CN103084171B - A kind of drippolene one section of selective hydrogenation catalyst and its preparation method and application - Google Patents
A kind of drippolene one section of selective hydrogenation catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of drippolene one section of selective hydrogenation catalyst and its preparation method and application.The metal active constituent of catalyst is prepared by microemulsion method and is passed through reduction back loading on carrier, and described active component is metallic atom or low valence metal ion, and the grain diameter of described main active component Pd is less than 10nm, size tunable, evenly, and good dispersion.Preparation method of the present invention is simple, easy to operate, and manufacturing conditions is gentle; Catalyst application of the present invention had in alkadienes, styrene selective hydrogenation reaction higher activity, preferably selective and good appearance colloidality energy.
Description
Technical field
The present invention relates to a kind of supported selective hydrogenation catalyst and its preparation method and application, specifically a kind of drippolene one section of selective hydrogenation catalyst and its preparation method and application.
Background technology
Drippolene is the important by-product that ethylene industry is produced, and comprises C5-C10 fraction.Drippolene composition is very complicated, mainly contain the organic compound etc. of benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine and heavy metal, more than totally 200 component, wherein benzene,toluene,xylene (being referred to as BTX) aromatic hydrocarbons is about 50-80%, unsaturated hydrocarbons 25-30%.Industrial drippolene one section of selec-tive hydrogenation removes alkadienes and styrene, after Secondary hydrodesulfurization removes the organic compound of monoolefine and sulphur, nitrogen, oxygen, for Aromatics Extractive Project.
The pyrolysis gasoline hydrogenation catalyst that current industrial production is applied mainly contains palladium system and nickel system two kinds of catalyst, based on palladium series catalyst.It is low that palladium series catalyst has initial temperature, and hydrogenation activity is large, adapts to air speed high, the advantages such as long service life, and the catalyst mode of existing commercial Application comprises Pd-Cr/Al
2o
3, Pd/Al
2o
3.
The conventional method preparing pyrolysis gasoline hydrogenation catalyst is carrier described in the solution impregnation with catalytically-active metals salt or organo-metallic compound, then fixing by precipitation, hydrolysis, heat treatment, roasting and/or reduction, catalytically-active metals is applied on porous carrier.This needs impregnated catalyst to be repeatedly heated to 200 DEG C-1200 DEG C usually, makes slaine or organo-metallic compound be decomposed into corresponding oxide, could be used for pyrolysis gasoline hydrogenation reaction after the catalyst after roasting needs logical hydrogen reducing before use.Catalyst decentralization prepared by tradition infusion process is often lower, have impact on giving full play to of active component catalytic performance.Make Kaolinite Preparation of Catalyst in this way, the greatest problem of existence is that high-temperature calcination process can cause active component to sinter, and makes the degradation of catalyst.In catalyst prepared by tradition infusion process, all there is diffusion or the metal migration of Metal Palladium ion in each step, each several part on carrier has palladium element to exist, and just concentration is different.Because various piece all exists Metal Palladium ion, and its hydrogenation selectivity is declined.
Chinese patent CN1184289C discloses a kind of Catalysts and its preparation method for selective hydrogenation of cracked gasoline and application, its carrier adopts Titanium oxide-aluminum oxide compound, and be carried on the activity component metal palladium of this complex carrier, the weight of active component palladium is the 0.25-0.35% based on total catalyst weight, although it is high that this catalyst has air speed, the features such as selective and good stability, but its antijamming capability is not described, holds glue ability and resistance to water.
Chinese patent CN85100761A discloses a kind of fiber catalyst carrier for pyrolysis gasoline cut fraction diolefin selective hydrogenation, owing to have employed η-Al
2o
3porous fibrous carrier, so this catalyst activity is high, but aperture is too little, and when in raw material, colloid, arsenic content, water content exceed standard, the easy coking and blocking in the hole on catalyst, affects catalyst hydrogenation stability.
Chinese patent CN100512955C discloses and relates to one for alkynes in C2 ~ C10 cut and diolefin hydrogenate Catalysts and its preparation method, major catalyst palladium and co-catalyst are only distributed in the aluminum oxide coating layer of catalyst coating, and the thickness of aluminum oxide coating layer only has 10 ~ 300 microns.Make major catalyst palladium and co-catalyst fully can both participate in selective acetylene hydrocarbon hydrogenation reaction like this, improve the hydrogenation efficiency of catalyst activity component.
Compared with conventional method, microemulsion method is as a kind of effective ways preparing nano particle, and form microemulsion droplets by the aqueous solution, surfactant and cosurfactant, this microemulsion droplets has microreactor function.Additionally by the adjustment aqueous solution and dosage of surfactant ratio, effectively nano particle diameter can be controlled.
Summary of the invention
For the problems of the prior art, the object of this invention is to provide a kind of drippolene one section of selective hydrogenation catalyst and its preparation method and application, the activity component load quantity of this catalyst is low, has higher activity and selective preferably.
One of the object of the invention is to provide a kind of drippolene one section of selective hydrogenation catalyst, this catalyst is used for drippolene one section of selec-tive hydrogenation and removes alkadienes and cinnamic reaction, comprise carrier and be carried on the active component on carrier, the active component of described catalyst utilizes microemulsion method prepare and obtain.
Described carrier is at least one in aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolin, cordierite, also comprises these carrier loaded complex carriers formed to the inert substrate such as metal, pottery.Preferred carrier is aluminium oxide, and specific area is 70-200m
2/ g, its shape be granular, spherical, profile of tooth, annular, tooth are spherical, sheet shape, the bar shaped such as bar shaped or clover.Preferred carrier is the aluminium oxide of lanthanum modification.
Described active component comprises main active component and/or helps active component;
Described main active component is simple substance palladium, and palladium content is the 0.01wt% ~ 1.0wt% of described carrier gross weight, is preferably the 0.05wt% ~ 0.5wt% of total weight of carrier;
The described active component that helps is one or more in Sn, Pb, Cu, Ga, ZnAg, Sb, Mn, Co, Mo, W, Si, Fe, alkali metal, alkaline-earth metal, and its content is the 0.0wt% ~ 3.0wt% of total catalyst weight; Be preferably Sn and/or Pb, its content is the 0wt%-2.0wt% of total weight of carrier; Help active component can also be selected from least one in K, Mg, Ca, Ba, preferred Mg and/or Ca, its content is preferably the 0wt%-0.8wt% of total weight of carrier.
The grain diameter of described main active component is less than 10nm;
In described catalyst of the present invention, active component adopts microemulsion method preparation and obtains, and be carried on carrier, comprises the following steps:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), wherein the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced loads on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained drippolene of the present invention one section of selective hydrogenation catalyst.
Wherein said non-ionic surface active agent is at least one in TX-100, Tween85, Tween80, Tween60, Tween20, Span80, Span40, NP-10, NP-4, OP-10; Described cosurfactant is C
3~ C
8alcohols, more preferably from normal propyl alcohol, isobutanol, n-amyl alcohol, the one in isooctanol; Described oil phase is selected from C
6~ C
12linear paraffin, cyclic alkane, at least one in branched paraffin, more preferably from cyclohexane, n-hexane, isooctane; Described salting liquid is selected from the one in described nitrate, sulfate, chloride, acetate.
Reduction reaction temperature in step (2) is 0 ~ 60 DEG C, and described reducing agent is be at least one in hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
The catalyst activity component above-mentioned reduction fully obtained loads on carrier by conventional methods such as dipping, sprayings, more preferably the catalyst activity component prepared of described microemulsion by a step dipping or step impregnation load on carrier.
Transmission electron microscope (TEM) test result shows, and use the obtained catalyst of microemulsion technology of the present invention to form nano particle in microemulsion, the particle diameter < 10nm of nano particle, can with reference to accompanying drawing 1.In addition, the particle of active component can control by regulating the mode of water/surfactant.
Another object of the present invention is to provide a kind of method preparing drippolene one section of selective hydrogenation catalyst.In the method, the aqueous solution of activity component metal salt is dispersed in oil phase through non-ionic surface active agent and cosurfactant parcel, load on carrier by the mode of dipping, spraying after reducing agent reduction, the metal nanoparticle average diameter formed in microemulsion is less than 10nm.Specifically comprise the following steps:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), wherein the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced loads on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained drippolene of the present invention one section of selective hydrogenation catalyst.
3rd object of the present invention is to provide the application of this catalyst in drippolene one section of selec-tive hydrogenation removal alkadienes and cinnamic reaction.
The present invention compared with prior art has the following advantages:
(1) preparation method of the present invention is simple, easy to operate, and experiment condition is gentle.
(2) drippolene one section of selective hydrogenation catalyst of preparing of the present invention, because adopting microemulsion method to be prepared from, its size tunable, evenly, good dispersion, good stability, considerably improves catalyst activity and selectivity in the reaction.
(3) catalyst using the method to prepare is compared with existing catalyst, and the selective height of diolefin hydrogenation, holds glue ability good, have good water-resistant capacity.
Accompanying drawing explanation
Fig. 1 is the distribution of catalyst nanoparticles in microemulsion system
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited in following embodiment.
Embodiment 1
Pipette the PdCl of 50mgPd/ml
2solution 5ml, uses deionized water to be diluted to 10ml; 15.8mlTx100 and 13.4ml normal propyl alcohol mixes with 25ml cyclohexane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the PdCl of dilute with water
2solution, magnetic agitation certain hour is until obtain transparent microemulsion; The PdCl that a certain amount of hydrazine hydrate makes in microemulsion is added in above-mentioned microemulsion
2be reduced into simple substance Pd; Take 100gAl
2o
3carrier, is impregnated into the microemulsion after reduction on carrier.Then dry, roasting is prepared into described catalyst A, and wherein Pd content is 0.25wt%.
Embodiment 2
Take the Pd (NO of 200mgPd/ml respectively
3)
2pb (the NO of solution 1.25ml, 200mgPb/ml
3)
2solution 2.5ml, uses deionized water to be diluted to 10ml; 16.2mlNP-10 and 12.2ml n-butanol mixes with 20ml isooctane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the metal salt solution of dilute with water, and magnetic agitation certain hour is until obtain transparent microemulsion; Pd (the NO that a certain amount of hydrazine hydrate makes in microemulsion is added in above-mentioned microemulsion
3)
2with Pb (NO
3)
2be reduced into simple substance Pd and Pb; Take 100gAl
2o
3carrier, is impregnated into the microemulsion after reduction on carrier.Then dry, roasting is prepared into described catalyst B, and wherein Pd content is 0.25wt%, Pb content is 0.50wt%.
Embodiment 3
Take the Pd (NO of 200mgPd/ml respectively
3)
2pb (the NO of solution 1.25ml, 200mgPb/ml
3)
2solution 2.5ml, mixing, then take 10.55gMg (NO
3)
26H
2o puts into the aqueous solution of Pd and Pb, uses deionized water to be diluted to 10ml; 15mlTween80 and 10ml n-butanol mixes with 25ml n-hexane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the metal salt solution of dilute with water, and magnetic agitation certain hour is until obtain transparent microemulsion; In above-mentioned microemulsion, add a certain amount of hydrazine hydrate makes the reducing metal ions in the metal salt solution in microemulsion become elemental stage.Take 100gAl
2o
3carrier, sprays on carrier by the microemulsion after reduction, and then dry, roasting is prepared into described catalyst C, and wherein Pd content is 0.25wt%, Pb content be 0.50wt%, Mg content is 1.0wt%.
Embodiment 4
Take the Pd (NO of 200mgPd/ml respectively
3)
2sn (the NO of solution 1.25ml, 200mgSn/ml
3)
2solution 2ml, mixing, uses deionized water to be diluted to 10ml; 15mlTween80 and 10ml n-butanol mixes with 25ml n-hexane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the metal salt solution of dilute with water, and magnetic agitation certain hour is until obtain transparent microemulsion; In above-mentioned microemulsion, add a certain amount of hydrazine hydrate makes the reducing metal ions in the metal salt solution in microemulsion become elemental stage.Take 100gAl
2o
3carrier, sprays on carrier by the microemulsion after reduction, and then dry, roasting is prepared into described catalyst D, and wherein Pd content is 0.25wt%, Sn content is 0.40wt%.
Comparative example
Take the Pd (NO of 100mgPd/ml
3)
2solution 3ml, uses deionized water dilution 50ml, takes 100gAl
2o
3the metal salt solution that carrier adds dilution leaves standstill 30min, and dry, roasting, obtains catalyst E.Wherein Pd content is 0.3wt%.
Evaluation test 1
Get catalyst A, each 100ml of B, C, D, E, adiabatic reactor carries out activity rating, raw materials used in evaluation is drippolene C6-C8 middle distillate, and diene value is 30-40 gram of iodine/100 gram oil, and colloid is less than 60mg/100ml.Reaction condition is: Hydrogen Vapor Pressure is 2.8MPa, and inlet temperature is 45 DEG C, and hydrogen to oil volume ratio is 50: 1, and Feed space velocities is 8h
-1..Wherein in oil product, the assay method of diene value is apple acid anhydrides method.React the evaluation result after 100 hours in table 1:
The Hydrogenation of table 1 catalyst
Evaluation test 2
Table 2 is comparative evaluation's results that catalyst D and comparative example catalyst E reacts the Hydrogenation after 100 hours, 500 hours on 100ml adiabatic reactor under larger space velocities.Raw materials used in evaluation is drippolene C6-C8 middle distillate, and diene value is 30-40 gram of iodine/100 gram oil, and colloid is less than 60mg/100ml.Reaction condition is: Hydrogen Vapor Pressure is 2.8MPa, and reaction temperature is 45 DEG C, and hydrogen to oil volume ratio is 50: 1, and green oil air speed is 8h
-1., product recycle ratio is 2: 1, and total air speed is 24h
-1.Wherein in oil product, the assay method of diene value is apple acid anhydrides method.
Table 2 catalyst D and comparative catalyst E Hydrogenation under larger space velocities compares
Evaluation test 3
The present embodiment is the active appraisal experiment of catalyst of the present invention.
Get catalyst A, each 100ml of B, C, D, adiabatic reactor is investigated the activity and selectivity of original catalyst particle size.Raw materials used in evaluation is drippolene C6 ~ C8 midbarrel, diene value 14.11 grams of iodine/100 gram oil, and iodine number 43.35 grams of iodine/100 gram oil, colloid is less than 60mg/100ml.Reaction condition is: reaction pressure is 2.8MPa, and reaction inlet temperature is 40 DEG C, and hydrogen to oil volume ratio is 80: 1, and charging green oil air speed is 8h
-1.
The Hydrogenation contrast of table 3 catalyst
From the data of table 1, table 2 and table 3, the Hydrogenation of drippolene one section of selective hydrogenation catalyst prepared by the present invention, selective and hold colloidality and can be better than catalyst prepared by infusion process.
Claims (11)
1. drippolene one section of selective hydrogenation catalyst, comprises carrier and is carried on the active component on carrier, it is characterized in that:
Described carrier is at least one in aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolin, cordierite, or these are carrier loadedly formed complex carrier to metal, ceramic inert substrate, its shape be granular, spherical, profile of tooth, annular, tooth are spherical, sheet shape, bar shaped or cloverleaf pattern;
Described active component comprises main active component and/or helps active component;
Described main active component is simple substance palladium, and palladium content is the 0.01wt% ~ 1.0wt% of described carrier gross weight;
The described active component that helps is at least one in Sn, Pb, Cu, Ga, Zn, Ag, Sb, Mn, Co, Mo, W, Si, Fe, alkali metal, alkaline-earth metal, and content is the 0.0wt% ~ 5.0wt% of described carrier gross weight;
The grain diameter of described main active component is less than 10nm;
Active component in described catalyst adopts microemulsion method preparation and obtains, and flood or be sprayed on carrier, concrete steps are as follows: (1) prepares microemulsion: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1:x:y:z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced is flooded or sprays on carrier;
(4) by dry for microemulsion obtained for step (3), roasting.
2. drippolene according to claim 1 one section of selective hydrogenation catalyst, is characterized in that described palladium content is the 0.05wt% ~ 0.5wt% of described carrier gross weight.
3. drippolene according to claim 1 one section of selective hydrogenation catalyst, it is characterized in that the described active component that helps is Sn and/or Pb, its content is the 0wt%-2.0wt% of total weight of carrier.
4. drippolene according to claim 1 one section of selective hydrogenation catalyst, it is characterized in that the described active component that helps is at least one in K, Mg, Ca, Ba, its content is the 0wt%-0.8wt% of total weight of carrier.
5. drippolene according to claim 1 one section of selective hydrogenation catalyst, is characterized in that described carrier is aluminium oxide, and the specific area of carrier is 70 ~ 200m
2/ g.
6. drippolene according to claim 1 one section of selective hydrogenation catalyst, is characterized in that described carrier is the aluminium oxide of lanthanum modification.
7. drippolene according to claim 1 one section of selective hydrogenation catalyst, it is characterized in that described non-ionic surface active agent is at least one in TX-100, Tween85, Tween80, Tween60, Tween20, Span80, Span40, NP-10, NP-4, OP-10, described cosurfactant is C
3~ C
8alcohols, described oil phase is C
6~ C
12linear paraffin, cyclic alkane, at least one in branched paraffin, described salting liquid is at least one in the nitrate of noble metal, sulfate, chloride, acetate.
8. drippolene according to claim 1 one section of selective hydrogenation catalyst, it is characterized in that described cosurfactant is normal propyl alcohol, isobutanol, n-amyl alcohol, isooctanol, described oil phase is cyclohexane, n-hexane, isooctane.
9. drippolene according to claim 1 one section of selective hydrogenation catalyst, the reduction reaction temperature that it is characterized in that described step (2) is 0 ~ 60 DEG C, and described reducing agent is hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
10. the preparation method of the drippolene one section of selective hydrogenation catalyst described in any one in claim 1-9, comprises the following steps:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1:x:y:z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced is flooded or sprays on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained selective hydrogenation catalyst.
11. drippolenes according to claim 1, one section of selective hydrogenation catalyst is applied to drippolene one section of selec-tive hydrogenation and removes alkadienes and cinnamic reaction.
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| WO2015007230A1 (en) * | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | Iron-based hydrogenation catalyst and applications thereof |
| CN104001526B (en) * | 2014-06-13 | 2016-04-13 | 西南化工研究设计院有限公司 | A kind of catalyst for acetic acid preparation of ethanol by hydrogenating and preparation method |
| JP7158953B2 (en) * | 2017-08-18 | 2022-10-24 | 中国石油化工股▲ふん▼有限公司 | Catalyst for producing light aromatic hydrocarbons from heavy aromatic hydrocarbons, production method and application thereof |
| CN109289868B (en) * | 2018-10-11 | 2022-04-01 | 烟台百川汇通科技有限公司 | Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof |
| CN112844406B (en) * | 2019-11-26 | 2023-02-28 | 中国石油天然气股份有限公司 | Preparation method of catalyst for selective hydrogenation of light hydrocarbon cracking carbon-depleted fraction |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
| CN114073966A (en) * | 2020-08-13 | 2022-02-22 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst |
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