CN104148070B - A kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method - Google Patents
A kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method Download PDFInfo
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Abstract
The present invention is a kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method, it is characterised in that: catalyzer is made up of main active ingredient, auxiliary agent and carrier three part, and main active ingredient is the oxide compound of chromium, and content is 1～30wt%; Auxiliary agent is one or more in Na, K, Ca, Mg, Cu, Zr, Ce, Ag, and the oxide content of auxiliary element is 0.01～10wt%; All the other are the alumina catalyst support containing Ag; Adopting pickling process or co-impregnation to come supported active metal and auxiliary agent, then dry, roasting obtains the catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver.
Description
Technical field
The invention belongs to field of catalyst preparation. Relate to a kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method, particularly improve the active method for preparing catalyst with stability of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation.
Background technology
In low-carbon alkene, propylene and iso-butylene are two kinds of important Organic Chemicals, and their consumption is only second to ethene. Propylene is except for the production of except polypropylene, or produces vinyl cyanide, the main raw material of the products such as butanols, octanol, propylene oxide, Virahol, propyl benzene, vinylformic acid, oxo-alcohols and nonyl phenol. Iso-butylene is extensively for the synthesis of multiple Organic Chemicals and fine chemicals such as rubber, isoprene-isobutylene rubber and polyisobutene. In traditional technology, these two kinds of low-carbon alkene main sources are the by-product C of naphtha vapor cracking ethylene preparation device3、C4Evaporate point and the byproduct of petrol and diesel oil is produced in plant catalytic cracking, iso-butylene also derive from Halcon method propylene oxide synthesize in the by product trimethyl carbinol (TAB). But, cracking naphtha technique is mainly for the production of basic petrochemical material ethene, instead of is devoted to produce the technique of propylene and iso-butylene. In recent years, along with the swift and violent growth of the olefin downstream derivative market requirement, the exploitation of propylene, butylene derived product are day by day extensive, the low-carbon alkene that traditional technology is produced can not meet the demand it day by day increased both at home and abroad at all, and the contradiction of global propylene, butylene shortage of resources is day by day outstanding. In order to meet the world to the huge demand of low-carbon alkene, extensively carry out the research and development that low-carbon alkene generates 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 oxydehydrogenation. Catalytic dehydrogenation is thermo-negative reaction, and is the reversible reaction that molecule number increases, and high-temperature low-pressure is conducive to it to react, but limits by thermodynamic(al)equilibrium. The current dehydrogenating technology for low-carbon alkanes has: the Oleflex technique of (1) UOP company; (2) the Catofin technique of Lummus; (3) the STAR technique of Phillips company; (4) the Linde technique of the FBD-4 technique of SnamprogettiSPA company and Linde company of (5) Germany.The catalyzer that these techniques use is mainly chromium-based catalysts and the big class of precious metals pt series catalysts two. Oxydehydrogenation is thermopositive reaction, and by thermodynamical restriction, reaction can carry out at a lower temperature, has comparatively tempting development prospect, but may due to some factors in technology, at present and have no industrialization report.
For dehydrogenating low-carbon alkane technique, industrial mainly taking the Catofin technique of Lummus as the Cr of representative at present2O3/Al2O3Catalyzer and taking the Oleflex technique of UOP company as the precious metals pt-Sn/Al of representative2O3Catalyzer. Catofin technique adopts fixed bed circulation multiple reactor system, it may also be useful to Cr2O3/Al2O3Catalyzer, for dehydrogenating propane, this reaction carries out more than 550 DEG C, pressure (3-5) × 104Pa, per pass conversion 48%-65%, selectivity ratios oleflex technique is high by more than 2%. But it is not high that this catalyzer Problems existing is catalyst stability, inactivation is fast, and reaction time is 15-30min only, catalyzer need to be carried out coke-burning regeneration, complicated operation every 7-15min, seriously affect production efficiency. So people are actively developing the method improving chromium-based catalysts activity and stability.
Patent CN102019178A discloses the catalyzer of a kind of preparing propylene by dehydrogenating propane, and consisting of of this catalyzer comprises Al2O3, the oxide compound of one or more Cr, one or more rare-earth oxidation things, a kind of composition that one or more alkalimetal oxides are formed, wherein Al2O3Accounting for 50-95%, the oxide compound of Cr accounts for 3-40%, and rare-earth oxidation thing accounts for 0-20%, and alkaline-earth metal accounts for 0-10%. Transformation efficiency for propane is 30-40%, propylene selectivity 80-90%.
Patent CN1185994A discloses a kind of K2O-CuO-La2O3-Cr2O3/Al2O3Catalyzer, it is possible to carry out preparing isobutene through dehydrogenation of iso-butane, at temperature of reaction 500-800 DEG C, the transformation efficiency for Trimethylmethane is greater than 50%, and selective isobutene is greater than 90%. This catalyzer can also be used for preparing propylene by dehydrogenating propane.
Patent CN103044180A discloses a kind of Cr preparing iso-butylene for dehydrogenation of isobutane containing auxiliary agent Ca and K2O3–CaO-K2O-Al2O3Catalyzer, at temperature of reaction 530-590 DEG C, reaction pressure 0.1-0.5MPa, Trimethylmethane is carried out catalytic dehydrogenating reaction, and after often reacting for some time (5-30min), with hydrogen, catalyzer is regenerated, more than 40% is remained on for Trimethylmethane transformation efficiency, selective isobutene more than 95%.
Patent EP0947247A1 discloses a kind of Cr containing auxiliary agent Zr and Ce2O3/Al2O3Catalyzer, while conversion of propane keeps, it is to increase the selectivity of propylene, decreases carbon deposition quantity.
Patent WO2005040075A1 discloses a kind of catalyzer Cr containing auxiliary agent Zr and Mg2O3/γ-Al2O3Catalyzer, compared to the catalyzer not having zirconium and magnesium, this catalyzer has the iso-butylene product rate of higher selectivity and Geng Gao for the dehydrogenation of Trimethylmethane.
Patent WO2003106388A1, US20060094914A1, US7279611B2 and US7012038B2 all disclose a kind of Cr containing Li and Na2O3/Al2O3Catalyzer, the typical feature of this catalyzer is high reactivity, highly selective, hydrothermal stability height, and the life-span is long, and inactivation rate is low.
Existing catalyzer is all that the method by adding auxiliary agent improves Cr to a certain extent2O3/γ-Al2O3The activity of catalyzer and stability, and to add auxiliary agent to improve the activity of catalyzer and stability 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, it may also be useful to Ag improves the example for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation stability as auxiliary agent and but rarely has report.High stability is a key property of silver catalyst, and the reaction of oxyethane extensively produced by silver catalyst for industrial ethylene epoxidizing. Silver is joined in carrier framework as catalyst aid by we, significantly improves the stability of chromium-based catalysts, solves the problem that chromium-based catalysts inactivation is fast well.
Summary of the invention
For the Cr being applied to Lummus company Catofin technique at present2O3/Al2O3Catalyst stability is not high, the shortcoming that inactivation is fast, wherein just includes the situation that catalyzer occurs crystalline phase to transform under conditions of use to more stable crystalline phase. The present invention provides a kind of Cr adding Ag on carrier framework2O3/Al2O3Catalyzer and method for preparing catalyst thereof, this catalyzer while transformation efficiency and selectivity keep, has the advantages such as stability height, inactivation is slow, carbon accumulation resisting ability is strong for dehydrogenating low-carbon alkane propylene.
The present invention is a kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method; It is specifically related to:
A kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver: it is characterized in that:
Catalyzer is made up of main active ingredient, auxiliary agent and carrier three part;
Wherein, main active ingredient is the oxide compound of chromium, and mass content is 1～30wt%; Auxiliary agent be Na, K, Ca, Mg,
One or more in Cu, Zr, Ce, the oxide mass content of auxiliary element is 0.01～10wt%; All the other be
Carrier, carrier is the aluminum oxide containing Ag element, and Ag is present on alumina backbone, and carrier selects ball type, circle
Column type, star, trifolium-shaped, four leaf or flap-type different shapes;
It is 50～200m that catalyst specific surface amasss2/ g, pore volume is 0.1～0.8ml/g.
The present invention also relates to the preparation method of a kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver, it is characterised in that:
Comprise following concrete steps:
1) preparation of aluminium hydroxide:
Adopt acid-base neutralisation to produce aluminium hydroxide powder, neutralization process adds silver nitrate solution, then 120 DEG C
Dry 1～24h, pulverizing obtain the aluminium hydroxide powder containing Ag, and silver suboxide content wherein is 0.1～5wt%;
By a certain amount of aluminium hydroxide powder, the sesbania powder that aluminium hydroxide powder massfraction is 1-10% mixes with accounting for, add citric acid that mass concentration is 1-10% again and mass concentration is that 1-30% dust technology carries out kneading, the kneading time is 10min-2h, finally carry out shaping again on forming machine, the forming machine used comprises tabletting machine, roll-type nodulizer, pellet processing machine, moulding machine; Carrier after banded extruder is shaping is after room temperature dries in the air 1-12h, then dries 1-12h in 80-150 DEG C, and the carrier of oven dry is 500-1000 DEG C of roasting 1-12h in retort furnace finally, obtains final alumina catalyst support;
2) preparation of catalyzer:
Step impregnation method or co-impregnation is adopted to come load active component and auxiliary agent, when wherein adopting step impregnation method, in advance formulation aid steep water solution soaking or spray pouring carry out incipient impregnation carrier, then after drying, roasting, prepare the steeping fluid aqueous solution of active metal again, soak or spray pouring and carry out incipient impregnation carrier so that active ingredient and adjuvant component metal enter in carrier hole, then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin;
When adopting co-impregnation method, prepare the steep water solution of main active ingredient and auxiliary agent, soak or spray pouring and carry out incipient impregnation carrier, then the obtained catalyst for dehydrogenation of low-carbon paraffin of dry, roasting.
According to catalyzer of the present invention, it is characterised in that: the oxide compound of chromium in the catalyst content be 5～28wt%;The auxiliary element added in catalyzer is one or more kinds in Na, K, Ca, Mg, Cu, Zr, Ce, Ag, and its oxide content is 0.05～8wt%; All the other are carrier.
According to method for preparing catalyst of the present invention, it is characterized in that: when acid-base neutralisation prepares aluminium hydroxide, acidic solution and basic solution has at least one containing Al, the method of neutralization comprises cocurrent adding material, positive addition, anti-addition, neutralization process adds Silver Nitrate, Silver Nitrate can either mix and add in an acidic solution, it is also possible to add with silver nitrate solution separately; Neutralization temperature is room temperature～60 DEG C, and neutralization pH value is 6.5～10.0; Neutralize and complete carry out aging in two steps, first neutralize the aging 1～8h of complete slurries; After aging end, being 8.5～12 at slurry pH value, slurry temperature is when 50～80 DEG C, more aging 0.5～3h; Then filtration washing, at 120 DEG C of drying 4～20h, pulverizes the aluminium hydroxide powder obtained containing silver, and silver suboxide content wherein is 0.01～4wt%.
According to method for preparing catalyst of the present invention, it is characterised in that the steep water solution containing chromium element and adjuvant component is soluble salt solution, comprises nitrate, hydrochloride or acylate solution; The chromium element added from the salt being dissolvable in water in water of chromium, comprise in chromium nitrate, chromic salt, chromium acid anhydride, chromium+oxalic acid, chromic tartrate one or more.
According to method for preparing catalyst of the present invention, it is characterized in that dipping rear catalyst is dry at 120～220 DEG C, carrying out roasting in the mixed gas of 500～850 DEG C, by comprising, volume percent is that the water vapour of 0～10% and the air of volume percent 90-100% form to mixed gas.
Hydrothermal treatment consists generally has the effect of adjustment hole structure for catalyzer and aluminum oxide, in method for preparing catalyst of the present invention, the pore structure of catalyzer and carrier is not only had certain regulating effect by the hydrothermal treatment consists under high temperature, for the interaction between active ingredient chromic oxide and alumina catalyst support, also there is regulating effect, make chromic oxide crystal grain on catalyzer more roomy, and present more crystal grain, improve active ingredient crystal grain dispersity on a catalyst, and then the stability of promoting catalyst.
When catalyzer of the present invention is used for dehydrogenating low-carbon alkane, generally carrying out dehydrogenation reaction under higher than the temperature of reaction of 500 DEG C, the general condition of reaction is reaction pressure: 0.01～1MPa, temperature of reaction 500～680 DEG C, and low-carbon alkanes gas space velocity is 150～1000h-1。
The low-carbon alkanes raw material that catalyzer of the present invention is suitable for is the liquefied petroleum gas (LPG) of low-carbon alkanes content more than 85%, and raw material low-carbon alkanes refers to the alkane gas mixture, particularly propane of below the C4 of arbitrary proportion and the mixed gas of butane. When taking propane as raw material, at reaction pressure 0.03～0.5MPa, temperature of reaction 570～600 DEG C, propane feed gas gas space velocity 200～500h-1When, conversion of propane is greater than 64%, and propylene selectivity is higher than 95%; When taking mixed alkanes as raw material, at reaction pressure 0.03～0.5MPa, temperature of reaction 550～580 DEG C, mixed gas air speed 200～500h-1When, the transformation efficiency of mixed alkanes is more than 50%, and the selectivity generating alkene, also more than 90%, achieves gratifying result.
The remarkable advantage of the technology of the present invention is: (1) adopts the remarkable feature of catalyzer of the present invention to be containing Ag in alumina catalyst support skeleton, the existence of Ag, effectively prevent aluminum oxide crystalline phase under hydrothermal conditions from transforming, keep the stable of carrier and catalyst structure crystalline phase;Simultaneously also can regulate the surface acidity of aluminum oxide and then affect catalyst surface acid distribution, it is to increase catalyzer anti-carbon performance, extending catalyst work-ing life; (2) the various auxiliary agent synergy that the remarkable feature of another aspect is the Ag on catalyst backbone and adds in catalyst preparation process, carry out the main active ingredient of catalyzer adjusting and become, what make catalyzer has good carbon accumulation resisting ability, on microcosmic, regulate the interaction of chromic oxide crystal grain and carrier simultaneously, the change of inhibiting grain growth and structure, effectively improve the selectivity of low-carbon alkanes transformation efficiency and low-carbon alkene, the work-ing life of extending catalyst; (3) in addition, by catalyzer is carried out hydrothermal treatment consists, increase the dispersing property of catalyst activity component crystal grain and regulate grain size, play 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 of existing invention and technology: 1) simple catalyst preparation technology; 2) excellent dehydrogenating low-carbon alkane activity and olefine selective; 3) excellent catalyst activity stability.
Embodiment
Below will by specific embodiment, the invention will be further described, but the present invention is not limited to these embodiments.
Embodiment 1
Prepared by aluminium hydroxide. Getting 3.5g Silver Nitrate is dissolved in the dust technology of 1L20%, with Al2O3Concentration is the sodium aluminate solution neutralization of 200g/L, and neutralization temperature is 60 DEG C, and neutralization pH is 8.5. Neutralization terminates rear aging 1h, and then slurries are 9.5 at pH, continue aging 0.5h, filtration washing when temperature is 60 DEG C, at 120 DEG C of dry 8h, pulverizes and obtains aluminium hydroxide powder A1.
Carrier A l2O3Preparation. By a certain amount of aluminium hydroxide powder A1 with account for alumina powder jointed massfraction be 8% sesbania powder mix, add again mass concentration be 6% citric acid and mass concentration be that 20% dust technology carries out kneading, the kneading time is 30min, finally carry out shaping again on forming machine, carrier after shaping is after room temperature dries in the air 8h, then dries 4h in 120 DEG C, and the carrier of oven dry is 900 DEG C of roasting 6h in retort furnace finally, obtaining final carrier, its water-intake rate is 63.7%.
Take chromium trioxide 18g, SODIUMNITRATE 3.0g, Zircosol ZN 2.4g, add 30ml deionized water and be made into steeping fluid, take the carrier A l of above-mentioned preparation2O320g carries out supersaturation dipping 1h, is then pulled out by the carrier after dipping, dries in the air 2h in room temperature, then dries 2h, roasting 6h under 760 DEG C of air atmospheres in 120 DEG C, and the component obtaining catalyzer finished product A is: Cr-Ag-Na-Zr/Al2O3, wherein each component is taking the mass percentage of oxide basis as Cr2O3: 20.5%, AgO:2.2%, Na2O:1.9%, ZrO2: 1.6%, Al2O3: 73.8%.
The dehydrogenating propane reactivity worth test of catalyst A: adopt 10ml fixed bed minisize reaction evaluation system, getting 10 milliliters, to load internal diameters be carry out dehydrogenating propane reactivity worth test in the stainless steel reactor of 8 millimeters, and relevant reaction conditions is: the mass space velocity of unstripped gas propane is 200h-1, reaction pressure: 0.1MPa, temperature of reaction 600 DEG C.
After reaction carries out 10 minutes and 60 minutes, sampling carries out stratographic analysis respectively, after analytical results shows this catalyzer successive reaction 60min, the transformation efficiency of propane and the selectivity of propylene is not significantly decreased, shows good stability. The dehydrogenating propane reactivity worth of catalyst A the results are shown in Table 1.
Embodiment 2
Prepared by aluminium hydroxide. Get 5.5g Silver Nitrate and 600 grams of aluminum nitrates are dissolved into 1L solution, with Al2O3Concentration is the sodium aluminate solution neutralization of 200g/L, and neutralization temperature is 30 DEG C, and neutralization pH is 10. Neutralization terminates rear aging 1h, and then slurries are 10.5 at pH, continue aging 1.5h, filtration washing when temperature is 80 DEG C, at 120 DEG C of dry 8h, pulverizes and obtains aluminium hydroxide powder A2.
Carrier A l2O3Preparation with embodiment 1, it may also be useful to aluminium hydroxide A2 is as alumina raw material, and the water-intake rate preparing the carrier is 57.9%.
Take chromium trioxide 18g, saltpetre 2.8g, nitrocalcite 3.2g, add 30ml deionized water and be made into steeping fluid, take the carrier A l of above-mentioned preparation2O320g carries out supersaturation dipping 1h, is then pulled out by the carrier after dipping, dries in the air 2h in room temperature, 2h is dried again in 120 DEG C, roasting 6h under 760 DEG C of mixed atmospheres, mixed gas is made up of 10% water vapour and 90% air, and the component obtaining catalyzer finished product B is: Cr-Ag-K-Ca/Al2O3, wherein each component is taking the mass percentage of oxide basis as Cr2O3: 20.5%, AgO:3.4%, K2O:2.2%, CaO:1.9%, Al2O3: 72.0%.
Evaluating catalyst condition is: in mixed alkanes, the mol ratio of propane and butane is 2:1, reaction pressure 0.1MPa, temperature of reaction 550 DEG C, mixed gas air speed 200h-1, other conditions are identical with embodiment 1. After analytical results shows this catalyzer successive reaction 60min, the transformation efficiency of mixed alkanes and the selectivity of alkene are not significantly decreased, shows good stability. The mixed alkanes dehydrogenation reaction results of property of catalyst B is in table 1.
Embodiment 3
Prepared by aluminium hydroxide. Getting 0.5g Silver Nitrate and 800 grams of Tai-Ace S 150 are dissolved into 1L solution, the sodium hydroxide solution with 20% neutralizes, and neutralization temperature is 40 DEG C, and neutralization pH is 6.5. Neutralization terminates rear aging 2h, and then slurries are 11.5 at pH, continue aging 2.5h, filtration washing when temperature is 50 DEG C, at 120 DEG C of dry 8h, pulverizes and obtains aluminium hydroxide powder A3.
Carrier A l2O3Preparation with embodiment 1, it may also be useful to aluminium hydroxide A3 is as alumina raw material, and preparing the carrier water-intake rate is 59.4%.
Take chromium trioxide 18g, magnesium nitrate 3.0g, cupric nitrate 2.9g, add 30ml deionized water and be made into steeping fluid, take the carrier A l of above-mentioned preparation2O320g carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, dry in the air 2h in room temperature, 2h is dried again in 120 DEG C, roasting 6h under 760 DEG C of mixed atmospheres, mixed gas is made up of 5% water vapour and 95% air, and mixed gas is made up of 5% water vapour and 95% air, and the component obtaining catalyzer finished product C is: Cr-Ag-Mg-Cu/Al2O3, wherein each component is taking the mass percentage of oxide basis as Cr2O3: 20.5%, AgO:0.62%, MgO:1.4%, CuO:2.1%, Al2O3: 75.4%.
Evaluating catalyst condition and stratographic analysis are with embodiment 1. After analytical results shows this catalyzer successive reaction 60min, the transformation efficiency of propane and the selectivity of propylene are not significantly decreased, shows good stability. The dehydrogenating propane reactivity worth of catalyzer C the results are shown in Table 1.
Embodiment 4
Carrier A l2O3Preparation with embodiment 1.
Take chromium trioxide 18g, nitrocalcite 3.2g, cerous nitrate 2.1g, add 30ml deionized water and be made into steeping fluid, take the carrier A l of above-mentioned preparation2O320g carries out supersaturation dipping 1h, is then pulled out by the carrier after dipping, dries in the air 2h in room temperature, then dries 2h, roasting 6h under 760 DEG C of air atmospheres in 120 DEG C, and the component obtaining catalyzer finished product D is: Cr-Ag-Ca-Ce/Al2O3, wherein each component is taking the mass percentage of oxide basis as Cr2O3: 20.5%, AgO:2.2%, CaO:1.9%, Ce2O3: 1.4%, Al2O3: 74.0%.
Evaluating catalyst condition and stratographic analysis are with embodiment 1. After analytical results shows this catalyzer successive reaction 60min, the transformation efficiency of propane and the selectivity of propylene are not significantly decreased, shows good stability. The dehydrogenating propane reactivity worth of catalyzer D the results are shown in Table 1.
Comparative example 1
Carrier A l2O3Preparation with embodiment 1, its aluminium hydroxide used does not add Silver Nitrate in preparation process, and carrier water-intake rate is 62.2%.
Take chromium trioxide 18g, SODIUMNITRATE 3.0g, Zircosol ZN 2.4g, add 30ml deionized water and be made into steeping fluid, take the carrier A l of above-mentioned preparation2O320g carries out supersaturation dipping 1h, is then pulled out by the carrier after dipping, dries in the air 2h in room temperature, then dries 2h, roasting 6h under 760 DEG C of air atmospheres in 120 DEG C, and the component obtaining catalyzer finished product a is: Cr-Na-Zr/Al2O3, wherein each component is taking the mass percentage of oxide basis as Cr2O3: 20.5%, Na2O:1.9%, ZrO2: 1.6%, Al2O3: 76.0%.
Evaluating catalyst condition and stratographic analysis are with embodiment 1. Analytical results shows, this catalyzer not containing skeleton silver is suitable with catalyst A to the transformation efficiency of propane and the selectivity of propylene when reacting 10min, but after successive reaction 60min, is declined clearly by the transformation efficiency of propane, illustrate that stability is very poor. The dehydrogenating propane reactivity worth of catalyzer a the results are shown in Table 1.
Comparative example 2
Carrier A l2O3Preparation with embodiment 2, the preparation process of aluminium hydroxide A2 does not add Silver Nitrate, the water-intake rate preparing the carrier is 59.1%.
Take chromium trioxide 18g, saltpetre 2.8g, nitrocalcite 3.2g, add 30ml deionized water and be made into steeping fluid, take the carrier A l of above-mentioned preparation2O320g carries out supersaturation dipping 1h, is then pulled out by the carrier after dipping, dries in the air 2h in room temperature, 2h is dried again in 120 DEG C, roasting 6h under 760 DEG C of mixed atmospheres, mixed gas is made up of 10% water vapour and 90% air, and the component obtaining catalyzer finished product b is: Cr-K-Ca/Al2O3, wherein each component is taking the mass percentage of oxide basis as Cr2O3: 20.5%, K2O:2.2%, CaO:1.9%, Al2O3: 75.4%.
Evaluating catalyst condition and stratographic analysis are with embodiment 2. Analytical results shows, this catalyzer not containing skeleton silver is suitable with catalyst B to the transformation efficiency of mixed alkanes and the selectivity of alkene when reacting 10min, but after successive reaction 60min, the transformation efficiency decline of mixed alkanes is obvious, less stable is described, but active reduction amplitude is less than the catalyzer a of comparative example 1. The mixed alkanes dehydrogenation reaction results of property of catalyzer b is in table 1.
The dehydrating alkanes performance of table 1 different catalysts
Claims (6)
1. the catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver: it is characterized in that:
Catalyzer is made up of main active ingredient, auxiliary agent and carrier three part;
Wherein, main active ingredient is the oxide compound of chromium, and mass content is 1～30wt%; Auxiliary agent is one or more in Na, K, Ca, Mg, Cu, Zr, Ce, and the oxide mass content of auxiliary element is 0.01～10wt%; All the other are carrier, and carrier is the aluminum oxide containing Ag element, and Ag is present on alumina backbone, and carrier selects ball type, cylinder shape, star, trifolium-shaped, four leaf or flap-type;
It is 50～200m that catalyst specific surface amasss2/ g, pore volume is 0.1～0.8mL/g.
2. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver according to claim 1, it is characterised in that: comprise following concrete steps:
1) preparation of alumina catalyst support:
Adopting acid-base neutralisation to produce aluminium hydroxide powder, add silver nitrate solution in neutralization process, then 120 DEG C of drying 1～24h, pulverizing obtain the aluminium hydroxide powder containing Ag, and silver suboxide content wherein is 0.1～5wt%;
By a certain amount of aluminium hydroxide powder, the sesbania powder that aluminium hydroxide powder massfraction is 1-10% mixes with accounting for, add citric acid that mass concentration is 1-10% again and mass concentration is that 1-30% dust technology carries out kneading, the kneading time is 10min-2h, finally carrying out shaping again on forming machine, the forming machine used comprises tabletting machine, roll-type nodulizer, pellet processing machine, moulding machine, banded extruder; Carrier after shaping is after room temperature dries in the air 1-12h, then dries 1-12h in 80-150 DEG C, and the carrier of oven dry is 500-1000 DEG C of roasting 1-12h in retort furnace finally, obtains final alumina catalyst support;
2) preparation of catalyzer:
Step impregnation method or co-impregnation is adopted to come load active component and auxiliary agent, when wherein adopting step impregnation method, in advance formulation aid steep water solution soaking or spray pouring carry out incipient impregnation carrier, then after drying, roasting, prepare the steeping fluid aqueous solution of active metal again, soak or spray pouring and carry out incipient impregnation carrier so that active ingredient and adjuvant component metal enter in carrier hole, then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin;
When adopting co-impregnation method, prepare the steep water solution of main active ingredient and auxiliary agent, soak or spray pouring and carry out incipient impregnation carrier, then the obtained catalyst for dehydrogenation of low-carbon paraffin of dry, roasting.
3. according to catalyzer according to claim 1, it is characterised in that: the oxide compound of chromium in the catalyst content be 5～28wt%; In catalyzer add auxiliary element be in Na, K, Ca, Mg, Cu, Zr, Ce one or more, its oxide content is 0.05～8wt%; All the other are carrier.
4. according to the preparation method of catalyzer according to claim 2, it is characterized in that: when acid-base neutralisation prepares aluminium hydroxide, acidic solution and basic solution has at least one containing Al, the method of neutralization comprises cocurrent adding material, positive addition, anti-addition, neutralization process adds Silver Nitrate, Silver Nitrate can either mix and add in an acidic solution, it is also possible to add with silver nitrate solution separately; Neutralization temperature is room temperature～60 DEG C, and neutralization pH value is 6.5～10.0; Neutralize and complete carry out aging in two steps, first neutralize the aging 1～8h of complete slurries; After aging end, being 8.5～12 at slurry pH value, slurry temperature is when 50～80 DEG C, more aging 0.5～3h; Then filtration washing, at 120 DEG C of drying 4～20h, pulverizes the aluminium hydroxide powder obtained containing silver, and silver suboxide content wherein is 0.1～4wt%.
5. according to the preparation method of catalyzer according to claim 2, it is characterised in that: the steep water solution containing chromium element and adjuvant component is soluble salt solution, comprises nitrate, hydrochloride or acylate solution; The chromium element added from the salt being dissolvable in water in water of chromium, comprise in chromium nitrate, chromic salt, chromium acid anhydride, chromium+oxalic acid, chromic tartrate one or more.
6. according to the preparation method of catalyzer according to claim 2, it is characterized in that: dipping rear catalyst is dry at 120～220 DEG C, carrying out roasting in the mixed gas of 500～850 DEG C, mixed gas is that the water vapour of 0～10% and the air of volume percent 90-100% form by volume percent.
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