CN103084171A - Pyrolysis gasoline first stage selective hydrogenation catalyst, preparation method and applications thereof - Google Patents
Pyrolysis gasoline first stage selective hydrogenation catalyst, preparation method and applications thereof Download PDFInfo
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- CN103084171A CN103084171A CN2011103326610A CN201110332661A CN103084171A CN 103084171 A CN103084171 A CN 103084171A CN 2011103326610 A CN2011103326610 A CN 2011103326610A CN 201110332661 A CN201110332661 A CN 201110332661A CN 103084171 A CN103084171 A CN 103084171A
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Abstract
The invention provides a pyrolysis gasoline first stage hydrogenation catalyst, a preparation method and applications thereof. According to the present invention, active components of the catalyst are prepared through a microemulsion method, and are loaded on a carrier, the active components are metal atoms or low valence metal ions, and the main active component Pd of the catalyst has characteristics of particle size of less than 10 nm, controllable and uniform particle size, and good dispersion; the catalyst preparation method has characteristics of simpleness, easy operation, and mild operation conditions; and with application of the catalyst in selective hydrogenation reactions of diene and styrene, high activity, good selectivity and good adhesive capacity performance are provided.
Description
Technical field
The present invention relates to a kind of supported selective hydrogenation catalyst and its preparation method and application, specifically one section selective hydrogenation catalyst of a kind of drippolene and its preparation method and application.
Background technology
Drippolene is the important by-product that ethylene industry is produced, and comprises the C5-C10 fraction.Drippolene forms very complicated, mainly contain the organic compound of benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine and heavy metal etc., more than totally 200 component, the about 50-80% of benzene,toluene,xylene (general designation BTX) aromatic hydrocarbons wherein, unsaturated hydrocarbons 25-30%.One section selection hydrogenation of industrial drippolene is removed alkadienes and styrene, after the organic compound of Secondary hydrodesulfurization removal monoolefine and sulphur, nitrogen, oxygen, is used for Aromatics Extractive Project.
The pyrolysis gasoline hydrogenation catalyst of using on industrial production at present mainly contains palladium system and nickel is two kinds of catalyst, take palladium series catalyst as main.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 of preparation pyrolysis gasoline hydrogenation catalyst is the described carrier of 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 need to repeatedly be heated to impregnated catalyst 200 ℃-1200 ℃ usually, makes slaine or organo-metallic compound be decomposed into corresponding oxide, and the catalyst after roasting could be used for the pyrolysis gasoline hydrogenation reaction after need leading to before use hydrogen reducing.The catalyst decentralization of tradition infusion process preparation is often lower, has affected 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 the active component sintering, makes the degradation of catalyst.In the catalyst of tradition infusion process preparation, all there be diffusion or the metal migration of Metal Palladium ion in each step, and the each several part on carrier has the palladium element to exist, and just concentration is different.Because all there is the Metal Palladium ion in various piece, and its hydrogenation selectivity is descended.
Chinese patent CN1184289C discloses a kind of Catalysts and its preparation method for selective hydrogenation of cracked gasoline and application, its carrier adopts the titanium dioxide-aluminum oxide compound, and the activity component metal palladium that is carried on 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 characteristics such as selective and good stability, but its antijamming capability, appearance glue ability and resistance to water are not described.
Chinese patent CN85100761A discloses a kind of fiber catalyst carrier for the pyrolysis gasoline cut fraction diolefin selective hydrogenation, owing to having adopted η-Al
2O
3Porous fibrous carrier, so this catalyst activity is high, but the aperture is too little, when colloid in raw material, arsenic content, when water content exceeds standard, the easy coking and blocking in the hole on catalyst affects catalyst hydrogenation stability.
Chinese patent CN 100512955C disclose relate to a kind of for C2～C10 cut alkynes and diolefin hydrogenate Catalysts and its preparation method, major catalyst palladium and co-catalyst only are distributed in the aluminum oxide coating layer of catalyst coating, and the thickness of aluminum oxide coating layer only has 10～300 microns.Make like this major catalyst palladium and co-catalyst can both fully participate in the selective acetylene hydrocarbon hydrogenation reaction, improved the hydrogenation efficiency of catalyst activity component.
Compare with conventional method, microemulsion method forms microemulsion droplets as a kind of effective ways that prepare nano particle by the aqueous solution, surfactant and cosurfactant, and this microemulsion droplets has the microreactor function.By adjusting the aqueous solution and dosage of surfactant ratio, can effectively control nano particle diameter in addition.
Summary of the invention
For the problems of the prior art, the purpose of this invention is to provide one section selective hydrogenation catalyst of a kind of drippolene 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 one section selective hydrogenation catalyst of a kind of drippolene, this catalyst is used for one section of drippolene and selects hydrogenation to remove alkadienes and cinnamic reaction, comprise carrier and the active component that is carried on carrier, the active component of described catalyst is utilize the microemulsion method preparation and get.
Described carrier is at least a in aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolin, cordierite, also comprises these carrier loaded complex carriers that forms to the inertia substrates such as metal, pottery.Preferred carrier is aluminium oxide, and specific area is 70-200m
2/ g, the bar shaped such as it is shaped as, and granular, spherical, profile of tooth, annular, tooth are spherical, sheet shape, 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 the 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, Zn Ag, 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 a 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 is adopt microemulsion method to prepare and get, and is carried on carrier, comprises the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, 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 that 0.1～10, z is 0.1～4;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and wherein the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains one section selective hydrogenation catalyst of drippolene of the present invention.
Wherein said non-ionic surface active agent is at least a 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, a kind of in isooctanol; Described oil phase is selected from C
6～C
12Linear paraffin, cyclic alkane, branched paraffin at least a, more preferably from cyclohexane, n-hexane, isooctane; Described salting liquid is selected from a kind of in described nitrate, sulfate, chloride, acetate.
Reduction reaction temperature in step (2) is 0～60 ℃, at least a for in hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde of described reducing agent.
The catalyst activity component that above-mentioned reduction is fully obtained loads on carrier by conventional methods such as dipping, sprayings, and more preferably the catalyst activity component of described microemulsion preparation loads on carrier by a step dipping or step impregnation.
The demonstration of transmission electron microscope (TEM) test result, the catalyst that uses microemulsion technology of the present invention to make forms nano particle in microemulsion, and the particle diameter＜10nm of nano particle can be with reference to accompanying drawing 1.In addition, the particle of active component can be controlled by the mode of regulating water/surfactant.
Another object of the present invention is to provide a kind of method for preparing one section selective hydrogenation catalyst of drippolene.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, mode by dipping, spraying after the reducing agent reduction loads on carrier, and the metal nanoparticle average diameter that forms in microemulsion is less than 10nm.Specifically comprise the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, 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 that 0.1～10, z is 0.1～4;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and wherein the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains one section selective hydrogenation catalyst of drippolene of the present invention.
The 3rd purpose of the present invention is to provide the application of this catalyst in one section selection hydrogenation of drippolene is removed alkadienes and cinnamic reaction.
The present invention compared with prior art has the following advantages:
(1) preparation method of the present invention is simple, and is easy to operate, and experiment condition is gentle.
(2) one section selective hydrogenation catalyst of drippolene of the present invention's preparation is prepared from because adopting microemulsion method, and its particle diameter is controlled, evenly, good dispersion, good stability has improved the activity and selectivity of catalyst in reaction significantly.
(3) use the catalyst of the method preparation to compare with existing catalyst, diolefin hydrogenation is selectively high, holds the glue ability good, and good water-resistant capacity is arranged.
Description of drawings
Fig. 1 is the distribution of catalyst nanoparticles in microemulsion system
The specific embodiment
The present invention will be further described below in conjunction with specific embodiment, 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; 25 ℃ are mixed 15.8mlTx100 and 13.4ml normal propyl alcohol under magnetic agitation in water bath with thermostatic control, and then add the PdCl of dilute with water with the 25ml cyclohexane
2Solution, the magnetic agitation certain hour is until obtain transparent microemulsion; Add in the above-mentioned microemulsion a certain amount of hydrazine hydrate to make PdCl in microemulsion
2Be reduced into simple substance Pd; Take 100g Al
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 respectively the Pd (NO of 200mgPd/ml
3)
2Solution 1.25ml, the Pb (NO of 200mgPb/ml
3)
2Solution 2.5ml uses deionized water to be diluted to 10ml; 25 ℃ are mixed 16.2ml NP-10 and 12.2ml n-butanol under magnetic agitation in water bath with thermostatic control with the 20ml isooctane, and then add the metal salt solution of dilute with water, and the magnetic agitation certain hour is until obtain transparent microemulsion; Add in the above-mentioned microemulsion a certain amount of hydrazine hydrate to make Pd (NO in microemulsion
3)
2And Pb (NO
3)
2Be reduced into simple substance Pd and Pb; Take 100g Al
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%, and Pb content is 0.50wt%.
Embodiment 3
Take respectively the Pd (NO of 200mgPd/ml
3)
2Solution 1.25ml, the Pb (NO of 200mgPb/ml
3)
2Solution 2.5ml mixes, then takes 10.55g Mg (NO
3)
26H
2O puts into the aqueous solution of Pd and Pb, uses deionized water to be diluted to 10ml; 25 ℃ are mixed 15mlTween80 and 10ml n-butanol under magnetic agitation in water bath with thermostatic control with the 25ml n-hexane, and then add the metal salt solution of dilute with water, and the magnetic agitation certain hour is until obtain transparent microemulsion; Add in the above-mentioned microemulsion a certain amount of hydrazine hydrate to make the metal ion in metal salt solution in microemulsion be reduced into the simple substance state.Take 100g Al
2O
3Carrier sprays to the microemulsion after reduction on carrier, and then dry, roasting is prepared into described catalyst C, and wherein Pd content is 0.25wt%, and Pb content is 0.50wt%, and Mg content is 1.0wt%.
Embodiment 4
Take respectively the Pd (NO of 200mgPd/ml
3)
2Solution 1.25ml, the Sn (NO of 200mgSn/ml
3)
2Solution 2ml mixes, and uses deionized water to be diluted to 10ml; 25 ℃ are mixed 15mlTween80 and 10ml n-butanol under magnetic agitation in water bath with thermostatic control with the 25ml n-hexane, and then add the metal salt solution of dilute with water, and the magnetic agitation certain hour is until obtain transparent microemulsion; Add in the above-mentioned microemulsion a certain amount of hydrazine hydrate to make the metal ion in metal salt solution in microemulsion be reduced into the simple substance state.Take 100g Al
2O
3Carrier sprays to the microemulsion after reduction on carrier, and then dry, roasting is prepared into described catalyst D, and wherein Pd content is 0.25wt%, and Sn content is 0.40wt%.
Comparative Examples
Take the Pd (NO of 100mgPd/ml
3)
2Solution 3ml uses deionized water dilution 50ml, takes 100gAl
2O
3Carrier adds the standing 30min of the metal salt solution of dilution, drying, and roasting obtains catalyst E.Wherein Pd content is 0.3wt%.
Evaluation test 1
Get catalyst A, B, C, each 100ml of D, E, carry out activity rating on adiabatic reactor, raw materials used in evaluation is drippolene C6-C8 middle distillate, and diene value is 30-40 gram 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 ℃, and hydrogen to oil volume ratio is 50: 1, and the charging air speed is 8h
-1..Wherein in oil product, the assay method of diene value is apple acid anhydrides method.The evaluation result of reacting after 100 hours sees Table 1:
The Hydrogenation of table 1 catalyst
Evaluation test 2
Table 2 be catalyst D and Comparative Examples catalyst E on the 100ml adiabatic reactor in comparative evaluation's result of the Hydrogenation of reaction after 100 hours, 500 hours under larger air speed condition.Raw materials used in evaluation is drippolene C6-C8 middle distillate, and diene value is 30-40 gram 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 ℃, and hydrogen to oil volume ratio is 50: 1, and the green oil air speed is 8h
-1., the product recycle ratio is 2: 1, total air speed is 24h
-1Wherein 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 air speed condition compares
Evaluation test 3
The present embodiment is the active appraisal experiment of catalyst of the present invention.
Get catalyst A, B, C, each 100ml of D, investigate the activity and selectivity of original catalyst particle size on adiabatic reactor.Raw materials used in evaluation is drippolene C6～C8 midbarrel, diene value 14.11 gram iodine/100 gram oil, and iodine number 43.35 gram iodine/100 gram oil, colloid is less than 60mg/100ml.Reaction condition is: reaction pressure is 2.8MPa, and the reaction inlet temperature is 40 ℃, 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 as can be known, the Hydrogenation of one section selective hydrogenation catalyst of drippolene of the present invention's preparation, selective and hold the catalyst that colloidality can be better than the infusion process preparation.
Claims (12)
1. one section selective hydrogenation catalyst of a drippolene, comprise carrier and the active component that is carried on carrier, it is characterized in that:
Described carrier is at least a in aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolin, cordierite, or these are carrier loadedly formed complex carrier to the inertia substrates such as metal, pottery;
Described active component comprises main active component and/or helps active component;
Described main active component is the 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 a 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 is adopt microemulsion method to prepare and get, and is carried on carrier.
2. one section selective hydrogenation catalyst of drippolene according to claim 1, is characterized in that described palladium content is the 0.05wt%～0.5wt% of described carrier gross weight.
3. one section selective hydrogenation catalyst of drippolene according to claim 1, is characterized in that the described active component that helps is Sn and/or Pb, and its content is the 0wt%-2.0wt% of total weight of carrier.
4. one section selective hydrogenation catalyst of drippolene according to claim 1 is characterized in that the described active component that helps is at least a in K, Mg, Ca, Ba, and its content is the 0wt%-0.8wt% of total weight of carrier.
5. one section selective hydrogenation catalyst of drippolene according to claim 1, is characterized in that described carrier is aluminium oxide, and the specific area of carrier is 70～200m
2/ g.
6. one section selective hydrogenation catalyst of drippolene according to claim 1, is characterized in that described carrier is the aluminium oxide of lanthanum modification.
7. one section selective hydrogenation catalyst of drippolene according to claim 1 is characterized in that described catalyst adopts the microemulsion preparation method in preparation process, comprise the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, 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 that 0.1～10, z is 0.1～4;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains one section selective hydrogenation catalyst of drippolene of the present invention.
8. one section selective hydrogenation catalyst of drippolene according to claim 7, it is characterized in that described non-ionic surface active agent is at least a 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, branched paraffin at least a, described salting liquid is at least a in the nitrate, sulfate, chloride, acetate of noble metal.
9. one section selective hydrogenation catalyst of drippolene according to claim 7, is characterized in that described cosurfactant is normal propyl alcohol, isobutanol, and n-amyl alcohol, isooctanol, described oil phase are cyclohexane, n-hexane, isooctane.
10. one section selective hydrogenation catalyst of drippolene according to claim 7, the reduction reaction temperature that it is characterized in that described step (2) is 0～60 ℃, and described reducing agent is hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
11. the preparation method of one section selective hydrogenation catalyst of the described drippolene of one of claim 1-10 comprises the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, 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 that 0.1～10, z is 0.1～4;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains selective hydrogenation catalyst.
12. being applied to one section of drippolene, one section selective hydrogenation catalyst of drippolene claimed in claim 1 select hydrogenation to remove alkadienes and cinnamic reaction.
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| ES2700899R1 (en) * | 2017-08-18 | 2019-06-13 | China Petroleum & Chem Corp | Catalyst to produce light aromatic compounds with heavy aromatics, method to prepare the catalyst and use it |
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| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
| CN112844406A (en) * | 2019-11-26 | 2021-05-28 | 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 |
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| 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 |
| CN112844406A (en) * | 2019-11-26 | 2021-05-28 | 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 |
| 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 |
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