CN102285860B - Selective hydrogenation process for C4 material flow with high concentration of alkyne - Google Patents
Selective hydrogenation process for C4 material flow with high concentration of alkyne Download PDFInfo
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Abstract
The invention relates to a selective hydrogenation process for a C4 material flow with high concentration of alkyne. The selective hydrogenation process comprises the following steps of: enabling the C4 material flow with the high concentration of alkyne to pass through one or more fixed bed hydrogenation reactors (I) with circulation pipelines, carrying out a selective hydrogenation reaction on the C4 mixture with high concentration of alkyne under the action of a catalyst to remove the alkine and generate butadiene and butylene, enabling the reactor to pass through a terminal reactor (II) without the circulation pipeline, and further removing the residual alkyne from the C4 material flow with the low concentration of alkyne. By utilizing the selective hydrogenation process and the catalyst provided by the invention, the concentration of the treated alkyne of the C4 material flow is as high as 20-50wt%, the concentration of alkyne of the hydrogenated C4 material flow can be reduced to below 1.5wt%, and the hydrogenated C4 material flow can be taken as the raw material for a butadiene extract device. According to the selective hydrogenation process disclosed by the invention, the C4 material flow is fully utilized and the yield of the butadiene is increased.
Description
Technical field
The present invention relates to the selection hydrogenation technique of a kind of high alkynes content C4 logistics, belong to petrochemical industry.
Technical background
1,3-butadiene is a kind of important industrial chemicals, is the main raw material of producing synthetic rubber and resin.The polymerization-grade divinyl requires purity greater than 99.7wt%, and alkynes content is lower than 25ppm.Be mainly derived from the mixed c 4 of hydrocarbon cracking ethylene by-product thing processed.The 1,3-butadiene that contains the 40-60wt% left and right in the cracking mixed c 4, the vinylacetylene of 0.5-2.0wt% (VA) and ethylacetylene (EA), all the other components are butane, butylene and a small amount of 1，2-butadiene, carbon three, carbon five.For the 1,3-butadiene of high-purity, make it satisfy polymerization-grade requirement or higher requirement, need to remove alkynes to the C4 logistics and process.Industrially mainly make with extra care product butadiene by the technique of two sections solvent extraction rectifying and one section direct rectifying.The alkynes of separating is except the VA that contains 20-40wt% and EA, also contain 1 of 10-20wt%, the 3-divinyl, this strand material is exactly so-called high alkynes C4, in industrial production, for the consideration of safety factors, usually process or do civil liquefied gas with making torch after the c4 fraction dilution, the alkynes incomplete combustion can cause environmental pollution, and this process energy consumption is large, loss of material is many, process economy is low.In addition, along with the heaviness of cracking stock and the increase of cracking severity, in the C4 logistics, alkynes content more and more comes high, the weight fraction of VA has surpassed 2%, adopt two sections traditional solvent extraction rectification process, increased the load of two extraction systems, energy consumption raises, the divinyl loss increases, and economical efficiency reduces.
Another removes the alkynes method for utilizing catalyzer to carry out catalysis selective hydrogenation.Namely utilize selective hydrogenation catalyst by hydrogenation reaction, the alkynes in the C4 logistics to be converted into divinyl, butylene and a small amount of butane.Alkynes in the C4 logistics reacts under the existence of selective hydrogenation catalyst and hydrogen, this hydrogenation reaction is thermopositive reaction, emit a large amount of heats in reaction process, cause temperature of reaction to rise suddenly, in addition, in the C4 logistics, the matter-pole such as divinyl is unstable, also can carry out polyreaction on catalyzer, thereby cause catalyzer to stop up and inactivation, the induce reaction raising of temperature of hydrogenation reaction heat release, can further accelerate polymer deposition speed again, this selective acetylene hydrocarbon hydrogenation technological operation not only be absolutely unsafe and also the life-span of catalyzer very short.If in the C4 logistics, alkynes and butadiene concentration are higher, consequence will be more serious.Therefore, the development selective hydrogenation catalyst is no doubt of crucial importance, but selects suitable selection acetylene hydrogenation technique even more important.
Accompanying drawing 2 is seen in traditional selection acetylene hydrogenation hydrocarbon technical process.To and/or enter the reactor I of a section or several sections series connection from the by-product C4 logistics 2 of hydrocarbon cracking ethene processed and hydrogen 1 and recycle stream 4 from the high alkynes C4 logistics of butadiene extraction unit, make the C4 logistics of high alkynes be transformed into the C4 logistics that contains lower concentration alkynes, as adopt the reactor of several sections series connection, must water cooler be set between each reactor region and allocate appropriate hydrogen into.Vapor-liquid separation tank II is sent in logistics 3 after hydrogenation, a part of logistics 4 of vapor-liquid separation tank liquid stream loops back the entrance of first paragraph/former sections reactor I for the dilution to high alkynes carbon 42 by pump, another part logistics 5 is hydrogenated products, can be used as the raw material of butadiene extraction unit.Recovery system is gone in the non-condensable gas phase logistics 6 that vapor-liquid separation tank goes out.The shortcoming of this technique is to dilute high alkynes carbon four with hydrogenated products as recycle stock, and the material treatment capacity is increased, and causes the increase of catalyst levels and the increase of process cost, but also can be because the hydrogenation again of hydrogenated products causes the loss of divinyl.
Patent CN1045950C invents a kind of process for selective hydrogenation, the operating time that a kind of extending catalyst is effectively feeded is proposed, catalyzer is distributed in a plurality of beds in same reactor, bed is come into operation successively, when the performance when catalyzer in operating process or the active product that is not suitable for obtaining to comply with relevant regulations, the additional new beds on the top just.This process for selective hydrogenation is complex process not only, and operation easier is high, invests larger.
A kind of selection acetylene hydrogenation method that can produce the high quality diene with extremely low acetylene content in long-time of patent CN1520387A invention, the method provides the selective hydrogenation district, in this reaction zone, when machining cell keeps on the go, in an implementation by selective hydrogenation catalyst is contacted in polymer solvent, diolefine charging and hydrogen, and the selective hydrogenation catalyst by will be in off-line the time only contacts with polymer solvent and hydrogen in second implementation, and catalyst activity is maintained on high level.This technique has been introduced polymer solvent, must add the device that removes polymer solvent.
Patent CN1872819A provides a kind of counter flow typed selective method for adding hydrogen, hybrid C 4 hydro carbons raw material and hydrogen respectively from the upper and lower of counter-current reactor in divider enters tower, the hydrocarbon fraction that flows downward and the mobile hydrogen that makes progress are in the catalyst surface counter current contact, be 0.1-3.0MPa at pressure, temperature of reaction is 40-100 ℃, volume space velocity 1-20h
-1Condition under react, simultaneously, the light gas in hybrid C 4 enters gas phase under the gas stripping of hydrogen, and unreacted hydrogen flows out from reactor head together; Hybrid C 4 product after refining flows out from reactor bottom.The hybrid C 4 hydro carbons raw material of this patent indication is the C4 mixture from the MTBE device.
Summary of the invention
The present invention provides a kind of improved C4 logistics selective hydrogenation that contains high alkynes to remove process of alkyne in order to reduce related shortcoming and the problem of technique of even avoiding prior art.
Adopt method of the present invention, by the fixed-bed reactor I of one or more series connection with circulation line, make the C4 logistics that contains high alkynes remove most of alkynes and generate divinyl and butylene by selective hydrogenation reaction under the effect of catalyzer, make the C4 logistics of high alkynes be transformed into the C4 logistics that contains lower concentration alkynes.The C4 logistics that makes low alkynes by the terminal fixed-bed reactor II without circulation line again with the effect of the identical or different catalyzer of leading portion fixed bed under select hydrogenation that hydrogen and alkynes are reacted, under the processing condition of the best, further remove the technique of remaining alkynes, can alleviate the load of butadiene extraction unit, making alkynes be converted into valuable cut is used, reduce the loss of butane, butylene and 1,3-butadiene, will increase economic efficiency widely.
Accompanying drawing 1 has been described process flow diagram of the present invention
In figure, I is that one or more series connection are with the fixed-bed reactor of circulation line; II is the terminal fixed-bed reactor without circulation line; III is vapor-liquid separating device; 1 hydrogen, 2 high alkynes C4 logistics, 3 circulation line logistics, 4 low alkynes C4,5 low alkynes C4 remove end reactor, and 6 gas phases are gone recovery system, and 7 products go butadiene extraction unit
Detailed technological process is as follows:
(1) will from the C4 logistics of the high alkynes content of butadiene extraction unit and/or from the by-product C4 logistics 2 of hydrocarbon cracking ethene processed with after recycle stock 3 from the vapor-liquid separating device III mixes, enter the fixed bed selective hydrogenation reaction device I of one or more series connection together with hydrogen, when adopting the fixed-bed reactor of a plurality of series connection, each reactor all should arrange water cooler and hydrogen make-up before each reactor; Under the effect of the selective hydrogenation catalyst that loads in reactor, alkynes wherein is converted into butylene and divinyl, and selective hydrogenation reaction device I operates under 0.6-4.0MPa, and temperature in is 20-80 ℃, and the liquid volume air speed is 1-100h
-1
(2) send into the vapor-liquid separating device III by the C4 logistics after hydrogenator I hydrogenation after heat exchange, be separated into gas and liquid, the partially liq material loops back the entrance of first paragraph fixed bed selective hydrogenation reaction device I by recycle pump, mix with high alkynes C4 logistics, hydrogenating materials as the first paragraph reactor, its internal circulating load is 5: 1～100: 1 with the feed weight ratio of high alkynes C4 logistics, and all the other liquid materials are sent into hypomere fixed bed selective hydrogenation reaction device, i.e. end reactor II.
(3) product liquid from the vapor-liquid separating device III enters the end reactor II together with hydrogen, the selective hydrogenation catalyst identical or different with I is housed in the end reactor II, under the effect of catalyzer, make residue alkynes wherein be converted into butylene and divinyl, the working pressure of end reactor II is 0.6-4.0MPa, temperature in is 30-80 ℃, and the liquid volume air speed is 0.2-50h
-1
The product 7 that obtains is rich in 1,3-butadiene, can be used as the raw material of butadiene extraction unit.Recovery system is gone in the non-condensable gas phase logistics 6 that vapor-liquid separation tank goes out.
The residual fraction that contains high concentration ethylene ethyl-acetylene and butine that high alkynes C4 logistics in this technique is mainly discharged from two extraction part alkynes washing towers of butadiene extraction unit.
The by-product C 4 fraction of hydrocarbon cracking ethene processed contains the cuts such as butane, butylene, divinyl, butine, vinylacetylene usually, and wherein the alkynes total amount is 10-50wt%.The hydrogenator I is the fixed bed selective hydrogenation reaction device of one or more series connection, can be single hop, two sections or multistage insulation formula bubbling bed or trickle-bed reactor, and reactor is with circulation line, and the mol ratio of every section reactor inlet place's hydrogen and the total alkynes amount of this section reactor inlet material is 0.2-4.0.The hydroprocessing condition that adopts in hydrogenator can suitably change according to the composition and property of processed C4 logistics, temperature is low as far as possible, to prevent the polymerization of divinyl and alkynes, temperature in 20-80 ℃, the selection of pressure should make the C4 logistics be in liquid state, be typically chosen in fixed bed selective hydrogenation reaction device and operate under 0.6-4.0MPa, the liquid volume air speed is 1-100h
-1From the weight ratio of the internal circulating load of vapor-liquid separation tank III logistics 3 out and the high alkynes C4 logistics 2 that enters the hydrogenator I 5: 1～100: 1, alkynes content according to the C4 logistics, choose reasonable reactor number of units, hydrogen alkynes ratio, recycle ratio, temperature of reaction guarantee the alkynes total content of hydrogenator C4 logistics out is down to below 2.5wt%.Final stage fixed bed selective hydrogenation reaction device II does not have circulation line, and in ingress hydrogen and C4 material, the mol ratio of alkynes total amount is 0.5-5.0, operates under 0.6-4.0MPa, and temperature in is 20-80 ℃, and the liquid volume air speed is 0.2-50h
-1
Selective hydrogenation catalyst is that one or more in palladium, rhodium, platinum, nickel are carried on carrier, preferred palladium, also contain one or both in lead, tin for promotor, preferred plumbous, it is promotor that catalyzer also contains the above mixture of one or two or more that is selected from potassium, sodium, lithium, calcium, magnesium, barium, fluorine, copper, silver, gold, zinc, manganese, bismuth, molybdenum, zirconium, rare earth element.The plumbous two-pack of the preferred palladium of catalyzer or the plumbous multicomponent catalyst of palladium.Carrier is selected from more than one the mixture in aluminum oxide, silicon oxide, spinel, diatomite, titanium oxide, zinc oxide, stannic oxide, molecular sieve.That preferential oxidation aluminium, its shape are selected from is granular, spherical, one or more in gear-like, foliated lamellar or strip.The method that the preparation method of catalyzer is well known to those skilled in the art.
The present invention directly selects hydrogenation to the C4 logistics of high alkynes, and alkynes is converted into butylene and divinyl, is mainly 1-butylene.Hydrogenation products can obtain the 1-butylene product by further refining.
The present invention adopts two kinds of different selective hydrogenation reaction devices, for selective hydrogenation reaction device I, because alkynes content in charging is too high, should adopt large-scale selective hydrogenation reaction device, reaction product is looped back the method for reactor inlet, and internal circulating load is larger, has reduced hydrogenator entrance alkynes content, thereby reduced the temperature rise of reaction bed, effectively suppressed the generation of polymkeric substance; Because having selected larger backflow linear speed, make material to catalyst surface, certain washing action be arranged again, effectively suppressed polymkeric substance and deposited on catalyst surface, make catalyzer can keep for a long time good catalytic performance.And in the hydrogenator II of terminal, due to this moment reactor inlet alkynes content be down to 1.5～2.5wt%, the excessive temperature rise of bed can not induce reaction, employing is directly sent vapour liquid separator III liquid phase C4 logistics and hydrogen out into selective hydrogenation reaction device II without the reactor of circulation line and adopt.Adopt such technique not only can be in the situation that do not affect selective hydrogenation catalyst work-ing life with the less relatively large C4 logistics of reactor for treatment.Avoid the repetition hydrogenation of the C4 logistics of lower concentration alkynes, also can greatly reduce the loss of divinyl.The selective hydrogenation catalyst of the present invention development is that to contain the plumbous two-pack of palladium and/or also contain the above mixture of one or two or more that is selected from potassium, sodium, lithium, calcium, magnesium, barium, fluorine, copper, silver, gold, zinc, manganese, bismuth, molybdenum, zirconium, rare earth element be promotor.This catalyzer has activity and selectivity and long life-span preferably.
Description of drawings Fig. 1 is process flow diagram of the present invention.
Fig. 2 is the contrast schema.I: several reactor II of first paragraph/series connection: vapor-liquid separation tank; 1 hydrogen, 2 high alkynes C4, carbon four, 4 circulation lines after 3 hydrogenation, 5. product goes butadiene extraction unit, and 6. gas phase is gone recovery system
Specific embodiment
Embodiment 1
The raw material that the present embodiment adopts is the high alkynes carbon four that industrial butadiene extraction unit is discharged, catalyzer adopts the described many metals selective hydrogenation catalyst of CN00107257.9, and support of the catalyst is Al2O3, and metal component content is: palladium 0.2wt%, copper 11.3wt%, silver-colored 0.2wt%.Adopt two sections insulation fix bed techniques, first stage reactor loaded catalyst 50ml, second stage reactor loaded catalyst 20ml.Fresh high alkynes C4 and the C4 that loops back after the first stage reactor are mixed into first stage reactor, and first stage reactor exit portion C4 is circulated to the first stage reactor entrance, and rest part enters second stage reactor, recycle ratio 19.Second stage reactor is as end reactor.30 ℃ of first stage reactor temperature ins, pressure 1.6MPa, hydrogen alkynes be than 0.6, air speed (LHSV) 16h
-134 ℃ of second stage reactor temperature ins, pressure 1.2MPa, hydrogen alkynes be than 0.8, air speed (LHSV) 2h
-1
Raw material product composition (wt%)
| Component | High alkynes raw material | The first stage reactor outlet | The second stage reactor outlet |
| C3H8+C3H6 | 0.68 | 1.45 | 1.47 |
| MA | 0.78 | 0.02 | 0.00 |
| i-C4H10 | 1.01 | 0.99 | 0.99 |
| n-C4H10 | 3.40 | 3.35 | 3.38 |
| c-C4H8 | 2.88 | 4.02 | 4.28 |
| 1-C4H8 | 7.42 | 22.31 | 22.80 |
| t-2-C4H8 | 3.64 | 5.95 | 6.02 |
| i-C4H8 | 14.20 | 13.96 | 13.95 |
| 1，2-BD | 18.12 | 12.65 | 12.38 |
| 1，3-BD | 12.75 | 32.38 | 32.57 |
| VA | 26.95 | 0.85 | 0.34 |
| EA | 7.90 | 1.29 | 1.03 |
| C5+ | 0.26 | 0.76 | 0.77 |
Embodiment 2
The raw material that the present embodiment adopts is the high alkynes carbon four that industrial butadiene extraction unit is discharged, and catalyzer adopts palladium/plumbous selective hydrogenation catalyst, and support of the catalyst is Al2O3, and metal component content is: palladium 0.3wt%, plumbous 0.2wt%.Adopt two sections insulation fix bed techniques, first stage reactor loaded catalyst 50ml, second stage reactor loaded catalyst 20ml.Fresh high alkynes C4 and the C4 that loops back after the first stage reactor are mixed into first stage reactor, and first stage reactor exit portion C4 is circulated to the first stage reactor entrance, and rest part enters second stage reactor, recycle ratio 19.Second stage reactor is as end reactor.29 ℃ of first stage reactor temperature ins, pressure 1.0MPa, hydrogen alkynes be than 0.75, air speed (LHSV) 40h
-136 ℃ of second stage reactor temperature ins, pressure 0.8MPa, hydrogen alkynes be than 1.0, air speed (LHSV) 5h
-1
Raw material product composition (wt%)
| Component | High alkynes raw material | The first stage reactor outlet | The second stage reactor outlet |
| C3H8+C3H6 | 0.68 | 1.45 | 1.47 |
| MA | 0.78 | 0.03 | 0.00 |
| i-C4H10 | 1.01 | 1.02 | 1.02 |
| n-C4H10 | 3.41 | 3.35 | 3.39 |
| c-C4H8 | 2.88 | 3.99 | 4.25 |
| 1-C4H8 | 7.42 | 21.92 | 22.39 |
| t-2-C4H8 | 3.64 | 5.90 | 5.97 |
| i-C4H8 | 14.20 | 14.08 | 14.11 |
| 1，2-BD | 18.12 | 12.65 | 12.38 |
| 1，3-BD | 12.75 | 32.79 | 32.97 |
| VA | 26.95 | 0.79 | 0.28 |
| EA | 7.90 | 1.36 | 1.09 |
| C5+ |
Comparative Examples 1
This Comparative Examples adopts raw material and the catalyzer identical with embodiment 2.Adopt two sections insulation fix bed techniques, first stage reactor loaded catalyst 50ml, second stage reactor loaded catalyst 50ml.Fresh high alkynes C4 and the C4 that loops back after the second stage reactor are mixed into first stage reactor, and first stage reactor enters second stage reactor; Second stage reactor exit portion C4 is circulated to the first stage reactor entrance, and rest part is exported as hydrogenation products, recycle ratio 19.30 ℃ of first stage reactor temperature ins, pressure 1.6MPa, hydrogen alkynes be than 0.55, air speed (LHSV) 16h
-135 ℃ of second stage reactor temperature ins, pressure 1.4MPa, hydrogen alkynes be than 0.8, air speed (LHSV) 16h
-1
Raw material product composition (wt%)
| Component | High alkynes raw material | The first stage reactor outlet | The second stage reactor outlet |
| C3H8+C3H6 | 0.68 | 1.45 | 1.47 |
| MA | 0.78 | 0.02 | 0.00 |
| i-C4H10 | 1.01 | 0.99 | 0.99 |
| n-C4H10 | 3.41 | 3.97 | 4.01 |
| c-C4H8 | 2.88 | 7.65 | 7.87 |
| 1-C4H8 | 7.42 | 22.03 | 22.51 |
| t-2-C4H8 | 3.64 | 5.87 | 5.93 |
| i-C4H8 | 14.20 | 13.93 | 13.93 |
| 1，2-BD | 18.12 | 10.87 | 10.64 |
| 1，3-BD | 12.75 | 30.76 | 30.80 |
| VA | 26.95 | 0.54 | 0.20 |
| EA | 7.90 | 1.27 | 1.02 |
| C5+ | 0.26 | 0.64 | 0.65 |
The raw material that the present embodiment adopts is the high alkynes carbon four that industrial butadiene extraction unit is discharged, and catalyzer adopts palladium/plumbous selective hydrogenation catalyst, and support of the catalyst is Al2O3, and metal component content is: palladium 0.3wt%, plumbous 0.2wt%.Adopt three sections insulation fix bed techniques, first stage reactor loaded catalyst 100ml, second stage reactor loaded catalyst 100ml, three sections reactor catalyst loadings 30ml.Fresh high alkynes C4 and the C4 that loops back after the second stage reactor mix and allocate a certain amount of hydrogen into after enter first stage reactor, allocate a certain amount of hydrogen after the first stage reactor outlet material is cooling into and enter second stage reactor, second stage reactor exit portion C4 is circulated to the first stage reactor entrance, rest part enters three sections reactors, recycle ratio 11.Three sections reactors are as end reactor.29 ℃ of first stage reactor temperature ins, pressure 1.2MPa, hydrogen alkynes be than 0.6, air speed (LHSV) 60h
-134 ℃ of second stage reactor temperature ins, pressure 1.0MPa, hydrogen alkynes be than 0.8, air speed (LHSV) 60h
-136 ℃ of three sections reactor inlet temperatures, pressure 0.8MPa, hydrogen alkynes be than 1.2, air speed (LHSV) 20h
-1
Raw material product composition (wt%)
| Component | High alkynes raw material | The first stage reactor outlet | The second stage reactor outlet | Three sections reactor outlets |
| C3H8+C3H6 | 0.68 | 1.45 | 1.47 | 1.47 |
| MA | 0.78 | 0.03 | 0.00 | 0.00 |
| i-C4H10 | 1.01 | 0.99 | 1.02 | 1.03 |
| n-C4H10 | 3.41 | 3.37 | 3.42 | 3.54 |
| c-C4H8 | 2.88 | 3.78 | 3.84 | 4.35 |
| 1-C4H8 | 7.42 | 19.72 | 20.46 | 21.82 |
| t-2-C4H8 | 3.64 | 5.48 | 5.59 | 6.12 |
| i-C4H8 | 14.20 | 13.98 | 13.97 | 13.96 |
| 1，2-BD | 18.12 | 13.06 | 12.79 | 11.53 |
| 1，3-BD | 12.75 | 33.31 | 33.98 | 34.08 |
| VA | 26.95 | 2.03 | 0.99 | 0.35 |
| EA | 7.90 | 2.21 | 1.85 | 1.13 |
| C5+ | 0.26 | 0.59 | 0.61 | 0.62 |
Claims (5)
1. selection hydrogenation technique that contains the C4 logistics of high alkynes, it is characterized in that, it is to contain the C4 logistics of high density alkynes by one or more fixed bed hydrogenation reactors with circulation line (I), make the C4 mixture that contains high density alkynes remove most of alkynes and generate divinyl and butylene by selective hydrogenation reaction under the effect of catalyzer, again by the end reactor (II) without circulation line, the C4 logistics that makes low alkynes with the effect of the identical or different catalyzer of leading portion fixed bed under select hydrogenation that hydrogen and alkynes are reacted, make the C4 logistics that contains low alkynes further remove remaining alkynes, this technique comprises the steps:
(1) the C4 logistics of high alkynes content is with after recycle stock mixes, enter the fixed bed selective hydrogenation reaction device (I) of one or more series connection together with hydrogen, when adopting the fixed-bed reactor of a plurality of series connection, water cooler all should be set and hydrogen make-up before each reactor after each reactor; Under the effect of the selective hydrogenation catalyst that loads in reactor, alkynes wherein is converted into butylene and divinyl, and fixed-bed reactor operate under 0.6-4.0MPa, and temperature in is 20-80 ℃, and the liquid volume air speed is 1-100h
-1
(2) send into vapor-liquid separating device (III) by the C4 logistics after hydrogenator (I) hydrogenation after heat exchange, be separated into gas and liquid, the partially liq material loops back the entrance of first paragraph fixed bed selective hydrogenation reaction device (I) by recycle pump, mix with high alkynes C4 logistics, hydrogenating materials as the first paragraph reactor, its internal circulating load is 5:1～100:1 with the feed weight ratio of high alkynes C4 logistics, all the other liquid materials are sent into hypomere fixed bed selective hydrogenation reaction device, i.e. end reactor (II);
(3) product liquid from vapor-liquid separating device (III) enters end reactor (II) together with hydrogen, the selective hydrogenation catalyst identical or different with (I) is housed in end reactor (II), under the effect of catalyzer, make residue alkynes wherein be converted into butylene and divinyl, the working pressure of end reactor (II) is 0.6-4.0MPa, temperature in is 20-80 ℃, and the liquid volume air speed is 0.2-50h
-1
Alkynes in described high alkynes C4 logistics comprises methylacetylene (MA), ethylacetylene (EA) and vinylacetylene (VA);
Described high alkynes C4 logistics derives from butadiene extraction unit, and in high alkynes C4 logistics, the alkynes total amount is up to 20-50wt%;
Described selective hydrogenation catalyst is that one or more in palladium, rhodium, platinum, nickel are carried on supported catalyst, and carrier is selected from one or more the mixture in aluminum oxide, silicon oxide, spinel, diatomite, titanium oxide, zinc oxide, stannic oxide, molecular sieve.That its shape is selected from is granular, spherical, one or more in gear-like, foliated lamellar or strip.
2. a kind of selection hydrogenation technique that contains high alkynes C4 logistics according to claim 1, is characterized in that, it is promotor that described hydrogenation catalyst also randomly contains lead and/or tin.
3. a kind of selection hydrogenation technique that contains high alkynes C4 logistics according to claim 1, it is characterized in that, it is promotor that described hydrogenation catalyst also randomly contains one or more the mixture that is selected from potassium, sodium, lithium, calcium, magnesium, barium, fluorine, copper, silver, gold, zinc, manganese, bismuth, molybdenum, zirconium, rare earth element.
4. a kind of selection hydrogenation technique that contains high alkynes C4 logistics according to claim 1, is characterized in that, described catalyzer is the plumbous two-pack of palladium or the plumbous multicomponent catalyst of palladium, and carrier is aluminum oxide.
5. a kind of selection hydrogenation technique that contains high alkynes C4 logistics according to claim 1, it is characterized in that described fixed bed selective hydrogenation reaction device (I) and (II) are heat-insulating bubbling bed or trickle-bed reactor, fixed bed selective hydrogenation reaction device (I) is the reactor of one or more series connection, with circulation line, in every section ingress hydrogen and C4 material, the mol ratio of alkynes total amount is 0.2-4.0; Terminal hydrogenator (II) does not have circulation line, and in ingress hydrogen and C4 material, the mol ratio of alkynes total amount is 0.5-5.0.
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| CN102627519B (en) * | 2012-03-28 | 2014-09-10 | 清华大学 | Method and system for preparing butadiene |
| CN103788317B (en) * | 2012-10-30 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of hydrogenation of polymer reaction method containing olefines unsaturated bond |
| CN104075909B (en) * | 2013-03-28 | 2017-02-08 | 中国石油天然气股份有限公司 | Method for sampling flammable and explosive high alkyne classes |
| WO2017170421A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Hydrogenation method |
| CN109485536B (en) * | 2017-09-13 | 2021-07-30 | 中国石油化工股份有限公司 | Selective hydrogenation method for alkyne and/or diene in carbon four fraction |
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