CN105732289B - A kind of method of selective acetylene hydrocarbon hydrogenation recycling butadiene - Google Patents
A kind of method of selective acetylene hydrocarbon hydrogenation recycling butadiene Download PDFInfo
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Abstract
A kind of method of selective acetylene hydrocarbon hydrogenation recycling butadiene, to be rich in the C-4-fraction of alkynes after Butadiene Extraction as raw material, in the presence of a catalyst, using isothermal reactor, selection plus hydrogen obtain 1,3 butadiene, the process condition used for：Reaction temperature is 30~80 DEG C, and reaction pressure is 1.0~3.0MPa, and liquid air speed is 7~18h‑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 the methods of the selection plus hydrogen retrieval butadiene of the height unsaturated hydrocarbons in a kind of C-4-fraction.
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 that selective acetylene hydrocarbon hydrogenation recycles butadiene, specifically provide a kind of fourth
The selection method of hydrotreating of C-4-fraction rich in alkynes after diene extracting, for handling containing butane, butylene, butadiene, ethylene
The C-4-fractions such as ethyl-acetylene, butine improve resource added value to recycle butadiene, reduce investment, improve device economic benefit.
A kind of method of selective acetylene hydrocarbon hydrogenation recycling butadiene of the present invention, this method includes waiting for hydrogenation material and H2
Into isothermal reactor, selective hydrocatalyst, hydrogen and the total alkynes content of reactor inlet are mounted in isothermal reactor
Molar ratio be 1.0~3.0；30~80 DEG C of reaction temperature, reaction pressure be 1.0~3.0MPa, liquid volume air speed be 7~
18h-1, reaction product detached into knockout drum after cooling；Described waits for that hydrogenation material is the carbon four rich in alkynes
The mixture of fraction, the C-4-fraction rich in alkynes and dilution material；The carrier of selective hydrocatalyst is aluminium oxide and oxidation
The complex carrier of niobium, 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 disclosed in the present, described waits for that hydrogenation material is the C-4-fraction rich in alkynes or the carbon rich in alkynes
The mixture of four fractions and dilution material.The C-4-fraction for being wherein rich in alkynes comes from butadiene extraction device, is Butadiene Extraction
The remaining higher C-4-fraction of alkynes content afterwards, usually contains butylene, butane, butadiene, vinylacetylene, butine mainly group
Point.Alkynes is mainly the content of vinylacetylene in C-4-fraction rich in alkynes, and the mass content of vinylacetylene is usually
15~25wt%, butadiene mass content are usually 12~20wt%.
The method disclosed in the present, when waiting for hydrogenation material and H2When into isotherm formula reactor, wait in hydrogenation material
Alkynes mass content is preferably not higher than 10wt%.Wait for that hydrogenation material is that the C-4-fraction rich in alkynes or the carbon rich in alkynes four evaporate
Divide the mixture with dilution material；When alkynes content is higher than 10wt% in the C-4-fraction rich in alkynes, alkynes preferably will be enriched in
C-4-fraction dilution material dilution, the weight ratio of C-4-fraction rich in alkynes and dilution material is preferably 1:0.5~3；Most often
Dilution material is carbon-4.
The method disclosed in the present, the isothermal reactor are trickle bed isothermal reactor or bubbling bed isothermal reaction
Two kinds of device.The present invention recommends bubbling bed isothermal reactor, preferably single hop or multistage isotherm formula bubbling bed reactor.For
Single hop isotherm formula bubbling bed reactor, hydrogen and the molar ratio of the total alkynes content of reactor inlet are preferably 1.0~3.0.It is described
Multistage isotherm formula bubbling bed reactor refer to containing isotherm formula bubbling bed reactor more than double sections or double sections, using multistage etc.
When warm formula bubbling bed reactor, every section of inlet amounts of hydrogen waits for the molar ratio of alkynes total amount in hydrogenation material most with this section of inlet
It is 1.0~2.0 well.The method disclosed in the present can select different reaction items in isothermal reactor according to raw material difference
Part, since the reaction is liquid phase reactor, the selection of temperature and pressure should all make raw material be in liquid, and temperature cannot be too
Height, to prevent the polymerization of alkene and alkynes；Reaction temperature is generally 30~80 DEG C, preferably 30~70 DEG C；Reaction pressure is general
For 1.0~3.0MPa, preferably 1.0~2.0MPa；Liquid air speed is 7~18h-1, preferably 8~15h-1；Raw material is expected with dilution
Weight ratio be preferably 1:0.5~1:3.
The method disclosed in the present, the carrier of selective hydrocatalyst therein are the compound of aluminium oxide and niobium oxide
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；The oxygen
Change aluminium is θ-Al2O3And/or δ-Al2O3。
The method disclosed in the present, the selective hydrocatalyst, carrier are answering for aluminium oxide and niobium oxide
Carrier is closed, no matter catalyst activity component is reduction-state or oxidation state, metal niobium exists with oxidation states always, and and oxygen
Change aluminium and forms complex carrier.The present invention is described its existing forms with niobium oxide, actually there are many niobiums in niobium oxide
Chemical valence state, 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 niobium pentaoxide.
The content of the method disclosed in the present, the niobium oxide is 0.5~3wt%.When content is less than 0.5wt%
When, it introduces niobium oxide and unobvious is acted on to the performance for improving catalyst carrier；When content is higher than 3wt%, the addition of niobium oxide
The acidity of catalyst carrier, especially B acid amount can be greatly improved to increase, this can cause catalyst choice poor and easy gum deposit loses
Living, the selection for being highly detrimental to catalyst adds hydrogen.
The method disclosed in the present, selective hydrocatalyst therein include alkali metal and/or alkaline-earth metal 0.5~
5wt%, preferably 1~4wt%；Also may include it is one or more in auxiliary agent gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, content be 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.
Following specific preparation sides of special recommendation of the present invention may be used in the method disclosed in the present, the catalyst
Method but catalyst used in the present invention is not limited in being obtained with the method, the preparation method specific steps of catalyst 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 preparation method of catalyst of the present invention, when catalyst is containing one in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium
Kind or when a variety of promoter metals, after step B activity metal impregnation, drying, roasting, impregnation aids metal, process conditions are：
It is obtained with one or more soluble salt solutions substeps or co-impregnation step B in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium
Product, through 100~130 DEG C of dry 2~6h, catalyst is made in 300~700 DEG C of 3~6h of roasting.
The preparation method of catalyst of the present invention, when in catalyst contain alkali metal and/or alkaline-earth metal, be selected from
When one or more promoter metals in gold, cobalt, molybdenum, tungsten, lanthanum, silver, cerium, first prepare containing alkali metal and/or alkaline-earth metal
Catalyst carrier, then impregnate active component, then impregnation aids metal.
In method for preparing catalyst of the present invention, niobium pentaoxide, niobium oxalate, niobium hydroxide are selected from containing niobium compound
Or one kind in ammonium niobium oxalate.
In method for preparing catalyst of the present invention, palladium is introduced in the form of soluble-salt, such as palladium bichloride, nitric acid
Palladium or palladium.
Method for preparing catalyst of the present invention, lead are introduced in the form of nitrate or acetate.
It is one or more in alkali metal Li, Na, K and Cs in method for preparing catalyst of the present invention, preferably Li
And/or K, alkali metal are introduced in the form of its soluble nitrate or acetate；Alkaline-earth metal is Be, Mg, Ca and Sr
In one or more, preferably Mg, alkaline-earth metal be in the form of its soluble nitrate or acetate introduce.
In method for preparing catalyst of the present invention, promoter metal be gold, cobalt, molybdenum, tungsten, lanthanum, silver, one kind in cerium or
It is a variety of.Promoter metal is introduced in the form of its soluble-salt.
The pH value of Catalyst Preparation Impregnation liquid of the present invention can be adjusted with ammonium hydroxide, sodium bicarbonate or sodium carbonate liquor
It is whole.
Boehmite can use the methods of carbonizatin method, ammonium method, nitrate method to prepare in the present invention, it is best to use ammonium
Prepared by method.
The method disclosed in the present, the catalyst carrier is the complex carrier of niobium oxide and aluminium oxide, because of oxygen
The Acidity of catalyst carrier can be improved by changing niobium, improved the thermal stability of catalyst carrier, extended the service life of catalyst.Together
When introduce niobium oxide and can also stablize the chain carrier of lower valency.Of particular note is that not cupric in the catalyst,
When containing niobia-alumina in catalyst, when containing copper under conditions of active component palladium, lead, in catalyst, reaction temperature phase
To higher, the unsaturated hydrocarbons easily caused in C-4-fraction polymerize, and generates green oil, causes catalyst gum deposit to inactivate, influences to be catalyzed
The service life of agent.And the presence of copper component can make catalyst regeneration conditions complicated harsh, security performance is not high.
The method disclosed in the present, the C-4-fraction to being rich in alkynes after Butadiene Extraction directly carry out selection plus hydrogen,
Use the catalyst of the complex carrier containing niobium oxide and aluminium oxide, the presence of niobium oxide preferable to improve in the process
The presence of the Acidity of catalyst carrier, niobium oxide and other components and synergistic effect so that catalyst has preferable heat steady
It is qualitative, it provides the chain carrier weapons of stable lower valency and there is longer service life；The method of hydrotreating of the present invention
By vinylacetylene butadiene therein and monoolefine, hydrogenation products, which can return to extraction device, to be continued to extract butadiene, is increased
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 5wt%, using the present invention
The method provided still is able to run well for a long time, and catalyst activity component palladium base is not originally lost in, and adds several in the material after hydrogen
It is produced without dimer, vinylacetylene content is less than 1.0wt%.The method major advantage of the present invention is：(1) use etc.
Warm formula reactor.Since four selective acetylene hydrocarbon hydrogenation of carbon is the higher reaction of thermal discharge, heat is easy aggregation, causes bed Wen Sheng
Height, easily makes unsaturated hydrocarbons polymerize gum deposit during the reaction, and blocking catalyst duct is caused catalyst inactivation, while can also be made
Side reaction aggravates, and uses isotherm formula reactor, can avoid these undesirable elements.The generation of polymer can effectively be inhibited in this way,
So that the polymer for a small amount of low molecular weight that catalyst surface deposits rapidly is taken away by reactant flushing, to make catalyst with it is anti-
It answers effective contact area of object to increase, the activity and selectivity of catalyst is enable all fully to be showed in a long time.(2)
The catalyst that the present invention uses is bimetallic or multimetal reforming catalyst, the strong interaction ethene suppressing ethyl-acetylene between metal with
Absorption between palladium effectively reduces active component palladium loss, extends the service life of catalyst, ensures the long-term smooth fortune of hydrogenation technique
Row.
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 2.
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 magnesium 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 the catalyst carrier containing magnesium, extraction raffinate is removed after twenty minutes, is washed with distilled water, aged, 120 DEG C of dry 3h, 440 DEG C
Roasting 3h obtains the catalyst precarsor containing palladium；Lead nitrate solution is prepared again, is immersed on the catalyst precarsor containing palladium, and 120 DEG C dry
Dry 3h, 500 DEG C of roasting 4h, are made selective hydrocatalyst 3.
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 is made in 110 DEG C of dry 4h, 980 DEG C of roasting 5h；The mixing for preparing palladium and lead acetate again is molten
Liquid, it is 2.9 to adjust pH value with sodium bicarbonate, is impregnated into the catalyst carrier containing potassium, removes extraction raffinate after twenty minutes, uses distilled water
Washing, aged, 120 DEG C of dry 2h, 450 DEG C of roasting 3h, is made selective hydrocatalyst 4.
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 5.
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 the catalyst carrier containing magnesium, removes extraction raffinate after twenty minutes, with distillation
Water washing, aged, 120 DEG C of dry 2h, 440 DEG C of roasting 5h obtain the catalyst precarsor containing palladium and lead；Finally prepare metatungstic acid
Ammonium salt solution is immersed on catalyst precarsor jointly, 120 DEG C of dry 4h, and selective hydrocatalyst 6 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.Isothermal reactor uses single hop isotherm 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.Isothermal reactor uses single hop isotherm 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, isothermal reactor uses single hop isotherm 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, isothermal reactor uses single hop isotherm 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, isothermal reactor is using double section isotherm formula 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.Isothermal reactor is using double section isotherm formula 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, isothermal reactor is using double section isotherm formula 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, isothermal reactor is using double section isotherm formula 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 from table 2,3,4,5,6,7,8
With, it is evident that there is catalyst preferable hydrogenation activity, selectivity and stability, product medium vinyl acetylene content to be less than
1.0wt%, for butadiene selective 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 selective acetylene hydrocarbon hydrogenation recycling butadiene, it is characterised in that this method includes waiting for hydrogenation material and H2Into
Isothermal reactor is mounted with selective hydrocatalyst in isothermal reactor, and hydrogen rubs with the total alkynes content of reactor inlet
You are than being 1.0~3.0；30~80 DEG C of reaction temperature, reaction pressure are 1.0~3.0MPa, and liquid volume air speed is 7~18h-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, 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 5, 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 1:0.5~3.
8. according to the method described in claim 1, it is characterized in that isothermal reactor be single hop isotherm formula bubbling bed reactor or
Multistage isotherm formula bubbling bed reactor.
9. according to the method described in claim 8, it is characterized in that single hop isotherm formula bubbling bed reactor, hydrogen enter with reactor
The molar ratio of the total alkynes content of mouth is 1.0~3.0；Multistage isotherm 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 30~70 DEG C of reaction temperature；Reaction pressure 1.0~
2.0MPa；8~15h of liquid air speed-1。
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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 |
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
| 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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| JP5831190B2 (en) * | 2011-12-09 | 2015-12-09 | 東ソー株式会社 | Catalyst for simultaneous production of 1,3-butadiene and methacrolein, and method for producing 1,3-butadiene and methacrolein using the same |
| WO2014061917A1 (en) * | 2012-10-19 | 2014-04-24 | 한국화학연구원 | Regular mesoporous silica-based catalyst for preparing 1,3-butadiene from ethanol, and method for preparing 1,3-butadiene using same |
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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 |
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
| 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 |
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