffin of argentiferous, is characterized in that:
Comprise following concrete steps:
1) preparation of catalyst carrier: get aluminium hydroxide powder, add that to account for aluminium hydroxide powder mass content be that 1～10% sesbania powder mixes, adding mass concentration is that 1～10% citric acid and mass concentration are that 1～30% rare nitric acid carries out kneading again, the kneading time is 10min～2h, finally on forming machine, carry out again moulding, carrier after moulding dries in the air after 1～12h in room temperature, dry 1～12h in 80～150 DEG C again, finally 500～1000 DEG C of roasting 1～12h in Muffle furnace of carrier of drying, obtain final alumina catalyst support;
Preparing the aluminium hydroxide powder granularity that alumina catalyst support uses is between 50 microns to 300 microns, comprises amorphous hydroted alumina, false boehmite, boehmite, diaspore, gibbsite, surge aluminium stone, promise diaspore; The alumina catalyst support making is chosen as a kind of alumina powder jointed, or selects the one of two or more different grain size scopes alumina powder jointed, or selects the identical or different alumina powder jointed mixture of two or more granularities;
The machine of preparing the moulding that alumina catalyst support uses comprises tablet press machine, roll-type granulator, pellet processing machine, moulding machine, banded extruder; That the shape of moulding rear oxidation aluminium mixture comprises is spherical, sheet, cylinder, star, trilobal, quatrefoil;
2) catalyst preparation: adopt step impregnation method or co-impregnation to come load active component and auxiliary agent:
While wherein adopting step impregnation method, the dipping aqueous solution soaking of formulation aid or spray saturated impregnated carrier in advance, then after dry, roasting, prepare again the maceration extract aqueous solution of active metal, soak or spray saturated impregnated carrier, active component and adjuvant component metal are entered in carrier hole, and then dry, roasting makes catalyst for dehydrogenation of low-carbon paraffin;
Adopt while being total to dipping method, prepare the steep water solution of main active component and auxiliary agent, soak or spray saturated impregnated carrier, the catalyst for dehydrogenation of low-carbon paraffin be then dried, roasting making argentiferous.
3. according to catalyst claimed in claim 1, it is characterized in that: the oxide of chromium mass content in catalyst is 5～28wt%; The auxiliary element adding in catalyst comprises in Na, K, Ca, Mg, Cu, Zr, Ce, Ag one or more, and its auxiliary element oxide mass content is 0.05～8.5wt%; All the other are alumina catalyst support.
4. according to catalyst claimed in claim 1, it is characterized in that: in the combination of the auxiliary element that adds in catalyst, at least will comprise Ag, and in catalyst, the ratio of the oxide mass content of Ag and the oxide mass content of Cr is 0.001～0.5.
5. according to the preparation method of catalyst claimed in claim 2, it is characterized in that: the steep water solution that contains chromium element and adjuvant component is soluble-salt solution, comprises nitrate, hydrochloride or acylate solution; The chromium element adding in catalyst preparation process is from the salt in water that is dissolvable in water of chromium, comprises one or more in chromic nitrate, chromate, chromic anhydride, chromium+oxalic acid, chromic tartrate.
6. according to the preparation method of catalyst claimed in claim 2, it is characterized in that: dipping rear catalyst is dry at 120～220 DEG C, in the mist of 500～850 DEG C, carry out roasting, mist is by comprising that percent by volume is that the air that 0～10% steam and percent by volume are 90～100% forms.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582613A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for propylene preparation through dehydrogenation of propane, and applications thereof |
| CN110114142A (en) * | 2017-02-02 | 2019-08-09 | 科莱恩公司 | Chrome catalysts material and the method for manufacturing and using it |
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| CN111468101A (en) * | 2019-01-24 | 2020-07-31 | 中国石油天然气股份有限公司 | Chromium-based catalyst and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996033151A1 (en) * | 1995-04-17 | 1996-10-24 | Mobil Oil Corporation | Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen |
| CN101624324A (en) * | 2008-07-10 | 2010-01-13 | 罗门哈斯公司 | Hybrid autothermal catalytic process for converting alkanes to alkenes and catalysts useful for same |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN103480359A (en) * | 2013-09-26 | 2014-01-01 | 中国海洋石油总公司 | Preparation method for light alkane dehydrogenation catalyst with non-uniformly distributed active components |
| CN103769078A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst for alkene production and its preparation method and application |
-
2014
- 2014-08-11 CN CN201410392585.6A patent/CN104174396B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996033151A1 (en) * | 1995-04-17 | 1996-10-24 | Mobil Oil Corporation | Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen |
| CN101624324A (en) * | 2008-07-10 | 2010-01-13 | 罗门哈斯公司 | Hybrid autothermal catalytic process for converting alkanes to alkenes and catalysts useful for same |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN103769078A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst for alkene production and its preparation method and application |
| CN103480359A (en) * | 2013-09-26 | 2014-01-01 | 中国海洋石油总公司 | Preparation method for light alkane dehydrogenation catalyst with non-uniformly distributed active components |
Cited By (21)
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| CN106582613A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for propylene preparation through dehydrogenation of propane, and applications thereof |
| CN110114142A (en) * | 2017-02-02 | 2019-08-09 | 科莱恩公司 | Chrome catalysts material and the method for manufacturing and using it |
| CN110560042B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
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| CN110560039A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | propane dehydrogenation catalyst and preparation method thereof |
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| CN110560042A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN110560043B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Method for producing propylene by propane dehydrogenation |
| CN110560037A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN110560039B (en) * | 2018-06-05 | 2021-09-03 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst and preparation method thereof |
| CN110560041B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for producing propylene by propane dehydrogenation |
| CN110560061B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Process for the dehydrogenation of propane |
| CN110560041A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | catalyst for producing propylene by propane dehydrogenation |
| CN111468101A (en) * | 2019-01-24 | 2020-07-31 | 中国石油天然气股份有限公司 | Chromium-based catalyst and preparation method and application thereof |
| CN111468101B (en) * | 2019-01-24 | 2024-03-01 | 中国石油天然气股份有限公司 | Chromium catalyst and preparation method and application thereof |
| CN115430457A (en) * | 2021-06-03 | 2022-12-06 | 中国科学院大连化学物理研究所 | Single-layer dispersed low-Cr-load propane dehydrogenation propylene preparation catalyst and preparation method thereof |
| CN115779886A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Sulfur-resistant alkane dehydrogenation catalyst, and preparation method and application thereof |
| CN115779886B (en) * | 2021-09-10 | 2024-03-26 | 中国石油化工股份有限公司 | Sulfur-resistant alkane dehydrogenation catalyst and preparation method and application thereof |
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