CN105312046A - Light alkane dehydrogenation catalyst and method for improving activity and stability thereof - Google Patents
Light alkane dehydrogenation catalyst and method for improving activity and stability thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a light alkane dehydrogenation catalyst. The light alkane dehydrogenation catalyst comprises the following components: 1-30 wt% of main active components (chromium oxides), 0.01-10 wt% of element oxides of an additive (one or more of Na, K, Ca, Mg, Cu and Zr) and the balance of a carrier. The invention also provides a method for improving the activity and the stability of the light alkane dehydrogenation catalyst in the light alkane dehydrogenation reaction process. According to the method, an adjusting gas for stabilizing the activity of the catalyst is added into a reaction system according to changes of the activity of the catalyst, the adjusting gas consists of an adjusting component and a dilution component, the adjusting component is one or more of compounds of sulfur, phosphorus and the seventh main-group elements and has the content of 0.001-1 v%, and the dilution component is one or more of water vapor, air, nitrogen gas and methane or ethane gas. The method can effectively decelerate deactivation and prolong the service life of the catalyst.
Description
Technical field
The present invention relates to dehydrogenation field, specifically relate to a kind of catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, and improve the method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation activity and stability.
Background introduction
Acidic catalyst uses a more class catalyst in petroleum refining and chemical industry, and as the alkylation of the isomerization of the cracking of hydro carbons, hydro carbons, aromatic hydrocarbons and alkene, the reaction such as the hydration alcohol of alkene, the dehydration of alcohol all uses acidic catalyst.Some reaction, although the oxidation reaction etc. as the dehydrogenation reaction of alkane, ethene and oxygen not exclusively relies on acidity of catalyst to carry out catalytic reaction, the acidity of catalyst still has certain facilitation to catalytic reaction.It is solid acid that the more class of current use possesses acid acidic catalyst.The solid that can provide proton or accept duplet is referred to as solid acid, as 1) natural clay class, their key components are silica and aluminium oxide; 2) the load carrier of liquid acid (comprising sulfuric acid, phosphoric acid etc.); 3) metal oxide or composite oxides, as ZrO
2, WO
3, MoO
3/ Al
2o
3, Fe
2o
3/ SiO
2, synthesis of molecular sieve etc.
Present acid corresponding with solid material, the solid of duplet or adsorber acid can be provided for those, also can be referred to as solid base.A lot of reactions, although by the acid site institute catalysis on catalyst, the existence at alkali center more or less play certain synergy with acid site, Acid-Base center synergy shows very high catalytic activity sometimes.This kind of reaction just comprises dehydrating alkanes reaction.
Low-carbon alkene is important Organic Chemicals, as larger in current propylene demand, traditional processing technology can not be met the need of market, and the emerging low-carbon alkene production technology thus substituted comprises five kinds of emerging techniques such as dehydrogenating propane (PDH), methanol-to-olefins (MTO, MTP), DCC (DCC), olefin cracking and olefin(e) disproportionation.Comparatively speaking, the advantages such as dehydrogenating low-carbon alkane technical advantage is more obvious, and it possesses technology maturation, good product quality, conversion ratio is high, accessory substance is few.Current industrialized dehydrogenating low-carbon alkane propylene production technology is the Oleflex technique of American UOP company and the Catofin technique of Lummus company of the U.S. mainly.Catofin technique uses Cr series catalysts, its low price, requires low, be suitable for the present situation that internal sources is in short supply to raw material impurity.
Relate in the reaction of hydro carbons at majority, such as dehydrogenating low-carbon alkane reaction, the parent of reactant molecule, product molecule and the many charcoals that likely becomes to make a living of reaction intermediates, they or be combined with each other, or the carbide-containing deposition being mutually condensed into multiple HMW is on a catalyst.With on the catalyst of metal oxide for main active component, its carbon deposit is acid site carbon distribution mainly, and the speed of carbon distribution is relevant with the Acidity of Aikalinity of catalyst surface.
Chromium oxide/aluminum oxide catalyst has relatively high dehydrogenation activity, but dehydrogenation reaction is carried out at relatively high temperatures, cracking, isomerization and deep dehydrogenation reaction can occur usually, due to existence acid on catalyst, accelerate the generation of coke on catalyst.But research shows, the acid initial activity for dehydrogenating propane reaction and selectively to count for much, if acidity is too low, then the activity of catalyst also can reduce.Therefore in catalyst preparation process, in order to reduce the impact of catalyst carbon deposit on its activity, generally in catalyst preparation process, adding alkali metal or alkali earth metal, being used for acting synergistically with acid centre on catalyst, regulate acidity of catalyst, improve catalyst stability and activity.Chinese patent CN102123790A discloses and in catalyst preparation process, to add sodium oxide molybdena and potassium oxide to improve chromium oxide/aluminum oxide catalyst, in order to improve catalyst activity and aging rear catalyst performance.The catalyst obtained shows higher selective and olefins yield, especially after aging.Chinese patent CN1668555A discloses a kind of substep and alkali metallic sodium and lithium is added in aluminium oxide, thus obtains a kind of preparation method of dehydrogenation catalyst complex of high-temperature stable.Chinese patent CN1309585A discloses a kind of method that FCC catalysts strengthens acid sites.Comprise and catalyst is contacted with the aqueous solution of aluminium with containing phosphorus, form water slurry, obtained the enhancing at acidity of catalyst position by stable pH value.Reduce the degree of many metal poisonings on catalyst, and improve the quantity of catalyst acid reactive site.
The current general method improving acidity of catalyst, mainly in catalyst preparation stages, by add alkaline metal ions or acid ion etc. regulate the intensity of acidic site on catalyst and quantity number, as Chinese patent CN1309585A, in catalyst preparation stages, with the addition of phosphorus etc. on a catalyst and the acidity of catalyst is strengthened.Patent WO2005040075A1 discloses a kind of catalyst Cr containing auxiliary agent Zr and Mg
2o
3/ Al
2o
3catalyst, compared to the catalyst not having zirconium and magnesium, this catalyst has higher selective and higher isobutene productive rate for the dehydrogenation of iso-butane.Patent WO2003106388A1, US20060094914A1, US7279611B2 and US7012038B2 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 improve Cr in catalyst preparation stages to a certain extent by the method for adding auxiliary agent
2o
3/ Al
2o
3the activity of catalyst and stability, and add auxiliary agent and improve the activity of catalyst and stability is a kind of simple method.But for the dehydrogenation reaction that low-carbon alkanes carries out on chromium-based catalysts, along with the carrying out of reaction, due to the impact of catalyst carbon deposition and hot environment, acidity of catalyst can reduce.Catalyst dehydrogenation activity needs the synergy of the acidity of some strength and distribution on catalyst, therefore, acidity of catalyst in use reduces the activity affecting catalyst, catalyst activity and selectivity is reduced, until Catalyst Conversion and selective being reduced to need more catalyst changeout.
Summary of the invention
For the current Cr for dehydrogenating low-carbon alkane
2o
3/ Al
2o
3catalyst, it is in use along with the carrying out of dehydrogenating propane reaction, catalyst activity reduces, the shortcoming that inactivation is fast, the invention discloses the preparation of a kind of catalyst for dehydrogenation of low-carbon paraffin and improve its method that is active and stability, make this catalyst catalyst activity in dehydrogenating low-carbon alkane process keep stable while, there is the advantages such as inactivation is slow, carbon accumulation resisting ability is strong.
The invention provides a kind of catalyst for dehydrogenation of low-carbon paraffin, this catalyst by main active component, auxiliary agent and carrier three part form, active component and auxiliary agent adopt the mode of dipping to load on carrier: wherein, main active component is the oxide of chromium, content is 1 ~ 30wt%, is preferably 10 ~ 30wt%; Auxiliary agent is one or more in Na, K, Ca, Mg, Zr, and the oxide content of auxiliary element is 0.01 ~ 10wt%, is preferably 0.1 ~ 8wt%; All the other are carrier, and carrier is that the mixture of aluminium oxide and silica is made, wherein aluminium oxide: silica weight ratio is 1 ~ 99:1.
Present invention also offers a kind of preparation method of above-mentioned catalyst for dehydrogenation of low-carbon paraffin, comprise step:
1) by a certain amount of aluminium hydroxide powder, silica powder and account for alumina powder jointed mass fraction be 0.5 ~ 5% sesbania powder mix, adding mass concentration is again after 1 ~ 30% dust technology carries out kneading, carry out shaping again on forming machine, carrier after shaping is after room temperature dries in the air 1 ~ 12h, 1 ~ 8h is dried again in 80 ~ 150 DEG C, carrier finally 500 ~ 1000 DEG C of roasting 1 ~ 12h in Muffle furnace of drying, obtain final carrier;
2) adopt co-impregnation to come supported active metals and auxiliary agent, preparation contains the soluble salt solutions of main active component and auxiliary agent as aqueous impregnation solution, soaks or sprays saturated impregnated carrier, and then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin.
The present invention still further provides and a kind ofly improves the catalyst activity of above-mentioned catalyst in manufacturing olefin by low-carbon alkane dehydrogenation reaction and the method for stability, the method comprises: adopt fixed bed to carry out dehydrogenating low-carbon alkane reaction, course of reaction comprises dehydrogenation reaction process and coke combustion hockets; Wherein said dehydrogenation reaction process is pass into unstrpped gas containing low-carbon alkanes 80 ~ 100% to reaction system, dehydrogenation reaction process carries out 1 ~ 20 minute, described coke combustion is for pass into oxygen containing gas to reaction system, and coke combustion carries out 0 ~ 40 minute, is preferably 5 ~ 40 minutes; Dehydrogenation reaction process temperature controls at 500 ~ 700 DEG C, and reaction pressure is normal pressure or negative pressure; In dehydrogenation reaction process or coke combustion, pass into a kind of adjustments of gas of stabilizing catalyst activity to reaction system with reaction raw materials, this adjustments of gas forms by regulating component and dilution component, wherein adjustment component is one or more in the compound of sulphur, phosphorus, the VIIth A race element, content is 0.001 ~ 1v%, with total adjustments of gas stereometer, surplus is dilution component, and dilution component is one or more in steam, air, nitrogen, methane or ethane gas.
According to the method described above, described adjustment component is preferably the gas of one or more elements in the VIIth A race element, and its content is 0.001 ~ 0.5%; Dilution component be preferably in steam, air, methane gas one or more.
According to the method described above, the adjustments of gas of the stabilizing catalyst activity passed into reaction system adds in dehydrogenation reaction process, or adds in coke combustion, or adds in dehydrogenation reaction process and coke combustion.
Technical solution of the present invention compared with prior art, its beneficial effect is: (1) catalyst alkalies and alkaline earth of the present invention auxiliary agent carries out modification to carrier, make carrier have suitable surface acidic-basic property, improve the dehydrating alkanes conversion ratio of catalyst and the selective of alkene; (2) the present invention improves the method for catalyst activity and stability, by in course of reaction, according to the change of catalyst activity, the adjustments of gas of stabilizing catalyst activity is passed into reaction system, namely contribute to stabilizing catalyst activity, well can promote again the elimination to carbon distribution, catalyst surface character can also be regulated, make catalyst surface Acidity of Aikalinity a rational scope, the service life of extending catalyst; (3) the present invention improves the method for catalyst activity and stability, be loaded with catalyst for dehydrogenation of low-carbon paraffin of the present invention, with alkali metal or alkaline-earth metal, surface nature adjustment is carried out to catalyst, change simultaneously according to catalyst in dehydrogenating low-carbon alkane course of reaction is adjusted, two processes cooperatively interact, make the performance that catalyst reaches optimum, and long service life.4) method for preparing catalyst of the present invention is simple.
Marginal data
Fig. 1 is the evaluation result of the catalyst A in embodiment 1, and in figure, curve conversion ratio 2 is the catalytic performance test result of catalyst A, and in figure, curve conversion ratio 1 is comparative evaluation's result of catalyst A.
Fig. 2 is the evaluation result of the catalyst B in embodiment 2, and in figure, curve conversion ratio 2 is the catalytic performance test result of catalyst B, and in figure, curve conversion ratio 1 is comparative evaluation's result of catalyst B.
Specific embodiment
Below will the invention will be further described by specific embodiment, but the present invention is not limited to these embodiments.
The preparation method of carrier used in the present invention is: by a certain amount of aluminium hydroxide powder, silica powder and account for alumina powder jointed mass fraction be 0.5 ~ 5% sesbania powder mix, adding mass concentration is again that 1 ~ 30% dust technology carries out kneading, the kneading time is 10min ~ 2h, finally carry out shaping again on forming machine, carrier after shaping is after room temperature dries in the air 1 ~ 12h, 1 ~ 8h is dried again in 80 ~ 150 DEG C, carrier finally 500 ~ 1000 DEG C of roasting 1 ~ 12h in Muffle furnace of drying, obtain final carrier.Adopt co-impregnation to come supported active metals and auxiliary agent, preparation contains the soluble salt solutions of main active component and auxiliary agent as aqueous impregnation solution, soaks or sprays saturated impregnated carrier, and then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin.
Prepare the shaping machine that carrier of the present invention uses and comprise tablet press machine, rolling granulators, pellet processing machine, moulding machine, banded extruder etc.The shape of shaping rear carrier comprises spherical, sheet, cylinder, star, trilobal, quatrefoil.
Dipping rear catalyst is dry at 120 ~ 220 DEG C, and in the mist of 500 ~ 850 DEG C, carry out roasting, mist is that the steam of 0 ~ 20% and the air of percent by volume 80 ~ 100% form by comprising percent by volume.
Hydrothermal treatment consists has the effect of adjustment hole structure for catalyst and carrier, 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 carrier, make chromium oxide crystal grain on catalyst more roomy, and present more crystal grain, improve active component crystal grain decentralization on a catalyst, and then the stability of promoting catalyst.
Because chromium-based catalysts carbon distribution is very fast, the industrial general mode of operation adopting interval.In the present invention, dehydrogenation reaction process and coke combustion hocket.Wherein certain embodiments carries out 1 ~ 20 minute, is switched to Burning Coke on Catalyst process and carries out 0 ~ 40 minute, is preferably 5 ~ 40 minutes.Reaction temperature controls at 500 ~ 700 DEG C, and reaction pressure is normal pressure or negative pressure.
Along with the carrying out that the dehydrogenating propane under existing at chromium-based catalysts reacts, under a reaction condition, in catalyst a period of time, as in the times of 2 days to 60 days, the mean value (representing with X) of alkane conversion or olefine selective mean value (representing with S) can reach a more stable stage, namely substantially keep becoming or slightly raising in the alkane conversion of catalyst during this period of time or olefine selective, the alkane conversion of this section or the mean value of olefine selective are labeled as initial value, are designated as original alkane conversion ratio X0 and the selective S0 of olefin streams.Along with proceeding of reaction, when the alkane conversion of catalyst or olefine selective are within the time of next 2 days to 60 days, its alkane conversion mean value general X's or olefine selective mean value S comparatively X0 or S0 reduces ratio T when being 0.01 ~ 2%, just need beginning to pass into the adjustments of gas possessing catalyst activity stabilization containing acidic materials to reaction system, regulate the volume flow that adds of gas to calculate with following formula:
Reduce ratio T=(variable-variable 0)/variable 0;
Adjustments of gas amasss flow=paraffinic feedstock volume flow × T;
Wherein, variable be catalyst at 2 days to the alkane conversion in 60 days or olefine selective mean value.
The stable adjustments of gas of the improvement catalyst activity passed into unstripped gas to reaction system is the gas regulating component containing 0.001 ~ 1v%, be preferably 0.01 ~ 1v%, adjustment component is one or more compositions containing comprising in the compound of sulphur, phosphorus, the VIIth A race element, and all the other are one or more in steam, air, nitrogen, methane or ethane gas; The organic matter formed after one or more hydrogen that the compound of these sulfur-bearings, phosphorus, the VIIth A race element can be sulphur, phosphorus, the VIIth A race element instead of in lower carbon number hydrocarbons, for chloride organic gas, can be monochloro methane, carrene.For the element of sulphur and the VIIth A race, also can be its hydride, be hydrogen sulfide for sulfide, and chloride is hydrogen chloride.
Catalyst of the present invention the low-carbon alkanes raw material that is suitable for be the liquefied petroleum gas of low-carbon alkanes content more than 80%, raw material low-carbon alkanes refers to the alkane gaseous mixture, particularly propane of below the C4 of arbitrary proportion and the mist of butane.When taking propane as raw material, at reaction pressure 0.01 ~ 0.5MPa, reaction temperature 570 ~ 600 DEG C, propane feed gas gas space velocity 200 ~ 500h
-1condition under, conversion of propane is greater than 55%, and Propylene Selectivity is higher than 90%; When the mixed alkanes pressing 1:1 with propane and butane is for raw material, at reaction pressure 0.03 ~ 0.5MPa, reaction temperature 550 ~ 580 DEG C, mist air speed 200 ~ 500h
-1condition under, the conversion ratio of mixed alkanes, more than 60%, generates alkene selective also more than 90%.Meanwhile, by carrying out situation according to what react, adopting pass into Active Regulation gas in reaction system after, catalyst life more than 10%, achieving gratifying result.
Embodiment 1
Carrier prepare: by a certain amount of aluminium oxide: silica be 1:1 mixed powder with account for mixed powder mass fraction be 8% sesbania powder mix, add again mass concentration be 5% citric acid and mass concentration be that 22% 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, 4h is dried again in 120 DEG C, carrier finally 900 DEG C of roasting 6h in Muffle furnace of drying, obtain final carrier A, its water absorption rate is 62.3%.
Take chromium trioxide 18.6g, sodium nitrate 3.0g, zirconyl nitrate 2.8g, add 30ml deionized water and be made into maceration extract, the carrier A 20g taking above-mentioned preparation carries out supersaturation dipping 1h, is then pulled out by the carrier after dipping, to dry in the air 2h in room temperature, dry 2h in 120 DEG C again, roasting 6h under 660 DEG C of air atmospheres, obtains finished catalyst A.
Consisting of of catalyst A: Cr-Na-Zr/Al
2o
3, wherein each component with the mass percentage of oxide basis is: Cr
2o
3: 20.5%, Na
2o:1.9%, ZrO
2: 1.6%, all the other are aluminium oxide and silica.
The catalytic activity of catalyst A is tested at twice: adopt 20ml fixed bed minisize reaction evaluation system, and getting 20 milliliters of loading internal diameters is carry out the test of dehydrogenating propane reactivity worth in the stainless steel reactor of 8 millimeters.
Catalytic performance test condition: unstripped gas is 250h containing the unstripped gas mass space velocity of propane 90%
-1, reaction pressure is 0.01MPa, and reaction temperature is 600 DEG C, and dehydrogenation reaction carries out 8 minutes, carries out air regenesis 15 minutes, after carry out dehydrogenation reaction again, so circulation is carried out.Chromatogram sample analysis when each dehydrogenation reaction proceeds to 4 minutes, the catalytic performance test of catalyst A the results are shown in Figure curve conversion ratio 2 in 1 and table 1.When conversion of propane lower than 45% time, think catalyst inactivation terminate evaluation response.
Comparative evaluation's condition: the comparative evaluation's test carrying out catalyst according to above-mentioned appreciation condition, difference is, react the time period in the time interval at 5 days, when conversion of propane reduction ratio reaches 0.05%, add chloride Active Regulation gas for 0.05v% with unstripped gas to reaction system in the dehydrogenation reaction stage, Active Regulation gas is the gas containing monochlorethane with nitrogen dilution.When conversion of propane lower than 45% time, think catalyst inactivation terminate evaluation response.The comparative evaluation of catalyst A the results are shown in Figure curve conversion ratio 1 in 1 and table 1.
In Fig. 1, the curve of conversion ratio 2 is the evaluating catalyst result not adding activity stabilized adjustments of gas, and the curve of conversion ratio 1 is the evaluating catalyst result under the condition adding activity stabilized adjustments of gas.Two curves as can be seen from figure, when dehydrogenating propane reaction is incipient, the conversion of propane of catalyst is basically identical, but along with the carrying out of reaction, the evaluation result of conversion ratio 1 is more stable, be because add Active Regulation gas, slow down dehydrogenating propane conversion ratio and decline, the extending catalyst life-span.
Embodiment 2
Prepared by carrier.By a certain amount of aluminium oxide: silica be 5:1 mixed powder with account for mixed powder mass fraction be 5% sesbania powder mix, add again mass concentration be 5% 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 after room temperature dries in the air 8h, then dries 4h, carrier finally 850 DEG C of roasting 12h in Muffle furnace of oven dry in 120 DEG C, obtain final carrier B, its water absorption rate is 55.1%.
Take chromium trioxide 16.5g, potassium nitrate 2.9g, calcium nitrate 3.5g, add 30ml deionized water and be made into maceration extract, the carrier B 20g taking above-mentioned preparation carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, to dry in the air 2h in room temperature, then dry 2h in 120 DEG C, roasting 6h under 790 DEG C of mixed atmospheres, mist is made up of 10% steam and 90% air, obtains finished catalyst B, and its component is: Cr-K-Ca/Al
2o
3, wherein each component with the mass percentage of oxide basis is: Cr
2o
3: 18.8%, K
2o:2.1%, CaO:2.3%, all the other are carrier.
The performance evaluation condition of catalyst B is with embodiment 1, and difference is that unstripped gas is the gas of the mixed alkanes 85% containing propane and butane, and propane wherein and the mol ratio of butane are 2:1, reaction pressure-0.02MPa, reaction temperature 580 DEG C, mist air speed 900h
-1, when conversion of propane lower than 45% time, think catalyst inactivation terminate evaluation response.The Evaluation results of catalyst B is shown in curve conversion ratio 2 in Fig. 2 and table 1.
Comparative evaluation's condition of catalyst B is with the performance evaluation condition of catalyst B, and difference is to add chloride Active Regulation gas for 0.01v% with unstripped gas to reaction system in the dehydrogenation reaction stage, and Active Regulation gas is the gas containing dichloroethanes with methane gas dilution.
When conversion of propane lower than 45% time, think catalyst inactivation terminate evaluation response.The comparative evaluation of catalyst B the results are shown in Figure curve conversion ratio 1 in 2 and table 1.
Embodiment 3
Prepared by carrier.By a certain amount of aluminium oxide: silica be 50:1 mixed powder with account for mixed powder mass fraction be 6% sesbania powder mix, add again mass concentration be 5% 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 after room temperature dries in the air 8h, then dries 4h, carrier finally 800 DEG C of roasting 6h in Muffle furnace of oven dry in 120 DEG C, obtain final support C, its water absorption rate is 58.6%.
Take chromium trioxide 18g, magnesium nitrate 4.8g, nickel nitrate 1.9g, add 30ml deionized water and be made into maceration extract, the support C 20g taking above-mentioned preparation carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, to dry in the air 2h in room temperature, then dry 2h in 120 DEG C, roasting 6h under 760 DEG C of mixed atmospheres, mist is made up of 5% steam and 95% air, obtains finished catalyst C, and its component is: Cr-Mg-Cu/Al
2o
3, wherein each component with the mass percentage of oxide basis is: Cr
2o
3: 19.8%, MgO:2.7%, NiO:1.2%, all the other are carrier.
The performance evaluation condition of catalyst C is with embodiment 1, and difference is that unstripped gas is butane gas, and wherein the volume content of butane is greater than 85%.Reaction pressure-0.02MPa, reaction temperature 580 DEG C, mist air speed 450h
-1.
Comparative evaluation's condition of catalyst C is with the performance evaluation condition with catalyst C, difference is to add chloride Active Regulation gas for 0.01v% with unstripped gas to reaction system in the dehydrogenation reaction stage, and Active Regulation gas is the gas containing monochlorethane with the dilution of steam gas.
When conversion of propane lower than 45% time, think catalyst inactivation terminate evaluation response.Evaluation result is in table 1.
Embodiment 4
Prepared by carrier.By a certain amount of aluminium oxide: silica be 99:1 mixed powder with account for mixed powder mass fraction be 9% sesbania powder mix, add again mass concentration be 6% citric acid and mass concentration be that 15% dust technology carries out kneading, the kneading time is 30min, finally carry out shaping again on forming machine, carrier after shaping after room temperature dries in the air 8h, then dries 4h, carrier finally 600 DEG C of roasting 8h in Muffle furnace of oven dry in 120 DEG C, obtain final carrier D, its water absorption rate is 51.3%.
Take chromium trioxide 18g, calcium nitrate 3.2g, cerous nitrate 2.1g, adds 30ml deionized water and is made into maceration extract, and the carrier D20g taking above-mentioned preparation carries out supersaturation dipping 1h, then the carrier after dipping is pulled out, to dry in the air 2h in room temperature, then dry 2h, roasting 6h under 720 DEG C of air atmospheres in 120 DEG C, obtain finished catalyst D, its component is: Cr-Ca-Ce/Al
2o
3, wherein each component with the mass percentage of oxide basis is: Cr
2o
3: 20.3%, CaO:2.1%, Ce
2o
3: 1.9%, all the other are carrier.
The performance evaluation condition of catalyst D is with embodiment 1, and difference is that unstripped gas is propane gas, and the volume content of propane is wherein greater than 90%.Reaction pressure-0.02MPa, reaction temperature 580 DEG C, mist air speed 200h
-1.
Comparative evaluation's condition of catalyst D is with the performance evaluation condition with catalyst B, difference is to add chloride Active Regulation gas for 0.1v% with unstripped gas to reaction system in the stage of reaction of making charcoal, and Active Regulation gas is the gas containing dichloroethanes with methane gas dilution.
When conversion of propane lower than 45% time, think catalyst inactivation terminate evaluation response.Evaluation result is in table 1.
The dehydrating alkanes performance of table 1 different catalysts
As can be seen from Table 1, in use, the service life of catalyst improves more than 10% to catalyst.
Claims (6)
1. a catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that, described catalyst by main active component, auxiliary agent and carrier three part form, active component and auxiliary agent adopt the mode of dipping to load on carrier: wherein, main active component is the oxide of chromium, and content is 1 ~ 30wt%; Auxiliary agent is one or more in Na, K, Ca, Mg, Zr, and the oxide content of auxiliary element is 0.01 ~ 10wt%; All the other are carrier, and carrier is that the mixture of aluminium oxide and silica is made, wherein aluminium oxide: silica weight ratio is 1 ~ 99:1.
2. catalyst for dehydrogenation of low-carbon paraffin according to claim 1, is characterized in that, the oxide content of chromium is 10 ~ 30wt%; The oxide content of auxiliary element is 0.1 ~ 8wt%.
3. a preparation method for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, is characterized in that, comprises step:
1) by a certain amount of aluminium hydroxide powder, silica powder and account for alumina powder jointed mass fraction be 0.5 ~ 5% sesbania powder mix, adding mass concentration is again after 1 ~ 30% dust technology carries out kneading, carry out shaping again on forming machine, carrier after shaping is after room temperature dries in the air 1 ~ 12h, 1 ~ 8h is dried again in 80 ~ 150 DEG C, carrier finally 500 ~ 1000 DEG C of roasting 1 ~ 12h in Muffle furnace of drying, obtain final carrier;
2) adopt co-impregnation to come supported active metals and auxiliary agent, preparation contains the soluble salt solutions of main active component and auxiliary agent as aqueous impregnation solution, soaks or sprays saturated impregnated carrier, and then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin.
4. one kind is improved the catalyst activity of catalyst according to claim 1 in manufacturing olefin by low-carbon alkane dehydrogenation reaction and the method for stability, it is characterized in that, fixed bed is adopted to carry out dehydrogenating low-carbon alkane reaction, and load catalyst for dehydrogenation of low-carbon paraffin according to claim 1, course of reaction comprises dehydrogenation reaction process and coke combustion hockets; Wherein said dehydrogenation reaction process is pass into unstrpped gas containing low-carbon alkanes 80 ~ 100% to reaction system, and dehydrogenation reaction process carries out 1 ~ 20 minute, and described coke combustion is for pass into oxygen containing gas to reaction system, and coke combustion carries out 0 ~ 40 minute; Dehydrogenation reaction process temperature controls at 500 ~ 700 DEG C, and reaction pressure is normal pressure or negative pressure; In dehydrogenation reaction process or coke combustion, pass into a kind of adjustments of gas of stabilizing catalyst activity to reaction system with reaction raw materials; Adjustments of gas forms by regulating component and dilution component, wherein adjustment component is one or more in the compound of sulphur, phosphorus, the VIIth A race element, content is 0.001 ~ 1v%, with total adjustments of gas stereometer, surplus is dilution component, and dilution component is one or more in steam, air, nitrogen, methane or ethane gas.
5. method according to claim 4, is characterized in that, described adjustment component is the gas of one or more elements in the VIIth A race element, and its content is 0.001 ~ 0.5%; Dilution component is one or more in steam, air, methane gas.
6. method according to claim 4, is characterized in that, the adjustments of gas of the stabilizing catalyst activity passed into reaction system adds in dehydrogenation reaction process, or adds in coke combustion, or adds in dehydrogenation reaction process and coke combustion.
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|---|---|---|---|
| CN201510745587.3A CN105312046B (en) | 2015-11-05 | 2015-11-05 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for improving its activity and stability |
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| CN107008260A (en) * | 2017-06-01 | 2017-08-04 | 高化学（江苏）化工新材料有限责任公司 | A kind of preparation method of low paraffin dehydrogenation catalyst |
| 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 |
| CN112536072A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Impregnation liquid and preparation method thereof, catalyst and preparation method and application thereof, and alkane dehydrogenation method |
| CN112717919A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing isobutene by dehydrogenating isobutane |
| CN113546651A (en) * | 2020-04-23 | 2021-10-26 | 中国科学院上海高等研究院 | Phosphorus-modified carbon-based catalyst and preparation method and application thereof |
| CN113968767A (en) * | 2020-07-23 | 2022-01-25 | 中国石油天然气股份有限公司 | Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane |
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| CN113546651A (en) * | 2020-04-23 | 2021-10-26 | 中国科学院上海高等研究院 | Phosphorus-modified carbon-based catalyst and preparation method and application thereof |
| CN113546651B (en) * | 2020-04-23 | 2022-11-11 | 中国科学院上海高等研究院 | Phosphorus-modified carbon-based catalyst and preparation method and application thereof |
| CN113968767A (en) * | 2020-07-23 | 2022-01-25 | 中国石油天然气股份有限公司 | Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane |
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