CN105312046B - A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for improving its activity and stability - Google Patents
A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for improving its activity and stability 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
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- 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 kind of catalyst for dehydrogenation of low-carbon paraffin, the catalytic component and content are：1~30wt% of oxide of main active component chromium, the oxide content of auxiliary element are 0.01~10wt%, and the one or more in auxiliary agent Na, K, Ca, Mg, Cu, Zr, remaining is carrier.Present invention also offers a kind of catalyst that improves in dehydrogenating low-carbon alkane reaction process activity and the method for stability, change in this method according to catalyst activity, a kind of adjusting gas of stabilizing catalyst activity is added into reaction system, the adjusting gas is made of adjusting component and dilution component, wherein adjust the one or more in the compound that component is sulphur, phosphorus, the VIIth A races element, content is 0.001~1v%, and dilution component is the one or more in vapor, air, nitrogen, methane or ethane gas.The method of the present invention can effectively slow down catalyst inactivation, extend catalyst life.
Description
Technical field
The present invention relates to dehydrogenation field, is specifically related to a kind of catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, with
And the method for improving catalyst for manufacturing olefin by low-carbon alkane dehydrogenation activity and stability.
Background introduction
Acidic catalyst is petroleum refining with using more a kind of catalyst, cracking, hydrocarbon such as hydro carbons in chemical industry
The reaction such as the alkylation of the isomerization of class, aromatic hydrocarbons and alkene, the dehydration of hydration alcohol processed, alcohol of alkene all uses acidic catalyst.
Some reactions, although the oxidation reaction of the dehydrogenation reaction of such as alkane, ethene and oxygen is not exclusively carried out by acidity of catalyst
Catalytic reaction, but the acidity of catalyst still has certain facilitation to catalytic reaction.More one kind is used at present
The acidic catalyst for possessing acidity is solid acid.Proton can be provided or receive the solid of electronics pair and be referred to as solid acid, such as 1)
Natural clay class, their key components are silica and aluminium oxide；2) load of liquid acid (including sulfuric acid, phosphoric acid etc.) has been loaded
Body；3) metal oxide or composite oxides, such as ZrO2, WO3, MoO3/Al2O3, Fe2O3/SiO2, synthesis of molecular sieve etc..
It is acid corresponding with solid material presentation, the solid of electronics pair or adsorber acid can be provided for those, can also
Referred to as solid base.Many reactions, although being catalyzed by the acid site on catalyst, the presence at alkali center is more or less
Certain synergistic effect is played with acid site, Acid-Base center synergistic effect shows very high catalytic activity sometimes.This kind of reaction is just
Reacted including dehydrating alkanes.
Low-carbon alkene is important Organic Chemicals, and such as current propylene demand is larger, and traditional processing technology cannot meet
The market demand, thus substitute emerging low-carbon alkene production technology include dehydrogenating propane (PDH), methanol-to-olefins (MTO, MTP),
Five kinds of emerging techniques such as deep catalytic cracking (DCC), olefin cracking and olefin(e) disproportionation.Comparatively speaking, dehydrogenating low-carbon alkane skill
Art advantage becomes apparent, it possesses the advantages that technology maturation, good product quality, high conversion rate, accessory substance are few.It is industrialized at present
Dehydrogenating low-carbon alkane propylene production technology is mainly the Oleflex techniques and Lummus companies of the U.S. of Uop Inc. of the U.S.
Catofin techniques.Catofin techniques use Cr series catalysts, its is cheap, low to raw material impurity requirement, suitable for domestic former
Expect present situation in short supply.
It is related in majority in the reaction of hydro carbons, such as dehydrogenating low-carbon alkane reaction, reactant molecule, product molecule and reaction
Intermediate is likely to become the parent of raw charcoal more, they either be combined with each other or be mutually condensed into containing for a variety of high molecular weight
Carbonaceous deposits is on a catalyst.On the catalyst using metal oxide as main active component, its carbon deposit is mainly acid site
Carbon distribution, the speed of carbon distribution are related with the acid-base property of catalyst surface.
Chromium oxide/aluminum oxide catalyst has of a relatively high dehydrogenation activity, but dehydrogenation reaction carries out at relatively high temperatures,
Cracking, isomerization and deep dehydrogenation reaction would generally occur, due to presence acid on catalyst, accelerate the catalyst part of the body cavity above the diaphragm housing the heart and lungs
The generation of charcoal.Studies have shown that acid initial activity and selectivity for dehydrogenating propane reaction counts for much, if acidity
Too low, then the activity of catalyst can also reduce.Therefore in catalyst preparation process, in order to reduce catalyst carbon deposit to its activity
Influence, generally in catalyst preparation process add alkali or alkaline earth metal element, for acid centre on catalyst
Act synergistically, adjust acidity of catalyst, improve catalyst stability and activity.Chinese patent CN102123790A is disclosed
Sodium oxide molybdena and potassium oxide are added in catalyst preparation process to improve chromium oxide/aluminum oxide catalyst, to improve catalyst
Activity and aging rear catalyst performance.Obtained catalyst shows higher selectivity and olefins yield, especially old
After change.Chinese patent CN1668555A discloses a kind of substep and adds alkali metallic sodium and lithium in aluminium oxide, so as to obtain one
The preparation method of the dehydrogenation catalyst complex of kind high-temperature stable.Chinese patent CN1309585A discloses a kind of fluidized bed catalytic
The method that Cracking catalyst strengthens acid sites.Including catalyst is contacted with the aqueous solution containing phosphorus and aluminium, water slurry is formed,
The enhancing at acidity of catalyst position is obtained by stable pH value.The degree of many metal poisonings on catalyst is reduced, and
Improve the quantity of catalyst acid reactive site.
The method for improving acidity of catalyst general at present, mainly in catalyst preparation stages, by adding alkalinous metal
Ion or acid ion etc. adjust the intensity of acidic site and quantity on catalyst number, such as Chinese patent CN1309585A,
Catalyst preparation stages, with the addition of phosphorus etc. so that the acidity of catalyst is enhanced on a catalyst.Patent WO
2005040075A1 discloses a kind of catalyst Cr of Zr containing auxiliary agent and Mg2O3/Al2O3Catalyst, compared to no zirconium and magnesium
Catalyst, dehydrogenation of the catalyst for iso-butane have the selectivity of higher and the isobutene yield of higher.Patent WO
2003106388A1, US 20060094914A1, US 7279611B2 and US 7012038B2 disclose one kind and contain Li and Na
Cr2O3/Al2O3Catalyst, the typical feature of the catalyst is high activity, high selectivity, and hydrothermal stability is high, long lifespan, loses
Motility rate is low.
Existing catalyst is all to be improved to a certain extent in catalyst preparation stages by adding the method for auxiliary agent
Cr2O3/Al2O3The activity and stability of catalyst, and auxiliary agent is added to improve the activity of catalyst and stability be a kind of letter
Single easy method.But for the dehydrogenation reaction that low-carbon alkanes carry out on chromium-based catalysts, with the progress of reaction, due to
The influence of catalyst carbon deposition and hot environment, acidity of catalyst can reduce.Catalyst dehydrogenation activity needs certain on catalyst
Intensity and the acid synergistic effect of distribution, therefore, acidity of catalyst reduces the activity for influencing catalyst in use, makes
Obtaining catalyst activity and selectivity reduces, until Catalyst Conversion and selectivity are reduced to and need replacing catalyst.
The content of the invention
For the Cr currently used for dehydrogenating low-carbon alkane2O3/Al2O3Catalyst, it is in use with dehydrogenating propane
The progress of reaction, catalyst activity reduce, and inactivate the shortcomings that fast, the invention discloses a kind of preparation of catalyst for dehydrogenation of low-carbon paraffin
And the method for improving its activity and stability so that catalyst catalyst activity during dehydrogenating low-carbon alkane keeps stablizing
While, have the advantages that inactivation is slow, carbon accumulation resisting ability is strong.
The present invention provides a kind of catalyst for dehydrogenation of low-carbon paraffin, and the catalyst is by main active component, auxiliary agent and carrier three
Part forms, and active component and auxiliary agent are loaded on carrier by the way of dipping：Wherein, main active component is the oxidation of chromium
Thing, content are 1~30wt%, are preferably 10~30wt%；Auxiliary agent is the one or more in Na, K, Ca, Mg, Zr, and auxiliary agent is first
The oxide content of element is 0.01~10wt%, is preferably 0.1~8wt%；Remaining is carrier, and carrier is aluminium oxide and silica
Mixture be 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, including step：
1) it is 0.5~5% with accounting for alumina powder mass fraction by a certain amount of aluminium hydroxide powder, silica powder
Sesbania powder is uniformly mixed, add mass concentration for 1~30% dust technology carry out kneading after, then on forming machine carry out into
Type, the carrier after shaping is after room temperature dries in the air 1~12h, and then at 80~150 DEG C of 1~8h of drying, the carrier of drying is finally in Muffle furnace
In 500~1000 DEG C roasting 1~12h, obtain final carrier；
2) using co-impregnation come supported active metals and auxiliary agent, soluble-salt of the preparation containing main active component and auxiliary agent
Dehydrogenating low-carbon alkane catalysis is made as aqueous impregnation solution, immersion or spray saturation impregnated carrier, then dry, roasting in solution
Agent.
The present invention still further provides a kind of above-mentioned catalyst of raising urging in manufacturing olefin by low-carbon alkane dehydrogenation reaction
The method of agent activity and stability, this method include：Dehydrogenating low-carbon alkane reaction is carried out using fixed bed, reaction process includes
Dehydrogenation reaction process and coke combustion are alternately；Wherein described dehydrogenation reaction process is to be passed through to reaction system containing low-carbon alkanes
80~100% unstrpped gas, dehydrogenation reaction process carry out 1~20 minute, and the coke combustion contains to be passed through to reaction system
The gas of oxygen, coke combustion carry out 0~40 minute, are preferably 5~40 minutes；Dehydrogenation reaction process temperature control is 500~700
DEG C, reaction pressure is normal pressure or negative pressure；In dehydrogenation reaction process or coke combustion, one is passed through to reaction system with reaction raw materials
The adjusting gas of kind stabilizing catalyst activity, the adjusting gas are made of adjusting component and dilution component, wherein adjusting component is
Sulphur, phosphorus, the VIIth A races element compound in one or more, content is 0.001~1v%, always to adjust volumescope,
Surplus is dilution component, and dilution component is the one or more in vapor, air, nitrogen, methane or ethane gas.
According to the method described above, it is described to adjust the gas that component is preferably one or more elements in the VIIth A races element, its
Content is 0.001~0.5%；Dilution component is preferably the one or more in vapor, air, methane gas.
According to the method described above, the adjusting gas for the stabilizing catalyst activity being passed through to reaction system is in dehydrogenation reaction process
Add, or added in coke combustion, or added in dehydrogenation reaction process and coke combustion.
Compared with prior art, its advantage is technical solution of the present invention：(1) catalyst alkali metal and alkali of the present invention
Earth metal auxiliary agent is modified carrier so that carrier has suitable surface acidic-basic property, and the dehydrating alkanes for improving catalyst turn
The selectivity of rate and alkene；(2) method that the present invention improves catalyst activity and stability, by during the reaction, root
According to the change of catalyst activity, the adjusting gas of stabilizing catalyst activity is passed through to reaction system, that is, contributes to rugged catalyst
Activity, and the elimination to carbon distribution can be promoted well, moreover it is possible to adjust catalyst surface property so that catalyst surface acid-base property exists
One rational scope, extends the service life of catalyst；(3) method that the present invention improves catalyst activity and stability, dress
Catalyst for dehydrogenation of low-carbon paraffin of the present invention has been carried, surface nature adjusting has been carried out to catalyst with alkali or alkaline earth metal, at the same time
Change according to catalyst in dehydrogenating low-carbon alkane reaction process is adjusted, and two processes cooperate so that urge
The performance that agent is optimal, and service life is grown.4) method for preparing catalyst of the present invention is simple and practicable.
Marginal data
Fig. 1 is the evaluation result of the catalyst A in embodiment 1, and curve conversion ratio 2 is the catalytic performance of catalyst A in figure
Evaluation result, curve conversion ratio 1 is comparative evaluation's result of catalyst A in figure.
Fig. 2 is the evaluation result of the catalyst B in embodiment 2, and curve conversion ratio 2 is the catalytic performance of catalyst B in figure
Evaluation result, curve conversion ratio 1 is comparative evaluation's result of catalyst B in figure.
Specific embodiment
Below will by specific embodiment, the invention will be further described, but the invention is not limited in these implement
Example.
The preparation method of carrier used in the present invention is：By a certain amount of aluminium hydroxide powder, silica powder with accounting for
Alumina powder mass fraction be 0.5~5% sesbania powder be uniformly mixed, add mass concentration for 1~30% dust technology into
Row kneading, kneading time are 10min~2h, are finally molded again on forming machine, the carrier after shaping dries in the air 1 in room temperature~
After 12h, then at 80~150 DEG C of 1~8h of drying, last 500~1000 DEG C of 1~12h of roasting in Muffle furnace of the carrier of drying, obtain
To final carrier.Using co-impregnation come supported active metals and auxiliary agent, prepare solvable containing main active component and auxiliary agent
Property salting liquid as aqueous impregnation solution, immersion or spray saturation impregnated carrier are then dry, roast and dehydrogenating low-carbon alkane is made urges
Agent.
Preparing molding machine used in the carrier of the present invention includes tablet press machine, rolling granulators, pellet processing machine, molding
Machine, banded extruder etc..The shape of carrier includes spherical, sheet, cylinder, star, trilobal, quatrefoil after shaping.
It is dry at 120~220 DEG C to impregnate rear catalyst, is roasted in 500~850 DEG C of mixed gas, mixes
Gas including the vapor that percent by volume is 0~20% and the air of percent by volume 80~100% by forming.
Hydro-thermal process has the function that to adjust pore structure, in the present invention, the hydro-thermal under high temperature for catalyst and carrier
Processing not only has certain adjustment effect to the pore structure of catalyst and carrier, between active component chromium oxide and carrier
Interaction also has adjustment effect so that chromium oxide crystal grain is more roomy on catalyst, and shows more crystal grain, improves
The dispersion degree of active component crystal grain on a catalyst, and then promote the stability of catalyst.
Since chromium-based catalysts carbon distribution is very fast, the industrial general mode of operation for using interval.Dehydrogenation reaction in the present invention
Process and coke combustion are alternately.Wherein certain embodiments carry out 1~20 minute, be switched to Burning Coke on Catalyst process carry out 0~
40 minutes, be preferably 5~40 minutes.Reaction temperature is controlled at 500~700 DEG C, and reaction pressure is normal pressure or negative pressure.
With the progress that the dehydrogenating propane in the presence of chromium-based catalysts reacts, under a reaction condition, catalyst one
In the section time, as in times of 2 days to 60 days, the average value (being represented with X) or olefine selective average value of alkane conversion (with
S is represented) can reach a relatively stable stage, i.e., this period catalyst alkane conversion or olefine selective protect substantially
Hold change or slightly raise, the average value of the alkane conversion of this section or olefine selective is labeled as initial value, is denoted as initial alkane
Hydrocarbon conversion rate X0 and olefin streams selectivity S0.With continuing for reaction, when the alkane conversion or alkene of catalyst are selected
Selecting property within the time of next 2 days to 60 days, its general alkane conversion average value X's or olefine selective average value S compared with
When X0 or S0 reduction ratios T is 0.01~2%, just need to start to be passed through possesses catalyst containing acidic materials to reaction system
The adjusting gas of activity stabilized effect, the addition volume flow for adjusting gas are calculated as follows：
Reduce ratio T=(variable-variable 0)/variable 0；
Adjust gas volumetric flow=paraffinic feedstock volume flow × T；
Wherein, variable is alkane conversion or olefine selective average value of the catalyst in 2 days to 60 days.
The adjusting gas for improving catalyst activity stabilization being passed through to reaction system with unstripped gas is containing 0.001~1v%
Adjust component gas, be preferably 0.01~1v%, adjust component be containing including sulphur, phosphorus, the VIIth A races element compound in
One or more compositions, remaining is the one or more in vapor, air, nitrogen, methane or ethane gas；These contain
Sulphur, phosphorus, the compound of the VIIth A races element, can be that sulphur, phosphorus, the VIIth A races element instead of one or more of lower carbon number hydrocarbons hydrogen
The organic matter formed afterwards, can be monochloro methane for chloride organic gas, dichloromethane.For sulphur and the VIIth A races
Element or its hydride, are hydrogen sulfide for sulfide, and chloride is hydrogen chloride.
The low-carbon alkanes raw material that catalyst of the present invention is applicable in is liquefied petroleum gas of the low-carbon alkanes content more than 80%,
Raw material low-carbon alkanes refer to the alkane gaseous mixture of below the C4 of arbitrary proportion, particularly the mixed gas of propane and butane.With third
When alkane is raw material, in 0.01~0.5MPa of reaction pressure, 570~600 DEG C of reaction temperature, propane feed gas gas space velocity 200~
500h-1Under conditions of, conversion of propane is more than 55%, and Propylene Selectivity is higher than 90%；1 is pressed with propane and butane:1 mixing alkane
When hydrocarbon is raw material, in 0.03~0.5MPa of reaction pressure, 550~580 DEG C of reaction temperature, 200~500h of mixed gas air speed-1's
Under the conditions of, the conversion ratio of mixed alkanes generates the selectivity of alkene also more than 90% more than 60%.Meanwhile pass through basis
The carry out situation of reaction, after Active Regulation gas is passed through into reaction system, catalyst life more than 10%, obtains
Gratifying result.
Embodiment 1
It is prepared by carrier：By a certain amount of aluminium oxide：Silica is 1:1 mixed powder is with accounting for mixed powder mass fraction
8% sesbania powder is uniformly mixed, and it is that 22% dust technology is mixed to add citric acid that mass concentration is 5% and mass concentration
Pinch, the kneading time is 30min, is finally molded again on forming machine, the carrier after shaping after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 900 DEG C of roasting 6h in Muffle furnace of the carrier of drying, obtain final carrier A, its water absorption rate is
62.3%.
Chromium trioxide 18.6g, sodium nitrate 3.0g, zirconyl nitrate 2.8g are weighed, 30ml deionized waters is added and is made into maceration extract,
The carrier A 20g for weighing above-mentioned preparation carry out supersaturation dipping 1h, then pull the carrier after dipping out, dry in the air 2h in room temperature, then
2h is dried in 120 DEG C, 6h is roasted under 660 DEG C of air atmospheres, obtains finished catalyst A.
The composition of catalyst A is：Cr-Na-Zr/Al2O3, wherein mass percentage of each component in terms of oxide be：
Cr2O3：20.5%, Na2O:1.9%, ZrO2:1.6%, remaining is aluminium oxide and silica.
The catalytic activity test of catalyst A is at twice：Using 20ml fixed bed minisize reaction evaluation systems, 20 milliliters of dresses are taken
Enter in the stainless steel reactor that internal diameter is 8 millimeters and carry out dehydrogenating propane reactivity worth test.
Catalytic performance test condition：Unstripped gas mass space velocity of the unstripped gas containing propane 90% is 250h-1, reaction pressure is
0.01MPa, reaction temperature are 600 DEG C, and dehydrogenation reaction carries out 8 minutes, carries out air regenesis 15 minutes, after to carry out dehydrogenation again anti-
Should, so circulation carries out.Each dehydrogenation reaction is carried out to chromatography sampling analysis at 4 minutes, the catalytic performance test knot of catalyst A
Fruit sees curve conversion ratio 2 and table 1 in Fig. 1.When conversion of propane is less than 45%, it is believed that catalyst has inactivated end evaluation
Reaction.
Comparative evaluation's condition：The comparative evaluation that catalyst is carried out according to above-mentioned appreciation condition tests, and difference is, instead
Should be in the time interval period of 5 days, when conversion of propane reduces ratio and reaches 0.05%, in the dehydrogenation reaction stage with unstripped gas
The chloride Active Regulation gas for 0.05v% is added to reaction system, Active Regulation gas is diluted containing monochlorethane with nitrogen
Gas.When conversion of propane is less than 45%, it is believed that catalyst has inactivated end evaluation response.The comparative evaluation of catalyst A
Curve conversion ratio 1 and table 1 in the result is shown in Figure 1.
In Fig. 1, the curve of conversion ratio 2 is the evaluating catalyst for not adding activity stabilized adjusting gas as a result, conversion ratio 1
Curve is the evaluating catalyst result under conditions of the activity stabilized adjusting gas of addition.Two curves can be seen that from figure
When dehydrogenating propane reaction is incipient, the conversion of propane of catalyst is basically identical, but with the progress of reaction, conversion ratio 1
Evaluation result it is more stable, be because add Active Regulation gas, slow down the decline of dehydrogenating propane conversion ratio, extend catalysis
The agent service life.
Embodiment 2
It is prepared by carrier.By a certain amount of aluminium oxide：Silica is 5:1 mixed powder is with accounting for mixed powder mass fraction
5% sesbania powder is uniformly mixed, and it is that 20% dust technology is mixed to add citric acid that mass concentration is 5% and mass concentration
Pinch, the kneading time is 30min, is finally molded again on forming machine, the carrier after shaping after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 850 DEG C of roasting 12h in Muffle furnace of the carrier of drying, obtain final carrier B, its water absorption rate is
55.1%.
Chromium trioxide 16.5g, potassium nitrate 2.9g, calcium nitrate 3.5g are weighed, 30ml deionized waters is added and is made into maceration extract, claim
Take the carrier B 20g of above-mentioned preparation to carry out supersaturation dipping 1h, then the carrier after dipping is pulled out, is dried in the air 2h in room temperature, then at
120 DEG C dry 2h, roast 6h under 790 DEG C of mixed atmospheres, mixed gas is made of 10% vapor and 90% air, obtains catalyst
Finished product B, its component are：Cr-K-Ca/Al2O3, wherein mass percentage of each component in terms of oxide be：Cr2O3：
18.8%, K2O:2.1%, CaO:2.3%, remaining is carrier.
The performance evaluation condition of catalyst B is the mixed alkanes containing propane and butane difference lies in unstripped gas with embodiment 1
85% gas, the molar ratio of propane and butane therein is 2:1, reaction pressure -0.02MPa, 580 DEG C of reaction temperature, mixing
Gas space velocity 900h-1, when conversion of propane is less than 45%, it is believed that catalyst has inactivated end evaluation response.Catalyst B's
Evaluation results are shown in curve conversion ratio 2 and table 1 in Fig. 2.
Comparative evaluation's condition of catalyst B with catalyst B performance evaluation condition, difference lies in the dehydrogenation reaction stage with
Unstripped gas adds the chloride Active Regulation gas for 0.01v% to reaction system, and Active Regulation gas is to contain two with methane gas is diluted
The gas of chloroethanes.
When conversion of propane is less than 45%, it is believed that catalyst has inactivated end evaluation response.The contrast of catalyst B is commented
The result is shown in the curve conversion ratio 1 and table 1 in Fig. 2 for valency.
Embodiment 3
It is prepared by carrier.By a certain amount of aluminium oxide：Silica is 50:1 mixed powder is with accounting for mixed powder mass fraction
It is uniformly mixed for 6% sesbania powder, it is that 20% dust technology is mixed to add citric acid that mass concentration is 5% and mass concentration
Pinch, the kneading time is 30min, is finally molded again on forming machine, the carrier after shaping after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 800 DEG C of roasting 6h in Muffle furnace of the carrier of drying, obtain final support C, its water absorption rate is
58.6%.
Chromium trioxide 18g, magnesium nitrate 4.8g, nickel nitrate 1.9g are weighed, 30ml deionized waters is added and is made into maceration extract, weigh
The support C 20g of above-mentioned preparation carries out supersaturation dipping 1h, then pulls the carrier after dipping out, dries in the air 2h in room temperature, then at 120
DEG C drying 2h, roasts 6h under 760 DEG C of mixed atmospheres, mixed gas is made of 5% vapor and 95% air, obtains finished catalyst
C, its component are：Cr-Mg-Cu/Al2O3, wherein mass percentage of each component in terms of oxide be：Cr2O3：19.8%,
MgO:2.7%, NiO:1.2%, remaining is carrier.
The performance evaluation condition of catalyst C is with embodiment 1, and difference lies in the body that unstripped gas is butane gas, wherein butane
Product content is more than 85%.Reaction pressure -0.02MPa, 580 DEG C of reaction temperature, mixed gas air speed 450h-1。
Comparative evaluation's condition of catalyst C is with the performance evaluation condition of same catalyst C, and difference lies in the dehydrogenation reaction stage
The chloride Active Regulation gas for 0.01v% is added to reaction system with unstripped gas, Active Regulation gas is diluted with vapor gas
Gas containing monochlorethane.
When conversion of propane is less than 45%, it is believed that catalyst has inactivated end evaluation response.Evaluation result is shown in Table 1.
Embodiment 4
It is prepared by carrier.By a certain amount of aluminium oxide：Silica is 99:1 mixed powder is with accounting for mixed powder mass fraction
It is uniformly mixed for 9% sesbania powder, it is that 15% dust technology is mixed to add citric acid that mass concentration is 6% and mass concentration
Pinch, the kneading time is 30min, is finally molded again on forming machine, the carrier after shaping after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 600 DEG C of roasting 8h in Muffle furnace of the carrier of drying, obtain final carrier D, its water absorption rate is
51.3%.
Chromium trioxide 18g, calcium nitrate 3.2g, cerous nitrate 2.1g are weighed, 30ml deionized waters is added and is made into maceration extract, weigh
The carrier D 20g of above-mentioned preparation carry out supersaturation dipping 1h, then pull the carrier after dipping out, dry in the air 2h in room temperature, then at 120
DEG C drying 2h, roasts 6h under 720 DEG C of air atmospheres, obtains finished catalyst D, its component is：Cr-Ca-Ce/Al2O3, wherein each group
Mass percentage point in terms of oxide is：Cr2O3：20.3%, CaO:2.1%, Ce2O3:1.9%, remaining is carrier.
The performance evaluation condition of catalyst D is propane gas difference lies in unstripped gas with embodiment 1, propane therein
Volume content is more than 90%.Reaction pressure -0.02MPa, 580 DEG C of reaction temperature, mixed gas air speed 200h-1。
Comparative evaluation's condition of catalyst D is with the performance evaluation condition of same catalyst B, and difference lies in the stage of reaction of making charcoal
The chloride Active Regulation gas for 0.1v% is added to reaction system with unstripped gas, Active Regulation gas is to contain two with methane gas is diluted
The gas of chloroethanes.
When conversion of propane is less than 45%, it is believed that catalyst has inactivated end evaluation response.Evaluation result is shown in Table 1.
The dehydrating alkanes performance of 1 different catalysts of table
As it can be seen from table 1 catalyst is in use, the service life of catalyst improves more than 10%.
Claims (4)
1. a kind of method of catalyst for dehydrogenation of low-carbon paraffin activity improved in manufacturing olefin by low-carbon alkane dehydrogenation reaction and stability,
It is characterized in that, carrying out dehydrogenating low-carbon alkane reaction using fixed bed, and catalyst for dehydrogenation of low-carbon paraffin is loaded, reaction process bag
Include dehydrogenation reaction process and coke combustion alternately；Wherein described dehydrogenation reaction process is to be passed through to reaction system containing lower alkanes
The unstrpped gas of hydrocarbon 80~100%, dehydrogenation reaction process carry out 1~20 minute, and the coke combustion is to be passed through to reaction system
Oxygen containing gas, coke combustion carry out 0~40 minute；At 500~700 DEG C, reaction pressure is dehydrogenation reaction process temperature control
Normal pressure or negative pressure；In dehydrogenation reaction process or coke combustion, a kind of rugged catalyst is passed through to reaction system with reaction raw materials
The adjusting gas of activity；Adjust gas to be made of adjusting component and dilution component, wherein adjusting component as sulphur, phosphorus, the VIIth A races member
One or more in the compound of element, content is 0.001~1v%, and always to adjust volumescope, surplus is dilution component,
Dilution component is the one or more in vapor, air, nitrogen, methane or ethane gas；
The catalyst for dehydrogenation of low-carbon paraffin is made of main active component, auxiliary agent and carrier three parts, and active component and auxiliary agent are adopted
Loaded to the mode of dipping 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, the oxide content of auxiliary element is 0.01~10wt%；Remaining is carrier, is carried
Body is made of the mixture of aluminium oxide and silica, wherein aluminium oxide：Silica weight ratio is 1~99:1.
2. according to the method described in claim 1, it is characterized in that, it is described adjust component be the VIIth A races element in one kind or
The gas of multiple element, its content are 0.001~0.5v%；Dilution component for vapor, air, one kind in methane gas or
It is a variety of.
3. the according to the method described in claim 1, it is characterized in that, adjusting for the stabilizing catalyst activity being passed through to reaction system
Gas adds in dehydrogenation reaction process, or is added in coke combustion, or is added in dehydrogenation reaction process and coke combustion.
4. according to the method described in claim 1, it is characterized in that, the oxide content of the chromium is 10~30wt%；Auxiliary agent
The oxide content of element is 0.1~8wt%.
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| 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 |
| CN112536072B (en) * | 2019-09-20 | 2023-09-29 | 中国石油化工股份有限公司 | Impregnating solution 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 |
| 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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