CN102220160B - Method of selective hydrogenation of alkyne in cracking C5 - Google Patents
Method of selective hydrogenation of alkyne in cracking C5 Download PDFInfo
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Abstract
The method of selective hydrogenation of alkynes in cracking C5 of the invention belongs to the technical field of hydrogenation; in order to meet the urgent requirement of a method of selective hydrogenation of alkynes in cracking C5, a method of selective hydrogenation of alkynes in cracking C5 is studied, wherein a cracking C5 fraction and hydrogen are added together into a hydrogenation reactor loaded with a supported metal catalyst so as to remove the alkynes in cracking C5 by selective hydrogenation under a condition with an inlet temperature of 20-70 DEG C, a C5 liquid space velocity of 1-10 h<-1>, a hydrogen/alkyne molar ratio of 1-10, and a reaction pressure of 0.1-4 MPa; the supported metal catalyst comprises a carrier and an active component loaded on the carrier, and the main active component is Pd; during the preparation of the catalyst, the carrier loaded with the active component precursor is treated by ionizing radiation so as to allow the main active component Pd to be in an elemental state at a condition with room temperature and air, and an average particle size of the active component is less than 10 nm. The method of the invention is a method for long-term operation.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, more particularly, the present invention relates to a kind of method for the cracking c_5 selective hydrogenation.
Background technology
The C5 fraction that petroleum cracking ethylene by-product processed is a large amount of, its main component is isoprene, m-pentadiene, cyclopentadiene, dicyclopentadiene, monoolefine and alkane, and its separation and utilization have realistic meaning for the economic benefit and the utilize resources synthetically that improve ethylene unit.The diolefin that accounts for C5 fraction 40-60% will pass through process for separating and purifying usually, reaches after certain purity and could effectively rationally utilize.Because C5 fraction forms complexity, boiling point approaches and easily generates each other azeotrope, and therefrom isolating carbon five dienes that added value is higher is very complicated engineerings.The isoprene separated is mainly used in polymerization and generates polyisoprene rubber, specialty elastomer, SIS isoprene-isobutylene rubber, is important Organic Chemicals.In isoprene, the alkynes of trace produces injurious effects to the isoprene polymerization catalyzer.
For the C 5 diene of high-purity, the industrial generally separation method of application is that the solvent extraction distillation method removes alkynes with extraction agent at present.But the defects such as the method has operation energy consumption and investment cost is higher, the loss of solvent and isoprene is larger, and easily produce black bits occluding device in the cycling extraction solvent.
Alkynes in C5 fraction is carried out to selective hydrogenation, thereby the method that obtains highly purified carbon pentaene hydrocarbon there is a small amount of disclosing.All or part of alkynes in C5 fraction is selected to hydrogenation, especially generate desirable product in C5 fraction by selective hydrogenation, in order to reduce the loss of corresponding valuable component, if possible, should avoid " excessive " hydrogenation to generate more saturated compound as far as possible.For example, by the hydrogenation Isoprenes such as valylene, 2-butyne, 1-pentyne, 2-butylene, 1-amylene etc. in C5 fraction, or at least make its residual content reach several ppm, avoid excessive monoolefine and the alkane of being hydrogenated to as far as possible.Thisly can simplify carbon five separation process except the alkynes method, but the catalyzer that requires to use needs higher selectivity, enough active and sufficiently long work-ing life, long-term to be suitable for, low-cost running.
But, the Catalyst And Method that carries out selective hydrogenation for the alkynes be present in C5 fraction, prior art can't meet the residual content that reduces alkynes after hydrogenation simultaneously and increase its selectivity, makes the loss amount of diolefine in C5 fraction be reduced to requirement to a certain degree.
Summary of the invention
, load defect little, poor selectivity short for hydrogenation of unsaturated hydrocarbons catalyst life in prior art that purpose of the present invention makes, propose that a kind of selectivity is high, good stability, long Catalysts and its preparation method and methods for using them of life-span, can be effectively in C5 fraction, selective hydrogenation is carried out in the C5 fraction that particularly removes cyclopentadiene.
Concrete technical scheme is as follows:
In a kind of cracking c_5, the selection method of hydrotreating of alkynes, is characterized in that, cracked C 5 fraction enters the hydrogenator that loaded catalyst is housed together with hydrogen, at 20～70 ℃ of temperature ins, carbon five liquid air speed 1～10h
-1, make selective acetylene hydrocarbon hydrogenation in cracking c_5 and remove under hydrogen/alkynes mol ratio 1～10 and reaction pressure 0.1～4MPa;
Described loaded catalyst comprises carrier and is carried on the active ingredient on carrier, main active ingredient is Pd, in catalyst preparation process, the carrier of load active component precursor is processed so that main active ingredient Pd is the simple substance state under room temperature and air conditions through ionizing radiation, and the median size of active ingredient is less than 10nm.
In order to show fully the excellent properties of catalyzer, preferably, described active ingredient comprises:
A) main active ingredient Pd, 0.01wt%～2wt% that its content is total catalyst weight;
B) be selected from one or more in Ag, Cu, Au, Ga, As, Bi, Pb, Sn, Cr, rare earth element, alkali and alkaline earth metal ions, 0wt%～20wt% that its content is total catalyst weight.
In addition, also can add in hydrogenation catalyst commonly used other to regulate the active ingredient that helps of catalyst performances, as haloid element etc.Metal active constituent content a) is 0.05wt%～15wt%, more preferably 0.05wt%～1wt% more preferably; Active ingredient b) content is the 0wt%～10wt% of carrier gross weight more preferably.
Preferably, described carrier is Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2, SiC, kaolin, violet cyanines stone or two or more mixture in them, or described carrier is by Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2, at least one in SiC, kaolin and violet cyanines stone load on formed complex carrier in the inertia substrate, described inertia substrate comprises metal base and pottery.
More preferably, the specific surface of described carrier is 3～200m
2/ g, mean pore size is 20～300nm, and pore volume is 0.2～1.0ml/g, and it is shaped as, and granular, spherical, profile of tooth, annular, tooth are spherical, sheet, strip, trifolium or Herba Galii Bungei.Described Herba Galii Bungei can be the short special-shaped strip of long and another two leaves of two leaves.Also can use other the special-shaped strip that is applicable to catalyzer of the present invention.
Preferably, described catalyzer is through ionizing radiation in preparation process, and irradiance method is selected one of following method:
A) load is had the carrier of described active ingredient precursor use containing after the solution-wet of free-radical scavengers, irradiation under wetting regime, preferably under vacuum or inert atmosphere;
B) load there is is the carrier of described active ingredient precursor add in the solution containing free-radical scavengers, irradiation under the solution submerged state;
C) described carrier is added in the solution containing free-radical scavengers and described active ingredient precursor to irradiation under the solution submerged state.
Preferably, ionizing rays used is gamma-rays, X ray or electron beam.
Preferably, described free-radical scavengers is selected from more than one in alcohols and formic acid, a kind of in particular methanol, ethanol, ethylene glycol, Virahol and formic acid, and volumetric concentration is 1%～80%.
Preferably the described splitting gas from olefin hydrocarbon apparatus is the product stream from steam cracking device or cat-cracker.
Preferably, described mixed phase hydrogenation reaction is operated under the temperature of 10 ℃～100 ℃ and 0.7MPa～4.0MPa pressure condition, and the gaseous phase volume air speed of splitting gas is 1000～20000h
-1, the liquid phase volume air speed of liquid phase stream is 0.5～10h
-1.
Irradiance method a) and b) in, at first use active ingredient precursor steeping fluid impregnated carrier, then add the solution containing free-radical scavengers, make it under moisture state or solution submerged state, carry out irradiation; At irradiance method c) in, be that carrier directly is immersed in the solution containing free-radical scavengers and active ingredient precursor.
Ionizing rays of the present invention can be gamma-rays, X ray or electronics, and gamma ray source is optional
60co (γ source),
137cs (γ source), x-ray source or rumbatron (electron beam), preferably
60co, x-ray source or rumbatron, more preferably
60co.Preferably, ionizing rays used is gamma-rays, X ray or electron beam.
Preferably, the absorbed dose rate of ionizing rays used is 10～10000Gy/min, more preferably 20～100Gy/min.Described ionizing rays reduction process can be carried out under room temperature or low temperature, preferably at room temperature carries out.
Preferred described active ingredient precursor is selected from muriate, nitrate, acetate, vitriol, oxide compound or the organometallics that the active ingredient element is corresponding.
More preferably, described active ingredient precursor can load on carrier by a step dipping or step impregnation; Described active ingredient precursor is formulated as solution in advance, and solvent is selected from one or more the mixture in water, hydrochloric acid, nitric acid, acetic acid, alcohols.More preferably water.
The pH value of active ingredient precursor solution can impact size of particles and the spreading depth that makes the catalyst activity component.Thereby, can carry out appropriate regulation to the activity and selectivity that makes catalyzer by the pH that regulates steeping fluid.In catalyzer of the present invention, preferably, it is 1～10 that the active ingredient precursor solution need to be used basic cpd to regulate the pH value, and described basic cpd is one or more the mixture be selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, ammoniacal liquor and organic amine.
Preferably, can use fixing agent to process the carrier of described carrier or described load active component precursor, regulate the step of the pH value of active ingredient precursor solution with replacement; Wherein said fixing agent is basic cpd, preferably sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammoniacal liquor or organic amine.
Described free-radical scavengers can be selected from alcohols and the derivative thereof of C1-C5, preferred described free-radical scavengers is selected from least one in alcohols and formic acid, preferred a kind of in methyl alcohol, ethanol, ethylene glycol, Virahol and formic acid, the volumetric concentration of described free-radical scavengers is 1%～80%, more preferably 20%～80%, more preferably 30%～60%, more preferably 5%～20%.At using method c) while being flooded, can determine by the volume ratio of free-radical scavengers and solution the dosage that adds of free-radical scavengers, the concentration of solution is got final product in above-mentioned scope.
The preparation method of loaded catalyst of the present invention.Particularly, comprise the following steps:
(1) one or more described active ingredient precursors are loaded to carrier surface;
(2) add free-radical scavengers, use ionizing radiation reducing metal active ingredient precursor under wetting regime or under the solution submerged state.
In preparation method of the present invention, described active ingredient precursor can be used dipping method commonly used in the catalyzer preparation to load on carrier, as spraying, incipient impregnation, supersaturation impregnating.While using the supersaturation pickling process, if the active ingredient precursor in steeping fluid can not adsorb by suppressed by vector fully, should determine according to ratio of adsorption and volume and the active ingredient concentration of steeping fluid meet pre-provisioning request with proof load to the active component content on carrier.
While comprising two or more active ingredient in catalyzer, can adopt step pickling process or a step impregnation method.Use a step pickling process, several active ingredient precursors can be dissolved in same solution carrier is flooded.For the active ingredient precursor that can not be formulated in same solution, can adopt the method for step impregnation, several active ingredient precursors are mixed with respectively to solution carrier is flooded, after each dipping, may need carrier drying.
Optionally, before using preparation method's irradiation reduction of the present invention, can be by the at high temperature roasting of carrier after the dipping active ingredient, making the active ingredient precursors decompose is oxide compound, then carries out the irradiation reduction.
In preparation method of the present invention, irradiation rear catalyst product needed is fully dry.Drying can be carried out under air atmosphere or vacuum, preferably under air atmosphere, carries out.Optional 50～200 ℃ of drying temperature, preferably 50～100 ℃.Optional 5～48 hours of time of drying, preferably 5～24 hours.Obtain catalyzer of the present invention after drying.
After mixing, cracked C 5 fraction and hydrogen enters beds, the alkynes under the effect of catalyzer in carbon five and hydrogen generation addition reaction and remove.
The catalyzer that method of the present invention is used has high activity, selectivity and satisfactory stability, thus method of the present invention have advantages of can long-term operation.
Embodiment
Below in the mode of embodiment, further explain catalyzer of the present invention, but the present invention is not limited to these embodiment.In the present invention, per-cent is mass percent.
Catalyst preparation example 1
Take the PdCl that concentration is 10mg Pd/ml
2solution 10ml, used deionized water to be diluted to 35ml, and using 1mol/L NaOH solution to regulate its pH value is 4.3, then by solution dilution to 46.5g.Take profile of tooth Al
2o
3carrier 100g, Al used
2o
3the carrier specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, to the spraying PdCl for preparing on it
2solution.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in the carrier that load has Pd, dispersed hypsokinesis goes out excess solution.Product is used under vacuum
60the Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample after irradiation is dry 6h under 120 ℃, obtains catalyst A, and its Pd content is 0.1%.
Catalyst preparation example 2
By got PdCl
2amount of solution changes 13.5ml into, and all the other operate all with embodiment 1, obtain catalyst B, and its Pd content is 0.135%.
Catalyst preparation example 3
Take the Pd (NO of 10mg Pd/ml
3)
2solution 10ml, add the AgNO of 10mg Ag/ml
3solution 20ml, used deionized water that mixing solutions is diluted to 46.5g.Take profile of tooth Al
2o
3carrier 100g, Al used
2o
3the carrier specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, the Pd-Ag mixing solutions of preparing to spraying on it.Get the NaOH solution 9ml of 1mo/L, use deionized water to be diluted to 18ml, be sprayed on the carrier containing Pd and Ag prepared above.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in product prepared by top two steps, dispersed hypsokinesis goes out excess solution.Products obtained therefrom is used under vacuum
60the Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample after irradiation is dry 6h under 120 ℃, obtains catalyzer C, and its Pd content is that 0.1%, Ag content is 0.2%.
Catalyst preparation example 4
Take the Cu (NO of 10mg Cu/ml
3)
2solution 20ml, be diluted with water to 46.5g, takes 100g Al
2o
3with violet cyanines stone, mix on the carrier formed, aluminum oxide and violet cyanines stone mix aftershaping by weight 8: 2 ratios, and the mixed carrier specific surface is 45m
2/ g, mean pore size 35nm, pore volume 0.45ml/g, by joined solution spraying, on above-mentioned carrier, blowing air decomposes 8 hours at 450 ℃ afterwards.Take the PdCl of 10mgPd/ml
2solution 10ml, used deionized water to be diluted to 35ml, and using 1mol/L NaOH solution to regulate its pH value is 4.3, then by solution dilution to 46.5g, be sprayed at after decomposing and contain on the carrier of Cu.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in product prepared by previous step, dispersed hypsokinesis goes out excess solution.Product is used under vacuum
60the Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample after irradiation is dry 6h under 120 ℃, obtains catalyzer D, and its Pd content is that 0.1%, Cu content is 0.2%.
Catalyst preparation example 5
Take the Pd (NO of 10mg Pd/ml
3)
2solution 13.5ml, add the HAuCl of 10mg Au/ml
4solution 10ml, used deionized water that mixing solutions is diluted to 46.5g.Take profile of tooth Al
2o
3carrier 100g, Al used
2o
3the carrier specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, the Pd-Au mixing solutions of preparing to spraying on it.Get the NaOH solution 9ml of 1mo/L, use deionized water to be diluted to 18ml, be sprayed on the carrier containing Pd and Au prepared above.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in product prepared by top two steps, dispersed hypsokinesis goes out excess solution.Products obtained therefrom is used under vacuum
60the Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample after irradiation is dry 6h under 120 ℃, obtains catalyzer E, and its Pd content is that 0.135%, Au content is 0.1%.
Catalyst preparation example 6
Take the Pd (NO of 10mg Pd/ml
3)
2solution 13.5ml, add the La (NO of 10mg La/ml
3)
3solution 20ml, used deionized water that mixing solutions is diluted to 46.5g.Take Al
2o
3carrier 100g, Al used
2o
3carrier is by Al
2o
3slurry is carried on inactive ceramic and makes, Al
2o
3the slurry specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, the Pd-La mixing solutions of preparing to spraying on it.Get the NaOH solution 9ml of 1mo/L, use deionized water to be diluted to 18ml, be sprayed on the carrier containing Pd and La prepared above.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in product prepared by top two steps, dispersed hypsokinesis goes out excess solution.Products obtained therefrom is used under vacuum
60the Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample after irradiation is dry 6h under 120 ℃, obtains catalyzer F, and its Pd content is that 0.135%, La content is 0.2%.
Embodiment 1
The present embodiment is the Evaluation operation example of catalyst A～F.
Respectively catalyst A～F being packed in fixed-bed reactor, is 10h with the volume hourly space velocity
-1hydrogen 250 ℃ of lower normal pressures reduction, also flow and entering bed from the bed lower end after the cracking c_5 material is mixed with hydrogen, in temperature in, be that 30 ℃, the volume ratio of hydrogen/carbon five are 70, the volume hourly space velocity is 3h
-1catalytic performance with evaluate catalysts under 3MPa.The cracking c_5 material used is provided by Yanshan Petrochemical company, and its composition is listed in table 1.Composition with material after gas chromatographic analysis raw material and hydrogenation.
Table 1
According to test-results, table 2 is listed in by the transformation efficiency of catalyzer and selectivity in concentrated area.
Table 2
| The catalyzer sequence number | Transformation efficiency | Selectivity |
| A | 98％ | 93％ |
| B | 98％ | 93％ |
| C | 100％ | 92％ |
| D | 100％ | 92％ |
| E | 98％ | 95％ |
| F | 97％ | 96％ |
Under these conditions, catalyst A～F estimates 1000 hours continuously, in carbon five, the transformation efficiency of alkynes and selectivity do not have noticeable change, show that catalyzer used in the present invention has satisfactory stability, and in cracking c_5 of the present invention, have advantages of can long-term operation for the selective acetylene hydrocarbon hydrogenation method.
Claims (7)
1. the selection method of hydrotreating of alkynes in a cracking c_5, is characterized in that, cracked C 5 fraction enters the hydrogenator that loaded catalyst is housed together with hydrogen, at 20～70 ℃ of temperature ins, carbon five liquid air speed 1～10h
-1, make selective acetylene hydrocarbon hydrogenation in cracking c_5 and remove under hydrogen/alkynes mol ratio 1～10 and reaction pressure 0.1～4MPa;
Described loaded catalyst comprises carrier and is carried on the active ingredient on carrier, main active ingredient is Pd, in catalyst preparation process, the carrier of load active component precursor through the ionizing rays radiation treatment so that main active ingredient Pd is the simple substance state under room temperature and air conditions; The median size of active ingredient is less than 10nm; Described catalyzer has load the carrier of described active ingredient precursor to use containing after the solution-wet of free-radical scavengers in preparation process, ionizing rays irradiation under wetting regime.
2. the method for claim 1, is characterized in that, described catalyzer is to carry out ionizing rays irradiation under vacuum or inert atmosphere.
3. the method for claim 1, is characterized in that, described active ingredient comprises:
A) main active ingredient Pd, 0.01wt%～2wt% that its content is total catalyst weight;
B) be selected from one or more in Ag, Cu, Au, Ga, As, Bi, Pb, Sn, Cr, rare earth element, alkali and alkaline earth metal ions, 0wt%～20wt% that its content is total catalyst weight.
4. the method for claim 1, is characterized in that, described carrier is Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2, SiC, kaolin, violet cyanines stone or two or more mixture in them, or described carrier is by Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2, at least one in SiC, kaolin and violet cyanines stone load on formed complex carrier in the inertia substrate, described inertia substrate comprises metal base and pottery.
5. the method for claim 1, is characterized in that, ionizing rays used is gamma-rays, X ray or electron beam.
6. the method for claim 1, is characterized in that, described free-radical scavengers is selected from more than one in alcohols and formic acid, and volumetric concentration is 1%～80%.
7. method as claimed in claim 6, is characterized in that, described free-radical scavengers is selected from a kind of in methyl alcohol, ethanol, ethylene glycol, Virahol and formic acid.
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| CN105771984B (en) * | 2014-12-25 | 2019-09-03 | 中国石油天然气股份有限公司 | C5 fraction selective hydrocatalyst and preparation method thereof |
| CN106588554A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Method for removing alkynes from C5 fraction |
| CN109772291B (en) * | 2019-03-13 | 2020-07-10 | 西南化工研究设计院有限公司 | Selective hydrogenation and dealkynization catalyst and preparation method and application thereof |
| CN112755998A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst, preparation method and application thereof, and selective hydrogenation alkyne removal method |
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| CN1508103A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Method for preparing alkane by hydrogenation of hydrocarbon raw material and catalyst used thereof |
| WO2008138785A1 (en) * | 2007-05-10 | 2008-11-20 | Basf Se | Selective hydrogenation catalyst |
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| CN1508103A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Method for preparing alkane by hydrogenation of hydrocarbon raw material and catalyst used thereof |
| WO2008138785A1 (en) * | 2007-05-10 | 2008-11-20 | Basf Se | Selective hydrogenation catalyst |
| CN101451077A (en) * | 2007-12-07 | 2009-06-10 | 中国石油化工股份有限公司 | Selective hydrogenation method of acetylene hydrocarbon and dialkene in cracking gas |
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