CN102220160A - 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 that is used for the cracking c_5 selective hydrogenation.
Background technology
The C5 fraction that petroleum cracking system ethylene by-product 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 the certain purity rationally to utilize effectively.Because C5 fraction is formed complicated, boiling point is approaching and easily generate azeotrope each other, and therefrom isolating the higher carbon of added value five dienes is very complex engineering.Isolating isoprene is mainly used in polymerization and generates polyisoprene rubber, specialty elastomer, SIS isoprene-isobutylene rubber, is important Organic Chemicals.The alkynes of trace produces injurious effects to the isoprene polymerization catalyzer in the isoprene.
In order to produce highly purified C 5 diene, the separation method of industrial widespread usage is that the solvent extraction distillation method is promptly removed alkynes with extraction agent at present.But defectives such as this method has operation energy consumption and investment cost is higher, the loss of solvent and isoprene is bigger, and in the cycling extraction solvent, easily produce black bits occluding device.
Alkynes in the C5 fraction is carried out selective hydrogenation, thereby the method that obtains highly purified carbon pentaene hydrocarbon has a spot of open.Promptly all or part of alkynes in the C5 fraction is selected hydrogenation, especially generate desirable product in the 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, hydrogenation such as valylene, 2-butyne, 1-pentyne in the C5 fraction are generated isoprene, 2-butylene, 1-amylene etc., or make its residual content reach several ppm at least, avoid excessive monoolefine and the alkane of being hydrogenated to as far as possible.This alkynes method of removing can be simplified carbon five separation process, but requires employed catalyzer to need 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 that is present in the C5 fraction, prior art can't satisfy the residual content that reduces alkynes behind the hydrogenation simultaneously and increase its selectivity, makes the loss amount of diolefine in the C5 fraction be reduced to a certain degree requirement.
Summary of the invention
, load defective little, poor selectivity short that purpose of the present invention makes at hydrogenation of unsaturated hydrocarbons catalyst life in the prior art, a kind of selectivity height, good stability, long Catalysts and its preparation method and methods for using them of life-span are proposed, can be effectively in the C5 fraction, selective hydrogenation is carried out in the C5 fraction that particularly removes cyclopentadiene.
Concrete technical scheme is as follows:
The selection method of hydrotreating of alkynes is characterized in that in a kind of cracking c_5, and cracked C 5 fraction enters the hydrogenator that loaded catalyst is housed with hydrogen, at 20～70 ℃ of temperature ins, carbon five liquid air speed 1～10h
-1, make selective acetylene hydrocarbon hydrogenation in the cracking c_5 under hydrogen/alkynes mol ratio 1～10 and the reaction pressure 0.1～4MPa and remove;
Described loaded catalyst comprises carrier and the active ingredient that is carried on the carrier, main active ingredient is Pd, in catalyst preparation process, the carrier of load active component precursor is handled so that main active ingredient Pd is the simple substance attitude under room temperature and air conditions through ionizing radiation, and the median size of active ingredient is less than 10nm.
In order to show the excellent properties of catalyzer fully, preferably, described active ingredient comprises:
A) main active ingredient Pd, its content are the 0.01wt%～2wt% of total catalyst weight;
B) be selected from Ag, Cu, Au, Ga, As, Bi, Pb, Sn, Cr, rare earth element, basic metal and the alkaline-earth metal one or more, its content is the 0wt%～20wt% of total catalyst weight.
In addition, also can add in the hydrogenation catalyst commonly used other and 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 with Al
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2, at least a in SiC, kaolin and the 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 granular, spherical, profile of tooth, annular, tooth sphere, sheet, strip, trifolium or Herba Galii Bungei.Described Herba Galii Bungei can be the short special-shaped strip of long two leaves in addition of two leaves.Also can use other the special-shaped strip that is fit to catalyzer of the present invention.
Preferably, through ionizing radiation, irradiance method is selected one of following method to described catalyzer in preparation process:
A) load is had the carrier of described active ingredient precursor use to contain the solution-wet of free-radical scavengers after, irradiation under wetting regime is preferably under vacuum or inert atmosphere;
B) load there is the carrier adding of described active ingredient precursor contain in the solution of free-radical scavengers irradiation under the solution submerged state;
C) described carrier adding is contained in the solution of free-radical scavengers and described active ingredient precursor irradiation under the solution submerged state.
Preferably, used ionizing rays is gamma-rays, X ray or electron beam.
Preferably, described free-radical scavengers is selected from more than one in alcohols and the formic acid, a kind of in particular methanol, ethanol, ethylene glycol, Virahol and the formic acid, and volumetric concentration is 1%～80%.
Preferred 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 10 ℃～100 ℃ temperature 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, add the solution contain free-radical scavengers again, it is under moisture state or the solution submerged state carries out irradiation; At irradiance method c) in, be that carrier directly is immersed in the solution that contains 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), preferred
60Co, x-ray source or rumbatron, more preferably
60Co.Preferably, used ionizing rays is gamma-rays, X ray or electron beam.
Preferably, the absorbed dose rate of used ionizing rays 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 of active ingredient element correspondence.
More preferably, described active ingredient precursor can load on the 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, acetate, the 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 come to carry out appropriate regulation by the pH that regulates steeping fluid making activity of such catalysts and selectivity.In catalyzer of the present invention, preferably, it is 1～10 that the active ingredient precursor solution need use basic cpd to regulate the pH value, and described basic cpd is one or more the mixture that is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, ammoniacal liquor and the organic amine.
Preferably, can use fixing agent to handle 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 a basic cpd, preferred 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 a in alcohols and the 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) when flooding, can determine the adding dosage of free-radical scavengers by the volume ratio of free-radical scavengers and solution, the concentration of solution is got final product in above-mentioned scope.
The preparation method of loaded catalyst of the present invention.Particularly, may further comprise the steps:
(1) one or more described active ingredient precursors is 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 use dipping method commonly used in the Preparation of Catalyst to load on the carrier, as spraying, incipient impregnation, supersaturation impregnating.When using the supersaturation pickling process, the active ingredient precursor in the steeping fluid then should be determined the volume and the active ingredient concentration of steeping fluid according to the absorption ratio if can not adsorb fully by suppressed by vector, satisfies pre-provisioning request with proof load to the active component content on the carrier.
When comprising two or more active ingredient in the catalyzer, can adopt a step pickling process or a step impregnation method.Use a step pickling process, several active ingredient precursors can be dissolved in the same solution carrier is flooded.For the active ingredient precursor that can not be formulated in the same solution, then can adopt the method for step impregnation, several active ingredient precursors are mixed with solution respectively carrier is flooded, may need behind each dipping carrier drying.
Optionally, before using preparation method's irradiation reduction of the present invention, can be with the carrier roasting at high temperature after the dipping active ingredient, making the active ingredient precursors decompose is oxide compound, carries out the irradiation reduction again.
In preparation method of the present invention, irradiation rear catalyst product needed thorough drying.Drying can be carried out under air atmosphere or vacuum, preferably carries out under air atmosphere.Optional 50～200 ℃ of drying temperature, preferred 50～100 ℃.Optional 5～48 hours of time of drying, preferred 5～24 hours.Promptly obtain catalyzer of the present invention after the drying.
After mixing, cracked C 5 fraction and hydrogen enters beds, alkynes under the effect of catalyzer in the carbon five and hydrogen generation addition reaction and remove.
The employed catalyzer of method of the present invention has high activity, selectivity and satisfactory stability, thus method of the present invention have can long-term operation advantage.
Embodiment
Further explain catalyzer of the present invention in the mode of embodiment below, but the present invention is not limited to these embodiment.In the present invention, per-cent is mass percent.
Catalyst preparation example 1
Take by weighing the PdCl that concentration is 10mg Pd/ml
2Solution 10ml uses deionized water to be diluted to 35ml, and using 1mol/L NaOH solution to regulate its pH value is 4.3, again with solution dilution to 46.5g.Take by weighing profile of tooth Al
2O
3Carrier 100g, used Al
2O
3The carrier specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, 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, the homodisperse hypsokinesis goes out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyst A, and its Pd content is 0.1%.
Catalyst preparation example 2
With the PdCl that is got
2Solution amount changes 13.5ml into, and all the other are operated all with embodiment 1, obtain catalyst B, and its Pd content is 0.135%.
Catalyst preparation example 3
Take by weighing the Pd (NO of 10mg Pd/ml
3)
2Solution 10ml, the AgNO of adding 10mg Ag/ml
3Solution 20ml uses deionized water that mixing solutions is diluted to 46.5g.Take by weighing profile of tooth Al
2O
3Carrier 100g, used Al
2O
3The carrier specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, the Pd-Ag mixing solutions that spraying is prepared on it.Get the NaOH solution 9ml of 1mo/L, use deionized water to be diluted to 18ml, be sprayed on the carrier that contains Pd and Ag for preparing above.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in the product of top two steps preparation, the homodisperse 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 behind the irradiation is dry 6h under 120 ℃, obtains catalyzer C, and its Pd content is 0.1%, and Ag content is 0.2%.
Catalyst preparation example 4
Take by weighing the Cu (NO of 10mg Cu/ml
3)
2Solution 20ml, thin up take by weighing 100g Al to 46.5g
2O
3Mix on the carrier of forming with violet cyanines stone, aluminum oxide and violet cyanines stone were by weight 8: 2 mixed aftershapings, and the mixed carrier specific surface is 45m
2/ g, mean pore size 35nm, pore volume 0.45ml/g, with joining solution spraying on above-mentioned carrier, blowing air decomposed 8 hours at 450 ℃ afterwards.Take by weighing the PdCl of 10mgPd/ml
2Solution 10ml uses deionized water to be diluted to 35ml, and using 1mol/L NaOH solution to regulate its pH value is 4.3, again with solution dilution to 46.5g, contain on the carrier of Cu after being sprayed at decomposition.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in the product of previous step preparation, the homodisperse hypsokinesis goes out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 15h under the 30Gy/min dose rate.Sample behind the irradiation is dry 6h under 120 ℃, obtains catalyzer D, and its Pd content is 0.1%, and Cu content is 0.2%.
Catalyst preparation example 5
Take by weighing the Pd (NO of 10mg Pd/ml
3)
2Solution 13.5ml, the HAuCl of adding 10mg Au/ml
4Solution 10ml uses deionized water that mixing solutions is diluted to 46.5g.Take by weighing profile of tooth Al
2O
3Carrier 100g, used Al
2O
3The carrier specific surface is 52m
2/ g, mean pore size 30nm, pore volume 0.47ml/g, the Pd-Au mixing solutions that spraying is prepared on it.Get the NaOH solution 9ml of 1mo/L, use deionized water to be diluted to 18ml, be sprayed on the carrier that contains Pd and Au for preparing above.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in the product of top two steps preparation, the homodisperse 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 behind the irradiation is dry 6h under 120 ℃, obtains catalyzer E, and its Pd content is 0.135%, and Au content is 0.1%.
Catalyst preparation example 6
Take by weighing the Pd (NO of 10mg Pd/ml
3)
2Solution 13.5ml, the La (NO of adding 10mg La/ml
3)
3Solution 20ml uses deionized water that mixing solutions is diluted to 46.5g.Take by weighing Al
2O
3Carrier 100g, used Al
2O
3Carrier is with Al
2O
3Slurry is carried on the 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 that spraying is prepared on it.Get the NaOH solution 9ml of 1mo/L, use deionized water to be diluted to 18ml, be sprayed on the carrier that contains Pd and La for preparing above.Get the mixing solutions of 20ml water and 20ml Virahol preparation, pour in the product of top two steps preparation, the homodisperse 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 behind the irradiation is dry 6h under 120 ℃, obtains catalyzer F, and its Pd content is 0.135%, and La content is 0.2%.
Embodiment 1
Present embodiment is the evaluation embodiment of catalyst A～F.
Respectively catalyst A～F being packed in the fixed-bed reactor, is 10h with the volume hourly space velocity
-1Hydrogen 250 ℃ of following normal pressures reduction, the cracking c_5 material is mixed the back also flow and entering bed with hydrogen from the bed lower end, be that 30 ℃, the volume ratio of hydrogen/carbon five are 70, the volume hourly space velocity is 3h in temperature in
-1Catalytic performance with evaluate catalysts under the 3MPa.Employed cracking c_5 material is provided by Yanshan Petrochemical company, and its composition is listed in table 1.Composition with material behind gas chromatographic analysis raw material and the hydrogenation.
Table 1
According to test-results, table 2 is listed in the transformation efficiency and the selectivity of catalyzer in the 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, the transformation efficiency of alkynes and selectivity do not have noticeable change in the carbon five, show that catalyzer used in the present invention has satisfactory stability, in the cracking c_5 of the present invention the selective acetylene hydrocarbon hydrogenation method have can long-term operation advantage.
Claims (6)
1. the selection method of hydrotreating of alkynes in the cracking c_5 is characterized in that cracked C 5 fraction enters the hydrogenator that loaded catalyst is housed with hydrogen, at 20～70 ℃ of temperature ins, carbon five liquid air speed 1～10h
-1, make selective acetylene hydrocarbon hydrogenation in the cracking c_5 under hydrogen/alkynes mol ratio 1～10 and the reaction pressure 0.1～4MPa and remove;
Described loaded catalyst comprises carrier and the active ingredient that is carried on the carrier, main active ingredient is Pd, in catalyst preparation process, the carrier of load active component precursor is handled so that main active ingredient Pd is the simple substance attitude under room temperature and air conditions through ionizing radiation, and the median size of active ingredient is less than 10nm.
2. the method for claim 1 is characterized in that, described active ingredient comprises:
A) main active ingredient Pd, its content are the 0.01wt%～2wt% of total catalyst weight;
B) be selected from Ag, Cu, Au, Ga, As, Bi, Pb, Sn, Cr, rare earth element, basic metal and the alkaline-earth metal one or more, its content is the 0wt%～20wt% of total catalyst weight.
3. 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 with Al
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2, at least a in SiC, kaolin and the violet cyanines stone load on formed complex carrier in the inertia substrate, described inertia substrate comprises metal base and pottery.
4. as the described method of one of claim 1～3, it is characterized in that through ionizing radiation, irradiance method is selected one of following method to described catalyzer in preparation process:
A) load is had the carrier of described active ingredient precursor use to contain the solution-wet of free-radical scavengers after, irradiation under wetting regime is preferably under vacuum or inert atmosphere;
B) load there is the carrier adding of described active ingredient precursor contain in the solution of free-radical scavengers irradiation under the solution submerged state;
C) described carrier adding is contained in the solution of free-radical scavengers and described active ingredient precursor irradiation under the solution submerged state.
5. method as claimed in claim 4 is characterized in that, used ionizing rays is gamma-rays, X ray or electron beam.
6. method as claimed in claim 4 is characterized in that described free-radical scavengers is selected from more than one in alcohols and the formic acid, a kind of in particular methanol, ethanol, ethylene glycol, Virahol and the formic acid, and volumetric concentration is 1%～80%.
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| CN105771984A (en) * | 2014-12-25 | 2016-07-20 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst for carbon five fraction 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 |
| CN109772291A (en) * | 2019-03-13 | 2019-05-21 | 西南化工研究设计院有限公司 | A kind of selective hydrogenation acetylene removal catalyst and the 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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| 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 |
| CN109772291A (en) * | 2019-03-13 | 2019-05-21 | 西南化工研究设计院有限公司 | A kind of selective hydrogenation acetylene removal catalyst and the preparation method and application thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN102220160B (en) | 2014-01-08 |
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