CN102381920B - Method for removing alkyne in carbon 4 fraction by selective hydrogenation - Google Patents
Method for removing alkyne in carbon 4 fraction by selective hydrogenation Download PDFInfo
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- CN102381920B CN102381920B CN2010102714258A CN201010271425A CN102381920B CN 102381920 B CN102381920 B CN 102381920B CN 2010102714258 A CN2010102714258 A CN 2010102714258A CN 201010271425 A CN201010271425 A CN 201010271425A CN 102381920 B CN102381920 B CN 102381920B
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Abstract
The invention relates to a method for removing alkyne in carbon 4 fraction by selective hydrogenation, comprising the steps of: introducing a liquid inside a tower in an appropriate position below a feedboard to a C4 alkyne hydrogenation reactor; and after reaction, returning a material flow to a rectifying column to remove alkyne in separation process. By adjusting a liquid phase extraction position and reflux ratio of a debutanizer, butadiene entering the C4 hydrogenation reactor is low in concentration, high in EA and VA concentration so as to reduce the reaction probability of converting butadiene to butane and butane conversion, improve the selectivity of converting C4 alkyne to butadiene to realize productive butadiene and remove the alkyne. Meanwhile, C4 alkyne hydrogenation is performed on a fixing bed outside the tower, the catalyst is easier to regenerate and change so as to meet the requirements of long term operation of ethylene unit. The invention can reduce the concentration of alkyne in C4 fraction entering the butadiene extracting device, lower a part of energy consumption of secondary extraction, save C4 hydrocarbon for dilution and reduce the environmental pollution.
Description
Technical field
The invention belongs to the method that selectivity is removed alkynes from unsaturated compound, specifically alkynes in the middle of the 1,3-butadiene is removed in selective hydrogenation from the mixture of unsaturated compound, belongs to petrochemical industry.
Background technology
1,3-butadiene mainly is to separate from the by product C 4 fraction of cracking ethylene preparation as elastomeric raw material.C-4-fraction almost comprises the various isomer of all butanes, alkene, diolefine and alkynes, also has a spot of C3, C5 hydrocarbon.Synthetic rubber requires the alkynes total content to be lower than 20ppm, and therein ethylene ethyl-acetylene VA is lower than 5ppm.At present, the technology of separating 1,3-butadiene is mainly solvent extraction process, and this method is come together, takes off light rectifying tower, taken off the 1,3-butadiene of heavy rectifying tower acquisition 99.5% through a collection, two, and wherein two collections mainly are to deviate from VA.
Along with the increase of cracking severity, alkynes content progressively increases in the C 4 fraction, and alkynes mass concentration even greater than 2% causes that two collection parts can't bear the heavy load in the butadiene extraction unit, and energy consumption increases, the processing power deficiency.
The method that fixed bed of increase selects shortening to remove alkynes before a collection is studied by people already.Usually, the C 4 fraction of separating from the debutylize cat head contains 40%～60% divinyl, 0.5%～2% EA, VA, and this material and an amount of hydrogen are mixed in the fixed bed C4 alkynes reactor and react.It is reported that full scale plant is when hydrogenator exports alkynes less than 15ppm at present, the loss of divinyl is about 1.5%-2.0%.1,3-butadiene does not have or little loss is the place of this method difficulty when removing alkynes.Fixed bed selects the advantage of hydrogenation technique to be: processing ease, catalyst regeneration and replacing are convenient, and shortcoming is: because butadiene concentration is higher in the raw material, selectivity is not high, and the divinyl loss is big.
Catalytic distillation process is at the rectifying section of debutanizing tower filling catalytic distillation assembly, in the method for C-4-fraction and carbon five above cut separating process being carried out simultaneously shortening.The catalytic distillation hydrogenation technique has the reaction preference height, the advantage that temperature of reaction is stable.Shortcoming is: because temperature of reaction is subjected to the restriction of debutanizing tower pressure, the temperature of reaction variation range is little, and the means of adjusting catalyst performance are few; After debutanizing tower moves for some time, the catalyst surface deposited polymer, catalyst activity reduces, catalyst regeneration, replacing difficulty, debutanizing tower can not satisfy the requirement of ethylene unit long-term operation working time.
For improving the selectivity of reaction, overcome short problem of the catalyzer cycle of operation, people have made big quantity research in Preparation of Catalyst and technology.
Copper-loading catalyst and palladium catalyst are the preferred catalysts of removing the acetylenic impurities in the olefin stream by selective hydrogenation.It is reported that the Cu-series catalyst selectivity that the KLP technology of UOP is used is outstanding, the loss of divinyl is zero when remaining alkynes less than 5ppm, the intensity height, and the life-span is 3 years.But because the accumulation of green oil, 2-3 month needs are regenerated once usually, and the recovery time is approximately 10 days.
Shortcomings such as palladium series catalyst is active high, and stability is better, but exists selectivity poor slightly, and palladium easily runs off, price is expensive.Because its selectivity is not good enough, so adopt the flow process of raw material and extrct alkynes mixed hydrogenation, selectivity of catalyst and life-span have much room for improvement.
CN1711226A discloses the method for selecting hydrogenation to remove alkynes in the 1,3-butadiene from the mixture of unsaturated compound.The method that this patent provides divided for two steps, and the first step is carried out part and selected hydrogenation in fixed bed, to reduce the concentration of alkynes in the logistics.In second step, logistics is carried out selective hydrogenation at catalytic distillation tower behind the fixed bed hydrogenation, removes remaining C4 acetylenic impurity.Or the first step, select hydrogenation in a catalytic distillation tower C4 alkynes part, the C4 logistics is from cat head separation, condensation, and a part refluxes, and a part is delivered to fixed bed and is continued hydrogenation.Tower reactor weight and solvent cycle are to cat head, and to dissolve and to wash away the polymkeric substance of catalyst surface, in second step, overhead stream is removed remaining C4 acetylenic impurity at selecting property of fixed bed hydrogenation.The solvent that this patent is used comprises C4-C12 alkane, hexanaphthene, methylcyclohexane, benzene,toluene,xylene etc.The purpose of this method is to select hydrogenation and catalytic distillation selective hydrogenation to make up on fixed bed by a kind of specific order, make the rate of recovery of divinyl big as far as possible, use the polymkeric substance of dissolution with solvents, flushing catalyst surface, prolong the working time of catalytic distillation tower.Because the operation cycle of present ethylene unit is long, reach more than 3 years, though this patent has used circulating solvent to slow down the speed that catalyst activity reduces at catalytic distillation tower, can not satisfy macrocyclic requirement, catalytic distillation tower regeneration difficulty.
CN1501840A discloses the method for selecting hydrogenation to remove alkynes in the 1,3-butadiene from the mixture of unsaturated compound.Hydrogenation catalyst is selected in rectifying section filling at debutanizing tower, the polymkeric substance successive sedimentation causes activity of such catalysts to reduce at catalyzer in hydrogenation process, hydrogenation interrupts off and on, to contact with catalyzer for the solvent of soluble polymer, remove partial polymer, recover the part activity of catalyzer.This method uses solvent can prolong the duration of service of catalyzer, recover the catalyst member activity, but this tower periodical operation can not be satisfied the requirement of ethylene unit long-term operation.
CN1965063A discloses feed process and the device that a kind of processing comprises olefinic compounds and acetylenic compound.When reclaiming C4 and C 5 fraction, the cut of drawing that comprises acetylenic compound is carried out the hydrogenation processing, the position that material returns behind the hydrogenation is higher than extracts the position out.Because reaction unit is outside distillation tower, therefore regeneration can be satisfied the requirement of ethylene unit long-term operation with more catalyst changeout is easy.But reacting rear material is delivered to more than the input of column position, made the interior feed entrance point of distillation tower increase to the liquid load on the column plate between the reacting rear material in-position, tower diameter increases; Owing to the material with lower position turns back to eminence, the material back-mixing is unfavorable for separating of C4 and C5 on the other hand, and as reaching certain separation requirement, the theoretical stage of distillation tower and actual plate number will increase.Debutanizing tower for existing ethylene unit can not meet the demands, and needs to change the purpose that tower diameter is big, distillation tower that stage number is high just can reach this patent, and investment cost will increase.
In sum, by catalyzer and process modification, further improve the selectivity of C4 reaction, reduce the influence of catalyst deactivation, realize C4 hydrogenation highly selective, stable, the operation efficiently of long period, have huge economic benefit and realistic meaning.
Summary of the invention
The method of alkynes in a kind of selective hydrogenation and removing C-4-fraction of the present invention, this method is that compressed, alkali cleaning, dried splitting gas are entered in the separating unit debutanizing tower separating process, near charging opening stripping section enrichment EA, the liquid of VA are drawn rectifying tower, enter C4 alkynes reactor and select hydrogenation, return debutanizing tower after removing part or all of alkynes, be implemented in C
4With C
5 +In the cut separating process liquid of enrichment EA, VA is drawn rectifying tower and remove alkynes outward; This method comprises the steps:
(A) logistics 1 that comes from the depropanizing tower reactor enters debutanizing tower 2, utilizes in the rectifying divinyl in rectifying section 3 concentrate gradually, and thinning gradually at stripping section 4, near EA, VA concentration feed entrance point is higher; From all or part of liquid 14 of stripping section 4 appropriate location extraction, enter C4 alkynes reactor 15 with hydrogen 13, C4 alkynes reactor 15 is filled with the selection hydrogenation catalyst, removes part or all of alkynes therein.
(B) material 16 that comes out from C4 alkynes reactor 15 returns in the debutanizing tower 2 again;
(C) from the condensation condenser 5 of the isolated C 4 fraction of cat head, a phlegma part is back to the debutylize cat head, and extraction part 9 is delivered to butadiene extraction unit, and the non-condensable gas that is rich in light constituents such as hydrogen, methane is discharged from return tank 6.
(D) isolate the above cut 11 of C5 from tower reactor.
Described EA, VA are respectively ethylacetylene and vinylacetylene.The reflux ratio of described debutanizing tower 2 is 1～3, preferred 1.5～2.3.The appropriate location of all or part of liquid of described extraction is the 1st to the 8th block of plate in feed plate below, and the preferred the 3rd to the 6th block of plate, the material that reactor comes out turn back to first block of plate below the extraction plate.
The temperature of reaction of described C4 alkynes reactor 15 is 20～70 ℃, and preferred 30～50 ℃ of reaction pressures are 0.5～1.0MPa, preferred 0.6～0.8MPa.Described C4 alkynes reactor 15 can or soak bed bioreactor for trickle-bed reactor.In C4 alkynes reactor 15, be filled with the selection hydrogenation catalyst, employed catalyzer is existing disclosed catalyzer.
The aluminum oxide that the present invention selects load master active ingredient for use and helps active ingredient is as catalyzer, and wherein main active ingredient is selected from VIII family metal, as Pd.Be on the basis of main active constituent with palladium, can adding components such as silver, copper, lead respectively as the promotor component, making bimetallic catalyst.Or add the third or multiple metallic element.
The present invention extracts position and reflux ratio out by adjusting liquid phase, the butadiene concentration that enters C4 alkynes reactor 15 can be low to moderate 7%～32%, reduce the probability that divinyl is converted into butylene, butane, improve the selectivity of alkynes hydrogenation reaction, make divinyl in the process of alkynes hydrogenation reaction, not lose or be lost in below 0.25%.
The present invention extracts sepn process and shortening PROCESS COUPLING out liquid flow rate, C4 alkynes reactor catalyst loadings, C4 alkynes reactor process condition by adjusting debutanizing tower, makes the transformation efficiency of alkynes can reach 99.9%.
The present invention carries out in C4 alkynes reactor owing to hydrogenation reaction is drawn debutanizing tower, so just make the regeneration of C4 alkynes catalyst reactor and replacing easier, debutanizing tower is not subjected to the influence of the reactor cycle of operation of C4 alkynes, can satisfy the macrocyclic requirement of ethylene unit.
In the method for the invention, C4 alkynes reactor can be one, two or more, before first reactor, between the reactor water cooler can be arranged, and last reactor outlet logistics is returned in the debutanizing tower.Light constituents such as the hydrogen that unreacted finishes, methane turn back to debutanizing tower with C4; The debutanizing tower condenser is partial condenser, and non-condensable gas is discharged from return tank 6;
In the method for the invention, this C4 reactor can be trickle bed, also can be to soak bed.
In the method for the invention, because the C4 reactor is outside debutanizing tower, it is reactor independently, so just standby reactor can be set, use in order to switch during catalyst deactivation, its technology realizes approaching with traditional fixed bed C4 hydrogenator, and temperature and pressure can independently be controlled, and hydrogenation process is carried out under liquid-phase condition.
In the method for the invention, divinyl reaction probability descends in the C4 reactor, and polymkeric substance is reduced, so the speed that catalyst activity reduces reduces the prolongation of reactor operational cycle.
Employing can reduce the alkynes concentration that enters in the butadiene extraction unit C-4-fraction in the present invention, reduces the part energy consumption of two collections, saves the C4 hydrocarbon that is used for dilution, reduces environmental pollution.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Wherein 1 is the material that comes from the depropanizing tower reactor; 2 is debutanizing tower; 3 is the debutanizing tower rectifying section; 4 debutanizing tower stripping sections; 5 overhead condensers; 6 return tanks; 7 phlegmas; 8 phegmas; 9 cat head C4 extraction; 10 non-condensable gas extraction; The above cut extraction of 11 tower reactor C5; 12 debutanizing tower side line extraction; 13 hydrogen feed; The charging of 14C4 hydrogenator; The 15C4 hydrogenator; 16 reactor dischargings;
Embodiment 1
As shown in Figure 1, material 1 flow that comes from the depropanizing tower reactor is about 40t/h, and wherein 1,3-butadiene, EA, VA content are respectively 26w%, 0.07%, 0.7%, enter debutanizing tower 2 from middle position.Tower top pressure 0.44MPaA, 45 ℃ of tower top temperatures, 113 ℃ of tower reactor temperature, reflux ratio 1.8.
The downtake bottom seal of the following second block of plate of debutanizing tower feed plate, form an intercepting basin, side line extraction liquid 12 is extracted out with pump from intercepting basin, flow is about 80t/h, wherein 1,3-divinyl, EA, VA concentration are respectively 13w%, 0.02%, 0.18%, be cooled to after 30 ℃ through water cooler and mix with the hydrogen 13 (95mol%H2,5mol% methane) of 10kmol/h, enter fixed-bed reactor 15 then, filling C4 selects the about 9m3 of hydrogenation catalyst in the reactor, and reacted material 16 returns the 3rd block of column plate under the debutanizing tower feed plate from extracting the plate below out.The C4 hydrotreater is adiabatic reactor, 30 ℃ of temperature ins, pressure 0.6-1.0MPaA, reactor outlet EA, the about 15ppm of VA concentration, butadiene concentration about 13.1%.EA, VA transformation efficiency are near 100%.The flow of cat head extraction 9 is 20.2t/h, and wherein 1,3-butadiene content is 52.3w%, and EA, VA content are respectively 0.061w%, 0.6w%, and tower reactor extraction 11 flows are 19.8t/h, are mainly the C5+ cut.
This technology is with sepn process and the hydrogenation process coupling of C4 and C5+, one liquid stream in the tower is introduced the outer reactor of rectifying tower, hydrogenation reaction is carried out in this logistics in liquid phase, total VA, EA in the debutanizing tower raw material about 53%, 57% in reactor by hydrogenation and removing, reduced the concentration of alkynes in the cat head C 4 fraction, and divinyl free of losses, catalyst system therefor is for being the aluminium oxide catalyst of main active ingredient with palladium, and add silver as the promotor component, Pd content is at 0.2%, Ag content 0.3%.
Claims (5)
1. the method for alkynes in the selective hydrogenation and removing C-4-fraction, it is characterized in that, splitting gas is compressed, enter in the separating unit debutanizing tower separating process after the alkali cleaning, drying, near charging opening stripping section enrichment EA, the liquid of VA are drawn rectifying tower, enter C4 alkynes reactor and select hydrogenation, return debutanizing tower after removing part or all of alkynes, be implemented in C
4With C
5 +In the cut separating process liquid of enrichment EA, VA is drawn rectifying tower and remove alkynes outward; This method comprises the steps:
(A) logistics (1) that comes from the depropanizing tower reactor enters debutanizing tower (2), utilizes in the rectifying divinyl in rectifying section (3) concentrate gradually, and thinning gradually at stripping section (4), near EA, VA concentration feed entrance point is higher; From all or part of liquid of stripping section (4) appropriate location extraction (14), enter C4 alkynes reactor (15) with hydrogen (13), C4 alkynes reactor (15) is filled with the selection hydrogenation catalyst, removes part or all of alkynes therein;
(B) material (16) that comes out from C4 alkynes reactor returns in the debutanizing tower (2) again;
(C) from the condensation condenser (5) of the isolated C 4 fraction of cat head, a phlegma part is back to the debutylize cat head, and extraction part (9) is delivered to butadiene extraction unit; The non-condensable gas that is rich in light constituents such as hydrogen, methane is discharged from return tank (6);
(D) isolate the above cut of C5 (11) from tower reactor;
The reflux ratio of described debutanizing tower (2) is 1～3;
Described EA, VA are respectively ethylacetylene and vinylacetylene;
The appropriate location of all or part of liquid of described extraction is the 1st to the 8th block of plate in feed plate below, and the material that reactor comes out turns back to first block of plate below the extraction plate;
The temperature of reaction of described C4 alkynes reactor (15) is 20～70 ℃, and reaction pressure is 0.5～1.0MPa.
2. the method for alkynes in a kind of selective hydrogenation and removing C-4-fraction according to claim 1 is characterized in that, the appropriate location of all or part of liquid of described extraction is the 3rd to the 6th block of plate in feed plate below.
3. the method for alkynes in a kind of selective hydrogenation and removing C-4-fraction according to claim 1 is characterized in that the temperature of reaction of described C4 alkynes reactor (15) is 30～50 ℃, and reaction pressure is 0.6～0.8MPa.
4. the method for alkynes in a kind of selective hydrogenation and removing C-4-fraction according to claim 1 is characterized in that the reflux ratio of described debutanizing tower (2) is 1.5～2.3.
5. the method for alkynes in a kind of selective hydrogenation and removing C-4-fraction according to claim 1 is characterized in that, described C4 alkynes reactor (15) is optional to be trickle-bed reactor or immersion bed bioreactor.
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| CN105566032B (en) * | 2014-10-09 | 2017-12-22 | 中国石油化工股份有限公司 | The selection hydrogenation technique of rich alkynes carbon four |
| WO2021048655A1 (en) | 2019-09-13 | 2021-03-18 | Sabic Global Technologies B.V. | Integrated systems and methods for producing 1,3-butadiene via extractive distillation, distillation, and/or selective hydrogenation |
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| CN1965063A (en) * | 2004-04-09 | 2007-05-16 | 法国石油公司 | Method and device for processing a butadiene-containing feedstock |
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