CN105732255B - A kind of method of alkynes selective hydrogenation - Google Patents
A kind of method of alkynes selective hydrogenation Download PDFInfo
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Abstract
A kind of method of alkynes selective hydrogenation, to be rich in the C-4-fraction of alkynes after Butadiene Extraction as raw material, in the presence of a catalyst, using adiabatic reactor, selection plus hydrogen obtain 1,3 butadiene, the process condition used for：It is 20~60 DEG C to react inlet temperature, and reaction pressure is 1.0~3.0MPa, and liquid air speed is 8~20h‑1.Catalyst is the palladium lead catalyst using niobium oxide aluminium oxide as carrier.Method using the present invention, for be rich in after Butadiene Extraction the efficiently using of C-4-fraction of alkynes, reduce the wasting of resources, increasing economic efficiency has fairly obvious good result.
Description
Technical field
The present invention relates to a kind of methods of the selection plus hydrogen of height unsaturated hydrocarbons.
Background technology
The fourth of mass fraction 40%~60% is usually contained in the cracking c_4 fraction of hydrocarbons pyrolysis ethylene by-product
Diene, butadiene are the important monomers of China Synthetic Rubber Industry.Butadiene generally use solvent is extracted from cracking c_4 fraction to take out
Formulation, such as acetonitrile method, N methylpyrrolidone process and dimethylformamide method.Due to alkyne concentration in the C-4-fraction after extracting
It is higher, and there is no industrial utility value at present, burning processing can only be made, but because high concentration alkynes has the danger of explosion, therefore
In the industrial production for safety factor the considerations of, to discharge the butadiene of equivalent when detaching alkynes simultaneously, and need to be with suitable
Torch burning can be just sent after the dilution of the fractions such as butylene, butane.This not only causes the prodigious wasting of resources, also polluted environment.
These factors have resulted in traditional four solvent extraction apparatus energy consumption of carbon and have risen, and butadiene loss is serious, and economy is deteriorated.Due to
The influence of the factors such as cracking severity and cracking technique, alkynes content causes to extract in trend is gradually increased in cracking c_4 fraction
The loss increase of butadiene and energy consumption increase in the process.Meanwhile with the development of organic synthesis industrial technology, to alkynes in butadiene
The limitation of hydrocarbon content is also more stringent, these factors cause the economy of butadiene extraction device to be deteriorated.In extracting butadiene
When, recovery section butadiene after selective acetylene hydrocarbon hydrogenation can not only achieve the purpose that turn waste into wealth, but also to reducing alkynes row
It puts and prevents the pollution of the environment and also function to important function.
Four acetylene hydrogenation technique of carbon is broadly divided into front-end hydrogenation technique and back end hydrogenation technique.Front-end hydrogenation technique is by C-4-fraction
In be stripped butadiene again after alkynes is chosen plus hydrogen；Back end hydrogenation technique is to be rich in alkynes to what is discharged after extracting butadiene
C-4-fraction carry out selection plus hydrogen, convert after 1,3-butadiene vinylacetylene to and return to extraction device and recycle butadiene.
ZL200810239462.3 discloses a kind of method of selective acetylene hydrocarbon hydrogenation, the fixed bed reactors that this method uses
For single hop or multistage isotherm formula bubbling bed reactor, the process condition used for：Reaction temperature is 30~90 DEG C, reaction pressure
Power is 1.0~4.0MPa, and liquid air speed is 7~20h-1.The catalyst used is palladium system Cu-contained catalyst.
CN102731240A discloses a kind of method that the selection of carbon four adds hydrogen to produce butadiene, which is front-end hydrogenation work
Skill, using two sections of fixed bed adiabatic formula reactors, process conditions are：30~60 DEG C of inlet temperature of reaction, reaction pressure 0.6~
2.0MPa, four 10~60h of liquid air speed of carbon-1, hydrogen alkynes is than 0.2~10mol/mol.The catalyst of use include alumina support,
0.01~1wt%Pd, 0.01~5wt%Pb and total content be the rare-earth elements La of 0.01~10wt%, one kind in Pr, Nd or
It is several.
ZL03159238.4 discloses a kind of selection hydrogenation technique of the hydrocarbon material flow rich in alkynes, and what which used consolidates
Fixed bed reactor is single hop or multistage insulation formula bubbling bed reactor, and 10~40 DEG C of inlet temperature, liquid air speed is 0.5~5h-1,
The recycle ratio of product circulation amount and fresh material is 6:1~30:1.Under this process condition, the conversion ratio of alkynes 98% with
On, the yield of 1,3-butadiene is 98% or so.But the liquid air speed of the technique is smaller, and product circulation amount and fresh material are followed
Ring is relatively high, and heat exchanger is housed between every section of multi-stage fixed-bed reactor.
CN85106117A discloses alkynes and alkadienes catalysis selective hydrogenation technique in a kind of monoolefine, exhausted using single hop
Hot type trickle bed reactor, to α-Al2O3For the palladium catalyst of carrier, mainly for the treatment of C3Fraction, alkynes after hydrogenation reaction
It is below 5% with diene content.
Invention content
The object of the present invention is to provide a kind of methods of alkynes selective hydrogenation, specifically provide a kind of Butadiene Extraction
Afterwards be rich in alkynes C-4-fraction process for selective hydrogenation, for handle containing butane, butylene, butadiene, vinylacetylene,
The C-4-fractions such as butine, carry out vinylacetylene therein plus hydrogen is to recycle butadiene, improve resource added value, reduce and throw
Money improves device economic benefit.
A kind of method of alkynes selective hydrogenation of the present invention, this method include waiting for hydrogenation material and H2Into thermal insulation
Reactor is mounted with selective hydrocatalyst, the molar ratio of hydrogen and the total alkynes content of reactor inlet in adiabatic reactor
It is 0.8~3.0；20~60 DEG C of inlet temperature is reacted, reaction pressure is 1.0~3.0MPa, and liquid volume air speed is 8~20h-1,
Reaction product is detached into knockout drum after cooling；It is described wait for hydrogenation material be C-4-fraction rich in alkynes,
The mixture of C-4-fraction and dilution material rich in alkynes；The carrier of selective hydrocatalyst is answering for aluminium oxide and niobium oxide
Close carrier, by total catalyst weight for 100wt% in terms of, catalyst include 0.1~1.0wt% of palladium, preferably 0.2~0.6wt%；Lead
2~10wt%, preferably 3~8wt%；0.5~3wt% of niobium oxide, preferably 1~3wt%, 80~97wt% of aluminium oxide；Described
Aluminium oxide is θ-Al2O3And/or δ-Al2O3。
A kind of method of alkynes selective hydrogenation disclosed in this invention, described waits for that hydrogenation material is the carbon rich in alkynes
The mixture of four fractions or C-4-fraction rich in alkynes and dilution material.The C-4-fraction for being wherein rich in alkynes is taken out from butadiene
Device is carried, is the higher C-4-fraction of alkynes content remaining after Butadiene Extraction, usually contains butylene, butane, butadiene, second
Vinyl acetylene, butine key component.C-4-fraction medium vinyl acetylene mass content rich in alkynes is usually 15~25wt%,
Butadiene mass content is usually 12~20wt%.
The method of alkynes selective hydrogenation disclosed in this invention, when waiting for hydrogenation material and H2Into adiabatic reactor
When, wait for that the alkynes mass content in hydrogenation material is preferably not higher than 10wt%.Wait for that hydrogenation material is the C-4-fraction rich in alkynes
Or the mixture of the C-4-fraction rich in alkynes and dilution material；When alkynes content is higher than 10wt% in the C-4-fraction rich in alkynes
When, the C-4-fraction that preferably will be enriched in alkynes expects dilution with dilution, and the weight ratio that the C-4-fraction rich in alkynes is expected with dilution is most
It is 1 well:1~4；Most common dilution material is carbon-4.
The method of alkynes selective hydrogenation disclosed in this invention, the adiabatic reactor are trickle bed adiabatic reactor
Or two kinds of bubbling bed adiabatic reactor.The present invention recommends bubbling bed adiabatic reactor, preferably single hop or multistage insulation formula
Bubbling bed reactor.For single stage adiabatic formula bubbling bed reactor, the molar ratio of hydrogen and the total alkynes content of reactor inlet is most
It is 1.0~2.5 well.The multistage insulation formula bubbling bed reactor refers to containing heat-insulating bubbling bed more than double sections or double sections
Reactor, when using multistage insulation formula bubbling bed reactor, every section of inlet amounts of hydrogen is waited for this section of inlet in hydrogenation material
The molar ratio of alkynes total amount is preferably 1.0~2.0.The method disclosed in the present, in adiabatic reactor can according to raw material difference,
Different reaction conditions is selected, since the reaction is liquid phase reactor, the selection of temperature and pressure should all make raw material be in liquid
State, and temperature cannot be too high, to prevent the polymerization of alkene and alkynes；Reaction inlet temperature is generally 20~60 DEG C, preferably
25~50 DEG C；Reaction pressure is generally 1.0~3.0MPa, preferably 1.0~2.0MPa；Liquid air speed is 8~20h-1, preferably
10~18h-1；The weight ratio of raw material and dilution material is preferably 1:1~4.
The carrier of the method for alkynes selective hydrogenation disclosed in this invention, selective hydrocatalyst therein is oxidation
The complex carrier of aluminium and niobium oxide, by total catalyst weight for 100wt% in terms of, catalyst include 0.1~1.0wt% of palladium, preferably
0.2~0.6wt%；2~10wt% of lead, preferably 3~8wt%；0.5~3wt% of niobium oxide, preferably 1~3wt%, aluminium oxide 80
~97wt%.
The method of alkynes selective hydrogenation disclosed in this invention, the selective hydrocatalyst, carrier are oxygen
The complex carrier for changing aluminium and niobium oxide, no matter catalyst activity component is reduction-state or oxidation state, metal niobium is always with oxidation
State form exists, and forms complex carrier with aluminium oxide.The present invention is described its existing forms with niobium oxide, actually oxygen
There are many chemical valence states for niobium in change niobium, such as have niobium pentaoxide (Nb2O5), columbium sesquioxide (Nb2O3), columbium dioxide
(NbO2) and columbium monoxide (NbO), the niobium oxide in the present invention can be niobium pentaoxide, columbium dioxide, preferably five oxidations two
Niobium.
The content of the method for alkynes selective hydrogenation disclosed in this invention, the niobium oxide is 0.5~3wt%.When
When content is less than 0.5wt%, introduces niobium oxide and unobvious are acted on to the performance for improving catalyst carrier；When content is higher than 3wt%
When, the addition of niobium oxide can greatly improve the acidity of catalyst carrier, especially B acid amount and increase, this can lead to catalyst choice
Property poor and easy gum deposit inactivation, the selection for being highly detrimental to catalyst adds hydrogen.
The method of alkynes selective hydrogenation disclosed in this invention, selective hydrocatalyst therein include alkali metal
And/or 0.5~5wt% of alkaline-earth metal, preferably 1~4wt%；Also it may include one kind in auxiliary agent gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium
Or it is a variety of, content is 0~2wt%, preferably 0.2~1.8wt%.The specific surface area of catalyst is 20~80m2/ g, specific pore volume are
0.2~0.7ml/g.
Special recommendation of the present invention may be used in the method for alkynes selective hydrogenation disclosed in this invention, the catalyst
Following specific preparation methods but catalyst used in the present invention be not limited in being obtained with the method, the preparation side of catalyst
Method specific steps include：
The preparation of A catalyst carriers
By boehmite and mixer kneader containing niobium compound, extruded moulding, 100~130 DEG C of dryings, 800~1100 DEG C
2~6h is roasted, catalyst carrier is made；
B impregnates active component
Prepare the solution containing 0.1~1.0wt% palladiums and 2~10wt% lead, adjustment pH value to 1.0~5.0, substep or total immersion
Stain is on catalyst complex carrier, through 100~130 DEG C of dry 2~6h, 300~700 DEG C of 3~6h of roasting.
The preparation of catalyst carrier of the present invention may be：Boehmite and the mixing containing niobium compound are pinched
It closes, extruded moulding, niobium oxide and alumina composite carrier is made in 100~130 DEG C of dryings, 400~700 DEG C of 2~6h of roasting.
The preparation method of catalyst of the present invention, when containing alkali metal and/or alkaline-earth metal in catalyst, alkali gold
Belong to and/or alkaline-earth metal is supported on aluminium oxide and niobium oxide complex carrier.Obtain urging containing alkali metal or/and alkaline-earth metal
Agent carrier is very versatile technology, and common in the art there are two types of approach：One is alkali is added before carrier is molded
Metal or/and alkaline-earth metal, one is after carrier shaping and roasting by prepare after corresponding soluble salt solutions dipping it is dry,
What roasting obtained.The present invention is not limited thereto.The method that one of the following may be used obtains：Method one：By aluminium oxide and oxygen
Change niobium complex carrier be impregnated in the solution of alkali metal containing and/or alkaline-earth metal, through 100~130 DEG C of dry 2~6h, 800~
1100 DEG C of 3~8h of roasting, are made the catalyst carrier of alkali metal containing and/or alkaline-earth metal.Method two：By alkali metal containing and/or
The compound of alkaline-earth metal is mixed together with boehmite, containing niobium compound, nitric acid and water, through mediating, be molded, then through 100
~130 DEG C of dry 2~6h, 800~1100 DEG C of 3~8h of roasting, are made the catalyst carrier of alkali metal containing and/or alkaline-earth metal.
The method of alkynes selective hydrogenation disclosed in this invention, the preparation method of the catalyst, when catalyst contains
When one or more promoter metals in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, in step B activity metal impregnation, drying, roasting
After burning, impregnation aids metal, process conditions are：With one or more solvable in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium
Property the salting liquid substep or obtained products of co-impregnation step B, through 100~130 DEG C of dry 2~6h, 300~700 DEG C roast 3~6h
Catalyst is made.
The method of alkynes selective hydrogenation disclosed in this invention, the preparation method of the catalyst, when in catalyst
When one or more promoter metals containing alkali metal and/or alkaline-earth metal, in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, first make
For the catalyst carrier containing alkali metal and/or alkaline-earth metal, then active component is impregnated, then impregnation aids metal.
The method of alkynes selective hydrogenation disclosed in this invention in the method for preparing catalyst, contains niobium compound
One kind in niobium pentaoxide, niobium oxalate, niobium hydroxide or ammonium niobium oxalate.
The method of alkynes selective hydrogenation disclosed in this invention, in the method for preparing catalyst, palladium is with solvable
Property salt form introduce, such as palladium bichloride, palladium nitrate or palladium.
The method of alkynes selective hydrogenation disclosed in this invention, the method for preparing catalyst, lead are with nitrate
Or the form introducing of acetate.
The method of alkynes selective hydrogenation disclosed in this invention, in the catalyst preparation side, alkali metal Li,
One or more in Na, K and Cs, preferably Li and/or K, alkali metal are in the form of its soluble nitrate or acetate
It introduces；Alkaline-earth metal is one or more, the preferably Mg in Be, Mg, Ca and Sr, and alkaline-earth metal is the soluble nitric acid with it
What the form of salt or acetate introduced.
The method of alkynes selective hydrogenation disclosed in this invention, in the method for preparing catalyst, promoter metal is
It is one or more in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium.Promoter metal is introduced in the form of its soluble-salt.
The pH value of the method for alkynes selective hydrogenation disclosed in this invention, the Catalyst Preparation Impregnation liquid can use ammonia
Water, sodium bicarbonate or sodium carbonate liquor adjust.
The method of alkynes selective hydrogenation disclosed in this invention, the boehmite can use carbonizatin method, ammonium
Prepared by the methods of method, nitrate method, it is best to use prepared by ammonium method.
The method of alkynes selective hydrogenation disclosed in this invention, the catalyst carrier are niobium oxide and aluminium oxide
Complex carrier improves the thermal stability of catalyst carrier because niobium oxide can improve the Acidity of catalyst carrier, extends catalysis
The service life of agent.The chain carrier of lower valency can also be stablized by introducing niobium oxide simultaneously.Of particular note is that described
Not cupric in catalyst under conditions of active component palladium, lead, contains when containing niobia-alumina in catalyst in catalyst
When copper, reaction temperature is relatively higher, easily causes the unsaturated hydrocarbons polymerization in C-4-fraction, generates green oil, lead to catalyst knot
Glue inactivates, and influences the service life of catalyst.And the presence of copper component can make catalyst regeneration conditions complicated harsh, security performance
It is not high.
The method of alkynes selective hydrogenation disclosed in this invention is straight to the C-4-fraction for being rich in alkynes after Butadiene Extraction
Row selection plus hydrogen are tapped into, has used the catalyst of the complex carrier containing niobium oxide and aluminium oxide in the process, niobium oxide
In the presence of, the preferable Acidity for improving catalyst carrier, the presence of niobium oxide and other components and synergistic effect so that catalyst
With preferable thermal stability, provides the chain carrier of stable lower valency and there is longer service life；The present invention
Method of hydrotreating convert alkynes therein to butadiene and monoolefine, hydrogenation products, which can return to extraction device, to be continued to extract fourth
Diene increases the yield of butadiene, improves the added value of this strand of material.Even if when the alkynes content of raw material is more than 4wt%, adopt
It still is able to run well for a long time with method provided by the present invention, catalyst activity component palladium base is not originally lost in, after adding hydrogen
It is produced almost without dimer in material, vinylacetylene content is less than 1.0wt%.The method major advantage of the present invention is：
(1) present invention process analoging industrial device, using heat-insulating fixed bed reactors, Catalyst packing goes into operation and regenerative operation side
Just, investment is small, is very beneficial for promoting to commercial plant.(2) the matching used catalyst of the present invention is bimetallic or more metals
Catalyst, the absorption between strong interaction ethene suppressing ethyl-acetylene and palladium between metal effectively reduce active component palladium damage
It loses, extends the service life of catalyst, it is ensured that hydrogenation technique is run steadily in the long term.
Description of the drawings
Fig. 1 is the XRD spectra of Examples 1 to 7 catalyst carrier, and the XRD spectra of these carriers is almost the same, and 2 θ values are main
It is the diffraction maximum of niobium oxide in 22~26 ° and 53~56 ° of sections, 2 θ values are mainly at 30~42 °, 42~49 ° and 64~70 °
Section is the diffraction maximum of aluminium oxide.
Specific implementation mode
Raw material sources and analysis method：
C-4-fraction rich in alkynes：It is derived from Lanzhou Petrochemical ethylene plant, contains vinylacetylene (VA) 15~25wt%, fourth two
12~20wt% of alkene；
Boehmite：Catalyst carrier Co., Ltd of Nanjing Olympic Thailand；
Specific surface area (m2/ g) and Kong Rong (ml/g)：Assay method is accumulated using national standard catalyst and adsorbent surface
GB/T 5816 is analyzed；
Raw material and product form：Using the composition measuring SH-T 1141-92 analyses of industrial cracking c_4；
Catalyst agent active component content assay method：Using national standard《Atomic absorption spectroscopy general rule》GB/
T15337-94 and《Chemical reagent flame atom absorption spectrophotography method general rule》GB19723-88 is analyzed.
Embodiment
The preparation of catalyst 1~7
The preparation of catalyst 1：
By boehmite, niobium pentaoxide, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 980 DEG C of roastings
Catalyst carrier is made in 3h；Palladium nitrate solution is prepared again, it is 2.6 to adjust pH value with sodium carbonate, is impregnated into catalyst carrier,
Extraction raffinate is removed after twenty minutes, is washed with distilled water, and aged, 120 DEG C of dry 2h, 420 DEG C of roasting 3h obtain the catalyst containing palladium
Precursor；Acetic acid lead solution is finally prepared again, is immersed on catalyst precarsor, and selection is made in 120 DEG C of dry 4h, 480 DEG C of roasting 4h
Property hydrogenation catalyst 1.
The preparation of catalyst 2：
By boehmite, niobium oxalate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 1020 DEG C of roasting 4h,
Catalyst carrier is made；Then palladium chloride solution is prepared, pH to 2.7 is adjusted with sodium bicarbonate, is impregnated into catalyst carrier, 20
Extraction raffinate is removed after minute, is washed with distilled water, before aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h obtain the catalyst containing palladium
Body；Lead nitrate solution is prepared again, is immersed on the catalyst precarsor containing palladium, and selection is made in 120 DEG C of dry 2h, 450 DEG C of roasting 4h
Property hydrogenation catalyst 2.
The preparation of catalyst 3：
By boehmite, niobium oxalate, magnesium nitrate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 1050 DEG C
4h is roasted, catalyst carrier is made；Then palladium chloride solution is prepared, pH to 2.7 is adjusted with sodium carbonate, is impregnated into catalyst carrier
On, extraction raffinate is removed after twenty minutes, is washed with distilled water, and aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h obtain the catalysis containing palladium
Agent precursor；Acetic acid lead solution is prepared again, is immersed on the catalyst precarsor containing palladium, and 120 DEG C of dry 2h, 460 DEG C of roasting 4h are made
Selective hydrocatalyst 3.
The preparation of catalyst 4：
By boehmite, niobium oxalate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 600 DEG C of roasting 3h, system
Obtain niobium oxide and alumina composite carrier；Then on a catalyst support by a certain amount of potassium nitrate solution dipping, 110 DEG C of dryings
The catalyst carrier containing potassium is made in 4h, 1050 DEG C of roasting 5h；Then palladium solution is prepared, pH to 2.8, leaching are adjusted with sodium carbonate
In stain to catalyst carrier, extraction raffinate is removed after twenty minutes, is washed with distilled water, aged, 120 DEG C of dry 3h, 440 DEG C of roasting 3h
Obtain the catalyst precarsor containing palladium；Lead nitrate solution is prepared again, is immersed on the catalyst precarsor containing palladium, 120 DEG C of dry 3h,
500 DEG C of roasting 4h, are made selective hydrocatalyst 4.
The preparation of catalyst 5：
By boehmite, niobium hydroxide, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 550 DEG C of roasting 3h,
Niobium oxide and alumina composite carrier is made；Then a certain amount of potassium nitrate and magnesium nitrate solution are immersed in catalyst carrier
On, the catalyst carrier containing potassium and magnesium is made in 110 DEG C of dry 4h, 980 DEG C of roasting 5h；The mixing of palladium and lead acetate is prepared again
Solution, it is 2.9 to adjust pH value with sodium bicarbonate, is impregnated into catalyst carrier, removes extraction raffinate after twenty minutes, is washed with distillation
It washs, selective hydrocatalyst 5 is made in aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h.
The preparation of catalyst 6：
By boehmite, ammonium niobium oxalate, magnesium nitrate, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 1000
DEG C roasting 3h, be made the catalyst carrier containing magnesium；Then palladium chloride solution is prepared, pH to 2.6 is adjusted with sodium bicarbonate, is impregnated into
In catalyst carrier, extraction raffinate is removed after twenty minutes, is washed with distilled water, and aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h are obtained
Catalyst precarsor containing palladium；Lead nitrate solution is prepared again, is immersed on the catalyst precarsor containing palladium, 120 DEG C of dry 2h, 550 DEG C
Roasting 4h obtains the catalyst precarsor containing palladium and lead；Silver nitrate solution is finally prepared, is immersed on catalyst precarsor, 120 DEG C dry
Dry 2h, 500 DEG C of roasting 3h, are made selective hydrocatalyst 6.
The preparation of catalyst 7：
By boehmite, niobium pentaoxide, nitric acid, water mixer kneader, extruded moulding, 120 DEG C of dryings, 620 DEG C of roastings
Niobium oxide and alumina composite carrier is made in 3h；Then a certain amount of magnesium nitrate solution is immersed in niobium oxide and aluminium oxide is answered
It closes on carrier, the catalyst carrier containing magnesium is made in 120 DEG C of dry 4h, 1100 DEG C of roasting 3h；Palladium and plumbi nitras are prepared again
Mixed solution, it is 2.8 to adjust pH value with ammonium hydroxide, is impregnated into catalyst carrier, removes extraction raffinate after twenty minutes, is washed with distillation
It washs, aged, 120 DEG C of dry 2h, 440 DEG C of roasting 5h obtain the catalyst precarsor containing palladium and lead；It is molten finally to prepare ammonium metatungstate
Liquid is immersed on catalyst precarsor jointly, 120 DEG C of dry 4h, and selective hydrocatalyst 7 is made in 550 DEG C of roasting 4h.
The physico-chemical property of catalyst 1~7 is as shown in table 1.
The physico-chemical property of catalyst prepared by 1 embodiment of table
Embodiment 1
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:2.5.Adiabatic reactor uses single stage adiabatic formula bubbling bed, and using catalyst 1, catalyst passes through in a hydrogen atmosphere
120 DEG C of reduction 6h.50 DEG C, reaction pressure 1.2MPa of reaction temperature, liquid air speed 8.5h-1, the molar ratio of hydrogen and alkynes is
1.5, table 2 is the composition of the front and back material of reaction.
Table 2 reacts front and back material composition
Embodiment 2
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:3.Adiabatic reactor uses single stage adiabatic formula bubbling bed, and using catalyst 2, catalyst passes through in a hydrogen atmosphere
120 DEG C of reduction 6h.45 DEG C, reaction pressure 1.5MPa of reaction temperature, liquid air speed 9.0h-1, the molar ratio of hydrogen and alkynes is
1.5, table 3 is the composition of the front and back material of reaction.
Table 3 reacts front and back material composition
Embodiment 3
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:3, adiabatic reactor uses single stage adiabatic formula bubbling bed, and using catalyst 3, catalyst passes through in a hydrogen atmosphere
120 DEG C of reduction 6h.45 DEG C, reaction pressure 2.0MPa of reaction temperature, liquid air speed 10.0h-1, the molar ratio of hydrogen and alkynes is
2.0, table 4 is the composition of the front and back material of reaction.
Table 4 reacts front and back material composition
Embodiment 4
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:0.5, adiabatic reactor uses single stage adiabatic formula bubbling bed, and using catalyst 4, catalyst passes through in a hydrogen atmosphere
120 DEG C of reduction 6h.40 DEG C, reaction pressure 2.0MPa of reaction temperature, liquid air speed 12h-1, the molar ratio of hydrogen and alkynes is 3.0,
Table 5 is the composition of the front and back material of reaction.
Table 5 reacts front and back material composition
Embodiment 5
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:2, adiabatic reactor is using double section heat-insulating bubbling beds, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One
Duan Caiyong catalyst 5, it is 40 DEG C that two sections, which use catalyst 6, one section of 40 DEG C of reaction temperature, second-stage reaction temperature, reaction pressure
1.5MPa, liquid air speed 15.0h-1, the molar ratio of every section of bed hydrogen and alkynes is 3.0, and table 6 be the composition of material before and after reaction.
Table 6 reacts front and back material composition
Embodiment 6
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:2.5.Adiabatic reactor is using double section heat-insulating bubbling beds, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.
Two sections of use catalyst 7, one section of 35 DEG C of reaction temperature, second-stage reaction temperature are 45 DEG C, reaction pressure 1.5MPa, liquid air speed
12h-1, the molar ratio of every section of bed hydrogen and alkynes is 2.0, and table 7 be the composition of material before and after reaction.
Table 7 reacts front and back material composition
Embodiment 7
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:3, adiabatic reactor is using double section heat-insulating bubbling beds, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One
Duan Caiyong catalyst 3, it is 40 DEG C that two sections, which use catalyst 6, one section of 40 DEG C of reaction temperature, second-stage reaction temperature, reaction pressure
2.0MPa, liquid air speed 18.0h-1, the molar ratio of every section of bed hydrogen and alkynes is 2.0, and table 8 be the composition of material before and after reaction.
Table 8 reacts front and back material composition
Embodiment 8
The C-4-fraction that will be enriched in alkynes is diluted with carbon-4, C-4-fraction and carbon-4 rich in alkynes
Weight ratio is 1:1, adiabatic reactor is using double section heat-insulating bubbling beds, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One
Duan Caiyong catalyst 1, two sections use catalyst 3, and catalyst is in a hydrogen atmosphere through 120 DEG C of reduction 6h.One section of reaction temperature 35
DEG C, second-stage reaction temperature is 40 DEG C, reaction pressure 2.0MPa, liquid air speed 10.0h-1, the molar ratio of every section of bed hydrogen and alkynes
It is 2.0, table 9 is the composition of the front and back material of reaction.
Table 9 reacts front and back material composition
In the selection hydrogenation process of four alkynes of carbon, main reaction is that vinylacetylene selection is hydrogenated to 1,3- fourths two
Alkene.In order to recycle butadiene to the greatest extent, it is desirable that the selectivity of catalyst will be got well.Data can be obviously from table 2~9
Go out, there is catalyst preferable hydrogenation activity, selectivity and stability, product medium vinyl acetylene content to be less than 1.0wt%, fourth
For diene selectivity all 45% or more, the 1,3-butadiene rate of recovery is higher, has been more than 100%.
Comparative example 1
1 used catalyst of comparative example is identical as 1 preparation method of catalyst, the difference is that 1 used catalyst of comparative example
In be free of niobium oxide.The evaluation process conditions of catalyst are same as Example 1.Table 10 is the composition of the front and back material of reaction.
Table 10 reacts front and back material composition
Comparative example 2
2 used catalyst of comparative example is identical as 2 preparation method of catalyst, the difference is that 2 used catalyst of comparative example
In be free of component lead.The evaluation process conditions of catalyst are same as Example 2.Table 11 is the composition of the front and back material of reaction.
Table 11 reacts front and back material composition
Comparative example 3
2 used catalyst of comparative example is identical as 2 preparation method of catalyst, the difference is that 2 used catalyst of comparative example
Middle lead content is 12.0wt%.The evaluation process conditions of catalyst are same as Example 2.Table 12 is the group of the front and back material of reaction
At.
Table 12 reacts front and back material composition
Comparative example 4
4 used catalyst of comparative example is identical as 4 preparation method of catalyst, the difference is that 4 used catalyst of comparative example
Middle oxidation content of niobium is 4.5wt%.The evaluation process conditions of catalyst are same as Example 4.Table 13 is the front and back material of reaction
Composition.
Table 13 reacts front and back material composition
Comparative example 5
5 used catalyst of comparative example is identical as 3 preparation method of catalyst, the difference is that 3 used catalyst of comparative example
In be free of niobium oxide.The evaluation process conditions of catalyst are same as Example 3.Table 14 is the composition of the front and back material of reaction.
Table 14 reacts front and back material composition
Comparative example 6
1 used catalyst of comparative example is identical as 1 preparation method of catalyst, the difference is that 1 used catalyst of comparative example
Middle oxidation content of niobium is 0.35wt%.The evaluation process conditions of catalyst are same as Example 1.Table 15 is the front and back material of reaction
Composition.
Table 15 reacts front and back material composition
Comparative example 7
Embodiment 7 of the 7 used catalyst preparation method of comparative example with CN101428228B.7 used catalyst of comparative example
Group becomes：Carrier is aluminium oxide, 0.45wt%Pd, 1.25wt%Mg, 3.65wt%Pb, 3.05wt%Cu.The evaluation of catalyst
Process conditions are same as Example 2.Table 16 is the composition of the front and back material of reaction.
Table 16 reacts front and back material composition
The method of hydrotreating using the present invention it can be seen from the data analysis of embodiment and comparative example, and it is mating with this
The palladium lead series catalysts of the niobia-alumina composite carrier load used are invented, hydrogenated products medium vinyl acetylene content is low
In 1.0wt%, butadiene selective is high, can farthest recycle butadiene, hydrogenated products meet butadiene extraction device into
Material requires.
Claims (10)
1. a kind of method of alkynes selective hydrogenation, it is characterised in that this method includes waiting for hydrogenation material and H2Into adiabatic reaction
Device, is mounted with selective hydrocatalyst in adiabatic reactor, and the molar ratio of hydrogen and the total alkynes content of reactor inlet is 0.8
~3.0,20~60 DEG C of inlet temperature is reacted, reaction pressure is 1.0~3.0MPa, and liquid volume air speed is 8~20h-1, reaction production
Object is detached into knockout drum after cooling；It is described to wait for that hydrogenation material is C-4-fraction rich in alkynes, is rich in alkynes
The mixture of the C-4-fraction of hydrocarbon and dilution material；The carrier of selective hydrocatalyst is the compound load of aluminium oxide and niobium oxide
Body, by total catalyst weight for 100wt% in terms of, catalyst include 0.1~1.0wt% of palladium, 2~10wt% of lead, niobium oxide 0.5~
3wt%, 80~97wt% of aluminium oxide；The aluminium oxide is θ-Al2O3And/or δ-Al2O3。
2. according to the method described in claim 1, it is characterized in that the catalyst include 0.2~0.6wt% of palladium, lead 3~
8wt%, 1~3wt% of niobium oxide.
3. according to the method described in claim 1, it is characterized in that niobium oxide indicate metal niobium exist always with oxidation states,
Niobium oxide is one or more in niobium pentaoxide, columbium sesquioxide, columbium dioxide, columbium monoxide.
4. according to the method described in claim 1, it is characterized in that the catalyst contains alkali metal and/or alkaline-earth metal, contain
Amount is 0.5~5wt% of total catalyst weight；It is described containing one or more in auxiliary agent gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium
Auxiliary agent content is 0~2wt% of total catalyst weight.
5. according to the method described in claim 1, it is characterized in that the alkynes mass content waited in hydrogenation material is not high
In 10wt%.
6. according to the method described in claim 1, it is characterized in that the C-4-fraction rich in alkynes, vinylacetylene matter
Amount content is 15~25wt%, and butadiene mass content is 12~20wt%.
7. according to the method described in claim 1, it is characterized in that waiting for that hydrogenation material is C-4-fraction and dilution rich in alkynes
The weight ratio of the mixture of material, C-4-fraction and dilution material rich in alkynes is 1:1~4.
8. according to the method described in claim 1, it is characterized in that adiabatic reactor be single stage adiabatic formula bubbling bed reactor or
Multistage insulation formula bubbling bed reactor.
9. according to the method described in claim 8, it is characterized in that single stage adiabatic formula bubbling bed reactor, hydrogen enter with reactor
The molar ratio of the total alkynes content of mouth is 1.0~2.5；Multistage insulation formula bubbling bed reactor, every section of inlet amounts of hydrogen and the section
Wait for that the molar ratio of alkynes total amount in hydrogenation material is 1.0~2.0 in inlet.
10. according to the method described in claim 1, it is characterized in that 25~50 DEG C of inlet temperature of reaction；Reaction pressure 1.0~
2.0MPa；10~18h of liquid air speed-1。
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| CN108863697B (en) * | 2017-05-15 | 2021-06-01 | 中国石油天然气股份有限公司 | Method for increasing yield of butadiene |
| CN112675870B (en) * | 2019-10-17 | 2022-10-04 | 中国石油天然气股份有限公司 | Preparation method of selective hydrogenation catalyst for carbon dioxide fraction alkyne |
| CN114075451B (en) * | 2020-08-13 | 2024-02-02 | 中国石油天然气股份有限公司 | Selective hydrogenation method |
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| CN1764617A (en) * | 2003-03-26 | 2006-04-26 | 巴斯福股份公司 | Palladium-based catalyst for selective hydrogenation of acetylene |
| CN102189001A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Wear-resistant and thermally stable alumina coating carrier |
| CN102731240A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | 1, 3-butadiene production process by C4 selective hydrogenation |
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| JPS63230643A (en) * | 1987-03-20 | 1988-09-27 | Showa Denko Kk | Selective hydrogenation of acetylene compound |
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| CN1764617A (en) * | 2003-03-26 | 2006-04-26 | 巴斯福股份公司 | Palladium-based catalyst for selective hydrogenation of acetylene |
| CN102189001A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Wear-resistant and thermally stable alumina coating carrier |
| CN102731240A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | 1, 3-butadiene production process by C4 selective hydrogenation |
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