CN108250019A - A kind of predepropanization front-end hydrogenation technique removes alkynes method - Google Patents

A kind of predepropanization front-end hydrogenation technique removes alkynes method Download PDF

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CN108250019A
CN108250019A CN201611245804.3A CN201611245804A CN108250019A CN 108250019 A CN108250019 A CN 108250019A CN 201611245804 A CN201611245804 A CN 201611245804A CN 108250019 A CN108250019 A CN 108250019A
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catalyst
temperature
carrier
hydrogenation
reaction
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韩伟
张峰
蔡小霞
钱颖
景喜林
梁玉龙
马好文
常晓昕
车春霞
景丽
杨珊珊
王斌
郭珺
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China Petroleum and Natural Gas Co Ltd
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    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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Abstract

A kind of predepropanization front-end hydrogenation technique removes alkynes method.Using Fe Co hydrogenation catalysts, alkynes a small amount of in the tower top effluent of depropanizing tower in predepropanization technique and alkadienes are subjected to selective hydrogenation refining, hydrogenating materials volume composition is mainly：Methane 30 40%, hydrogen 15 25%, ethane 8 15%, ethylene 30 45%, propane 5 10%, propylene 5 10%, allene 0.1 0.5%, acetylene 0.5 1.0%, propine 0.1 0.5%.Reaction condition is：Anti- 50~100 DEG C of one section of inlet temperature, two sections of 50~100 DEG C of inlet temperatures, three sections of 50~100 DEG C, 1.5~4.0MPa of reaction pressure, 10000~20000h of reaction velocity of inlet temperatures‑1.Hydrogenation catalyst is Fe systems selective hydrogenation catalyst, and carrier is high-temperature inorganic oxide, and active component is at least containing Fe, Co, and in terms of catalyst quality 100%, catalyst contains 5~12%Co of Fe 0.8~2.5%.Catalyst specific surface is 10~300m20.2~0.65ml/g of/g, Kong Rongwei.Using the present invention except alkynes method, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene selectivity is good, and green oil generating amount is far below noble metal catalyst.

Description

A kind of predepropanization front-end hydrogenation technique removes alkynes method
Technical field
The present invention relates to a kind of predepropanization front-end hydrogenation technique except alkynes method, particularly one kind is in predepropanization front-end hydrogenation In technique, using Fe-Co hydrogenation catalysts, the process for selective hydrogenation of alkynes, alkadienes is carried out.
Background technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the most bases of downstream polymerisation device This raw material.The selection of wherein acetylene adds hydrogen to have extremely important influence to ethylene processing industry, in addition to ensureing going out for hydrogenation reactor Mouth acetylene content is up to standard outer, and the selectivity of catalyst is excellent, can make the generation ethane that ethylene is as few as possible, to improving entire work It is significant to improve device economic benefit for the yield of ethene of skill process.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%~2.5%, when producing polyethylene, in ethylene A small amount of acetylene can reduce the activity of polymerization catalyst, and make the deterioration in physical properties of polymer, so must be by the second in ethylene Alkynes content drops to certain limit, could be as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are ethylene unit flows In one of important process.
Catalysis selective hydrogenation is divided into front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene adds Hydrogen reactor is for domethanizing column position, and it is before front-end hydrogenation that hydrogenation reactor, which is located at domethanizing column, hydrogenation reactor It is back end hydrogenation after domethanizing column.It is more and more using two front-end hydrogenation of carbon in current C-2-fraction acetylene hydrogenation The characteristics of process, the process be hydrogenation reactor before domethanizing column, before being predepropanization important is flow Add hydrogen, its main feature is that cracking fraction is separated by gas-liquid, carry out carbon fraction below three adds hydrogen, and acetylene is completed to convert, and Most propine allene is removed,
The key reaction occurred in the reactor is as follows：
Main reaction
C2H2+H2→C2H4 (1)
MAPD+H2→CH3- CH=CH2 (2)
MAPD is propine and allene
Side reaction
C2H4+H2→C2H6 (3)
C2H2+2H2→C2H6 (4)
2C2H2+H2→C4H6 (5)
C3H6+H2→C3H8 (6)
In these are answered, what reaction (1) and (2) was desirable to, acetylene, propine and allene were not only stripped of, but also increased production second Alkene and propylene；It is undesirable to react (3), (4), (5) and (6).
Due to there is a large amount of hydrogen in reaction mass, the selectivity of catalyst shows particularly important, otherwise can lead to pair Excessive generation is reacted, causes catalytic reactor temperature runaway.Since the selectivity reacted during low-speed is low, it be easy to cause temperature runaway, mesh Preceding minimum safe air speed is 4500/h, that is to say, that when device air speed is less than the numerical value, reactor is just easy to occur to fly Temperature brings threat to the operation of device.After the important difference of two front-end hydrogenation process of carbon and two back end hydrogenation process of carbon is Hydrogen is artificially incorporated in hydrogenation method, and the degree of reaction progress can be controlled by amounts of hydrogen.And front-end hydrogenation work In process, hydrogen content is higher, does not need to match hydrogen again, therefore few to the control means of reaction in hydrogenation process, and mutually reply is urged The performance requirement of agent just greatly improves.
For predepropanization front-end hydrogenation method, with the raising of reaction temperature, catalyst choice declines, and works as catalyst When selectivity drops to initial reaction temperature 1/3 when, it is believed that reached the maximum operation (service) temperature of catalyst, the temperature and starting The difference of reaction temperature is known as the action pane of catalyst, and the temperature range is wider, and the processing safety of catalyst is just higher.It passes Catalyst unite due to selective limitation, generally only 10~15 DEG C of the action pane.
Two front-end hydrogenation of carbon for the front-end hydrogenation technique of predepropanization, is mainly adopted mainly using fixed bed reactors at present With three sections of adiabatic reactor reactors, preceding two reactor is mainly the acetylene for removing the overwhelming majority, and third section reactor is used to remove More than 50% propine (MA) and allene (PD).So third section outlet acetylene is less than 1 μ L/L, MAPD and is less than 0.3% (v)。
Patent US4484015 discloses a kind of predepropanization front-end hydrogenation method, used by this method catalyst using Pd as Main active component, using Alpha-alumina as carrier, addition co-catalyst silver, the C2 hydrogenation that function admirable is prepared for infusion process is urged Agent.The catalyst can effectively reduce the excessive hydrogenation of ethylene, reduce the risk of bed temperature runaway.Catalysis disclosed in the patent The preparation method of agent is using infusion process.Because the surface polar groups of alpha-alumina supports are few, in the dipping of catalyst and dry Influenced to be especially apparent by maceration extract surface tension and solvation effect in dry processing procedure, metal active constituent presoma with Aggregate form is deposited on carrier surface.In addition, strong interaction cannot be formed between metal salt species and carrier after dipping, it is high Temperature roasting is easy to cause metallic migration aggregation and forms big crystal grain.
Patent CN201110086174.0 discloses a kind of method of C 2 fraction selective hydrogenation, the catalysis that this method uses Agent, using Pd as main active component, using Alpha-alumina as carrier, addition co-catalyst silver.It is specific high by being adsorbed on carrier Molecular compound forms macromolecule wrapped layer in carrier surface certain thickness, anti-with the compound with functional base and macromolecule Should, with the function base that can be complexed with active component, it is complexed on carrier surface function base by active component Reaction, ensure active component orderly and high degree of dispersion.Using the patented method, the specific high-molecular compound of carrier adsorption passes through The hydroxyl of aluminium oxide carries out chemisorbed with macromolecule, and the amount of carrier adsorption high-molecular compound will be by the hydroxyl value of aluminium oxide The limitation of amount；The complexing of macromolecule and Pd by functionalization is not strong, and activity component load quantity does not reach requirement sometimes, leaching Residual fraction active component is gone back in stain liquid, catalyst cost is caused to improve；C2 hydrogenation catalyst is prepared using this method also to deposit Technological process is complicated the shortcomings that.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material Agent, the catalyst is by being selected from the first component of copper, gold, silver and selecting second of component group of nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium Into in addition catalyst further includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound.It urges Fluorite structure is formed after agent calcining, use or regeneration.Catalyst oxide total content 0.01~50%, preferably calcination temperature 700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice With activity, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. for active component, nickel, platinum, palladium, iron, cobalt, Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide One or several kinds, additionally include 1~10% auxiliary agent.The inventive technique is mainly used for second in coal-to-oil industry tail gas The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, have good deep hydrogenation ability.The technology be mainly used for rich in CO and The complete plus hydrogen of ethylene, propylene, butylene etc., is not suitable for alkynes, the selection of alkadienes adds hydrogen in the various industrial tail gas of hydrogen.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst, The intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、 FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between the metal Object is closed to be prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead Temperature 473K is answered, after stablizing reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%, Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And And catalyst is prepared using heat melting method, condition is harsh.
In conclusion the selective hydrogenation of low-carbon alkynes and alkadienes, at present mainly using noble metal catalyst, for non- Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this Problem, the present invention provide a kind of novel Fe series hydrocatalysts and preparation method thereof.
Invention content
Alkynes method is removed the purpose of the present invention is to provide a kind of predepropanization front-end hydrogenation technique.It is particularly a kind of to be taken off preceding In propane front-end hydrogenation technique, using Fe-Co hydrogenation catalysts by contained acetylene in the tower top effluent of predepropanization tower Selective hydrogenation, is fully converted to ethylene, and by propine, allene partial hydrogenation, is converted into propylene.
Predepropanization front-end hydrogenation removal methods of the present invention refer in three sections of adiabatic reactor reactors of connecting, by object Contained acetylene, propine, allene selective hydrogenation, are converted into ethylene, propylene in material.
A kind of predepropanization front-end hydrogenation technique of the present invention removes alkynes method, using the front-end hydrogenation technique side of predepropanization Tower top effluent from predepropanization tower in ethylene unit is entered fixed bed reactors and carries out selection plus hydrogen, with removing by method Alkynes and alkadienes therein.It is aoxidized in adiabatic reactor reactor equipped with Fe-Co selective hydrogenation catalysts, carrier for high temperature resistant inorganic Object, active component is at least containing Fe and Co, and in terms of catalyst quality 100%, catalyst contains Fe 5~12%, preferred content 6 ~10%, Co 0.5~2.5%, preferred content are 1.0~2.2%；The specific surface of catalyst is 10~300m2/ g, preferably 90 ~170m2/ g, Kong Rongwei 0.2~0.65ml/g, wherein preferably 0.40~0.60ml/g, Fe are to be loaded with by impregnation method in load Fired on body, hydrogen atmosphere reduction is made；Reaction condition：50 DEG C~100 DEG C, 1.5~4.0MPa of reactor inlet temperature, 10000~20000h of reaction velocity-1。
It is of the present invention to remove alkynes method, hydrogenation catalyst is used, carrier is high-temperature inorganic oxide, is such as aoxidized One or more of aluminium, silica, zirconium oxide, magnesia etc..It is preferred that aluminium oxide or alumina series carrier, alumina series Carrier refers to the complex carrier of aluminium oxide and other oxides, and wherein aluminium oxide accounts for more than the 50% of carrier quality, such as can be The compound of the oxides such as aluminium oxide and silica, zirconium oxide, magnesia, preferably alumina-zirconia composite carrier, wherein Alumina content is more than 60%.Aluminium oxide can be θ, α, γ type or the mixture of its a variety of crystal form, preferably α-Al2O3Or - the Al containing α2O3Mixing crystal form aluminium oxide.
The present invention uses the preparation process of Fe-Co selective hydrogenation catalysts to include except alkynes method：
Catalyst is aged by preparing Fe predecessors aqueous solution, Co predecessor aqueous solutions, difference impregnated carrier, is dry respectively Dry, roasting or with its mixed solution impregnated carrier, obtains after rear ageing, dry, roasting.
The present invention use hydrogenation catalyst preparation condition for：
30~60 DEG C, 10~60min of dip time of dipping temperature, maceration extract pH value 1.5~5.0；Aging Temperature 20~60 DEG C, 30~120mi of digestion time；300~600 DEG C of calcination temperature, 240~300min of roasting time.Calcination temperature preferably 400~ 500℃。
Dry in the present invention is preferably temperature programming drying, and drying temperature program setting is：
Roasting is activation process in the present invention, and preferably temperature-programmed calcination, calcination temperature program setting is：
Incipient impregnation may be used in heretofore described catalyst, excessive dipping, surface spray, vacuum impregnation and repeatedly It is prepared by any one impregnation method in infusion process.
It is as follows：
(1) carrier is weighed after measuring carrier water absorption rate.
(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity, According to carrier water absorption rate and dipping method, dipping solution is prepared, and adjust maceration extract pH value 1.5~5.0 as required, and by solution Be heated to 30~60 DEG C it is spare.
(3) using incipient impregnation or when spraying method, the carrier weighed can be put into rotary drum, adjusts rotary drum rotating speed 25~30 turns/min, carrier is totally turned over, prepared 30~60 DEG C of maceration extract is poured into or sprayed with given pace It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier weighed is placed in container, then adds in 30~60 DEG C of dipping of preparation Solution, the visibly moved device of Quick shaking, discharges rapidly the heat released in adsorption process, and makes active component uniform load to carrier On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier weighed is placed in cyclonic evaporator, is vacuumized, add in 30~60 DEG C Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution extra after dipping is filtered out, is then dried in an oven using the method for temperature programming, it is dry Temperature program(me)：
(6) dried catalyst using temperature programming method is roasted, roasts temperature program：
Catalyst Co components are loaded using above-mentioned same steps, 300~600 DEG C of calcination temperature, preferably 400~ 500 DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
In catalyst preparation process can also first supported cobalt component load Fe components again.
Two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
It can also contain other active components in addition to containing Fe, Co in catalyst composition in the present invention.
Catalyst of the present invention is before use, need to be restored with hydrogen-containing gas, H2Content is preferably 10~50%, and reduction temperature is most It is 200~350 DEG C well, the condition of recommendation is to use N2+H2Gaseous mixture is restored for 250~335 DEG C under the conditions of micro-positive pressure, also The former time is preferably 240~360min, the best 60~500h of volume space velocity-1, reduction pressure is preferably 0.1~0.5MPa.
Fe elements can be with Fe, Fe in catalyst of the present invention2O3、Fe3O4, several forms exist in FeO, preferably mainly With α-Fe2O3Form exist, more preferably also contain a certain amount of Fe3O4.Recommend in the present invention in iron-containing activity composition at least Co is added, and preferably Co mainly exists in the form of CoO, be conducive to formation, the dispersion of catalyst activity phase, and be conducive to The stabilization of active phase improves catalyst activity, selectivity and anticoking capability.Meanwhile it adds in Co and is conducive to improve propine, the third two The conversion ratio of alkene.
Fe, Co and its different oxide relative amounts, pass through XRD diffraction peak areas integration method meters in catalyst of the present invention It calculates.
The activation temperature of catalyst and activity composition, content and carrier related, the activated mistake of catalyst in the present invention α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be excessively high；On the other hand, activation degree is again It determines the reducing condition of catalyst, is provided in the catalyst used still with α-Fe in the present invention2O3The Fe of form for mainly into Point, the excessively high effect that can influence catalyst instead of reduction temperature reduces activity, selectivity, easy coking.
Of the present invention to remove alkynes method, it is few in the tower top effluent of depropanizing tower in predepropanization technique to add hydrogen object Measure alkynes and alkadienes.Raw material volume forms：Methane 30~40%, hydrogen 15~12%, ethane 8~15%, ethylene 30~45%, propane 5~10%, propylene 5~10%, allene 0.1~0.5%, acetylene 0.5~1.0%, propine 0.1~ 0.5%.
In the present invention, hydrogenation material is reacted in two sections or three sections adiabatic reactor reactors of connecting, and is catalyzed in Fe-Co Under agent effect, by trace acetylene selective hydrogenation contained in material, ethylene is converted into, and part propine, allene are selected Hydro-conversion is propylene.
Except alkynes method, reaction condition is the invention predepropanization front-end hydrogenation：One section of 50~100 DEG C of inlet temperature, two 50~100 DEG C of inlet temperature of section, three sections of 50~100 DEG C, 1.5~4.0MPa of reaction pressure of inlet temperatures, reaction velocity 10000~ 20000h-1。
Using the present invention except alkynes method, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene loss rate is low or even does not have There is ethylene loss, " green oil " production quantity is far below noble metal catalyst, and catalyst anticoking capability is excellent, and S in anti-material, NOx、COxPoisoning performances is waited to greatly improve.
Description of the drawings
Fig. 1 is the C2 hydrogenation process flow chart using predepropanization technique.
In figure：1-oil scrubber；2-water scrubber；3-caustic wash tower；4-drier；5-predepropanization tower；Before 6-carbon two Hydrogenation reactor；7-domethanizing column；8-heat exchanger.
Attached drawing 2 is using XRD spectra after 1 catalyst reduction of the embodiment of the present invention.
Attached drawing 3 is 4 catalyst XRD spectra of comparative example
Attached drawing 4 is XRD spectra after 6 catalyst reduction of comparative example.
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s scanning ranges, 25 DEG C of temperature
1 wavelength of Co K α, abscissa is 2 θ of the angle of diffraction in figure, and ordinate is diffracted intensity
Different crystal forms Fe oxide contents are obtained using XRD diffraction peak areas integration method in catalyst, and benchmark is metal oxygen Compound total amount.
Symbol description in Fig. 2：
● it is α-Fe2O3, ■ Fe3O4, ▲ be CoO.
Symbol description in Fig. 3：
★ is α-Fe, ▲ it is CoO, ■ Fe3O4。
Symbol description in Fig. 4：
■ is Fe3O4, ★ is α-Fe, ◆ it is Co.
Fig. 2 is using XED diffraction spectrograms after the technology of the present invention catalyst reduction, and Fe is mainly with α-Fe in catalyst2O3Form Occur, relative amount 7.28% has Fe3O4In the presence of the second component exists with CoO crystal forms.
Fig. 3 is XRD diffraction spectrogram of the comparative example Fe contents compared with low catalyst, and Fe is reduced into Fe in catalyst3O4, α-Fe, Second of component Co exists with CoO.
Fig. 4 is XRD diffraction spectrogram of the comparative example catalyst after high temperature reduction, wherein without α-Fe2O3Phase, Fe are main With Fe3O4, simple substance α-Fe forms occur, Fe3O4Relative amount 4.92%, α-Fe relative amounts 4.23%.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation Test method without specific conditions in example, usually according to normal condition.
Analysis test method：
Specific surface：GB/T-5816
Kong Rong：GB/T-5816
Different crystal forms Fe oxide contents：XRD
Active component content in catalyst：Atomic absorption method
Conversion ratio and selectivity are calculated by formula below in embodiment：
Conversion of alkyne (%)=100 × △ acetylene/entrance acetylene content
Ethylene selectivity (%)=100 × △ ethylene/△ acetylene
Embodiment 1
Weigh the trifolium-shaped alumina support of 4.5 × 4.5mm of Φ.Take appropriate ferric nitrate, dissolve by heating in 60ml go from In sub- water, pH value 2.5, maceration extract temperature 50 C are adjusted, incipient impregnation stirs rapidly carrier impregnation 6min in carrier surface, Static 30min is to adsorption equilibrium, and 60 DEG C are aged 30min, then in an oven according to program：Catalyst is dried, activation of catalyst is then carried out using programmed temperature method, Activation procedure： Claim Appropriate cobalt nitrate is taken, is impregnated according to above-mentioned preparation process.Carrier and catalyst physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with+60% nitrogen of 40% hydrogen before use, restored, 300 DEG C of reduction temperature, pressure 0.5MPa, recovery time 4h.Adopt reduction rear catalyst XRD analysis as shown in Figure 2.With attached drawing 1 Suo Shi plus hydrogen flow, catalyst It is loaded in fixed-bed reactor.
Reaction mass composition is as shown in table 1：
1 hydrogenating materials of table composition is as shown in the table
Reaction condition：Material air speed：10000h-1；Operating pressure：1.5MPa.The results are shown in Table 7 for catalyst test.
Embodiment 2
At 50 DEG C, by a certain amount of NaAlO2Solution and ZrCl4Solution is stirred, and is then neutralized with salpeter solution, stirring 10h, co-precipitation generate uniform Al-Zr particles.Product is filtered, Na therein is washed with deionized+And Cl-Ion, so Add in afterwards appropriate mass concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C of dry 2h, 650 DEG C of roasting 4h Obtain Zr-Al complex carriers.Aluminium oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Take appropriate iron chloride and cobalt chloride, dissolve by heating in go from In sub- water, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, beaker dipping 10min is shaken, by extra leaching Stain liquid filters out, and catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：Catalyst is dried, activation of catalyst, activation are carried out using programmed temperature method Program： Carrier with Catalyst physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with+60% nitrogen of 30% hydrogen before use, restored, 280 DEG C of reduction temperature, pressure 0.5MPa, recovery time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 14000h-1, pressure 2.5MPa.
Raw material composition is as shown in table 2.
2 hydrogenating materials of table form
The results are shown in Table 7 for catalyst test.
Embodiment 3
The ball-type aluminium oxide for weighing Φ 1.5mm prepares catalyst.Appropriate ferric nitrate is taken to be dissolved in deionized water, adjusts pH Value 3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and load 10min makes active component upload uniformly, then in baking oven According to program： Catalyst is dried, is urged using programmed temperature method Agent activates, activation procedure： Obtain a leaching catalyst.
Using first step same procedure, appropriate cobalt nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried, Roasting, obtains final catalyst.Drying program： Calcination procedure： Carrier and catalyst Physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 280 DEG C, pressure 0.5MPa of reduction temperature, also Former time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 18000h-1, operating pressure 3.2MPa.
Raw material composition is as shown in table 3.
3 hydrogenating materials of table form
The results are shown in Table 7 for catalyst test.
Embodiment 4
Ball-aluminium oxide-titanium dioxide carrier of the Φ 2.0mm weighed is placed in vacuum impregnation plant.Take a certain amount of ferric nitrate molten It is spare to adjust pH value 3.5 in deionized water for solution.Vacuum impregnation plant vacuum pumping pump is opened, until vacuum degree 0.1mmHg, then from adding Material mouth is slowly added to prepared maceration extract, and 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is completely disappeared, Complete load, the catalyst that will have been loaded, in an oven according to program： Drying, in Muffle furnace according to： Roasting.Obtain a leaching catalyst.
Appropriate cobalt nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, roasts, obtains final catalyst.Drying program：Calcination procedure： Carrier and catalyst physical property Index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with 15% hydrogen before use, restored, 260 DEG C, pressure 0.5MPa of reduction temperature, also Former time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 20000h-1, operating pressure：3.8MPa.
Reaction raw materials composition is as shown in table 4.
4 hydrogenating materials of table form
The results are shown in Table 7 for catalyst test.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using 3 same procedure of embodiment.Activation temperature 650℃.Carrier and catalyst physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 250 DEG C, pressure 0.5MPa of temperature, during reduction Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 12000h-1, operating pressure：2.0MPa.
Reaction raw materials composition is as shown in table 5.
5 hydrogenating materials of table form
The results are shown in Table 7 for catalyst test.
Embodiment 6
Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are pressed according to aluminium oxide：Silica：Zirconium oxide =8:1:3 ratios are uniformly mixed, then the extruded moulding on banded extruder, 120 DEG C of dryings, and 550 DEG C of roasting 3h, obtain in Muffle furnace To Zr-Si-Al composite oxide carriers.Catalyst is prepared using 4 same procedure of embodiment.Carrier and catalyst physical index, Catalyst components content is shown in Table 6.
Catalyst is before use, with+55% nitrogen of 45% hydrogen, 250 DEG C, pressure 0.5MPa of temperature, activation in reduction furnace Time 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 16000h-1, operating pressure：2.0MPa.Reaction raw materials composition is as shown in table 6.
The results are shown in Table 7 for catalyst test.
Embodiment 7
The aluminium oxide of Φ 4.0mm is taken to make carrier, catalyst is prepared using 1 same procedure of embodiment, is lived at 450 DEG C Change.Carrier and catalyst physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with 30% hydrogen before use, restored, 250 DEG C, pressure 0.5MPa of temperature, during activation Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 18000h-1, pressure 2.5MPa.Reaction raw materials composition is as shown in table 6.
The results are shown in Table 7 for catalyst test.
Comparative example 1
Take Φ 4.0mm alumina supports, specific surface 4.5m2/ g, Kong Rongwei 0.32ml/g.Using equi-volume impregnating, By on a certain amount of silver nitrate solution incipient impregnation to carrier, ageing-drying-roasting obtains a leaching catalyst, then by one Quantitative palladium bichloride dissolving, incipient impregnation, ageing-drying-roasting, obtaining final catalyst, (petrochemical industry research institute PEC-01 adds Hydrogen catalyst).Catalyst Pd contents are that 0.03%, Ag contents are 0.08%.
Catalyst is at 100 DEG C with hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h-1.Added with attached drawing 1 Suo Shi Hydrogen flow, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 16000h-1, operating pressure：3.5MPa.Reaction raw materials composition is as shown in table 6.
Reaction result is as shown in table 7.
Comparative example 2
Carrier is made with Φ 4.0mm aluminium oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1 850℃.Carrier and catalyst physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 350 DEG C, pressure 0.5MPa of temperature, during activation Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.Restore the XRD diffraction spectras of rear catalyst Figure is as shown in Figure 3.
Raw material forms same as Example 2, reaction condition：Air speed 10000h-1, operating pressure：3.0MPa.
Reaction result is as shown in table 7.
Comparative example 3
The aluminium oxide for weighing Φ 4.0mm makees carrier, low iron content catalyst is prepared using 1 same procedure of embodiment, 450 It DEG C is activated.Carrier and catalyst physical index, catalyst components content are shown in Table 6.
Catalyst in reduction furnace with 45% hydrogen before use, restored, 300 DEG C, pressure 0.5MPa of temperature, during activation Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Raw material forms same as Example 3, reaction condition：Air speed 15000h-1, operating pressure：3.0MPa.
Reaction result is as shown in table 7.
Comparative example 4
1 same catalyst of Example, in 450 DEG C of activation.Carrier and catalyst physical index, catalyst components content It is shown in Table 6.
Catalyst in reduction furnace with 40% hydrogen before use, restored, 300 DEG C, pressure 0.5MPa of temperature, during activation Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Raw material forms same as Example 2, reaction condition：Air speed 18000h-1, operating pressure：2.5MPa.
Reaction result is as shown in table 7.
Comparative example 5
1 same catalyst of Example, in 450 DEG C of activation.Carrier and catalyst physical index, catalyst components content It is shown in Table 6.
Catalyst is restored in tube furnace, atmosphere be+55% nitrogen of 30% hydrogen, 200 DEG C of temperature, pressure 0.5MPa, soak time 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.It is catalyzed after reduction The XRD diffraction spectrograms of agent are as shown in Figure 4.
Raw material forms same as Example 3, reaction condition：Air speed 15000h-1, pressure 2.0MPa.
Reaction result is as shown in table 7.
Comparative example 6
1 same catalyst of Example, carrier and catalyst physical index, catalyst components content are shown in Table 6.
It directly drives after 450 DEG C of activation, is restored without hydrogen.With attached drawing 1 Suo Shi plus hydrogen flow, Catalyst packing In fixed-bed reactor.
Raw material forms same as Example 3, reaction condition：Air speed 18000h-1, operating pressure：2.5MPa.
Reaction result is as shown in table 7.
Catalyst, carrier calcination temperature transitivity index are as shown in table 6.
6 catalyst of table, carrier calcination temperature transitivity index
Reaction result is as shown in table 7.
7 process conditions of table and catalyst performance
Note：Acetylene and ethylene gather and generate n-butene, further gather and generate " green oil ", are usually given birth in analysis with n-butene Into scale sign catalyst green oil " production quantity.
Using Fe-Co as the hydrogenation catalyst of active component, Pd-Ag is reached to the hydrogenation activity of acetylene in predepropanization material Noble metal catalyst is horizontal, and to MAPD hydrogenation activities higher than noble metal catalyst, ethylene selectivity is apparently higher than Pd-Ag catalysis Agent, " green oil " production quantity are far below noble metal catalyst.When Fe is mainly with α-Fe2O3In the presence of, while have a small amount of Fe3O4When, catalysis Agent has good activity, and without reduction or low-temperature reduction, Fe is all with α-Fe2O3In the presence of catalyst is without activity；Transition Occurring α-Fe during reduction, catalyst activity reduction, with the raising of Fe contents, certain raising trend is presented in catalyst activity, Selectivity can be reduced accordingly.The addition of Co, helps to improve active component dispersion degree, and catalyst activity is improved, helped to improve To the hydrogenation activity of MAPD, in the presence of helping component Co in the form of CoO, the dispersion of Fe and its oxide is best, and calcination temperature is excessively high CoFe can be formed2O4, active component is agglomerated into larger particles, active to reduce, the raising of " green oil " production quantity.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art The protection domain of the claims in the present invention should all be belonged to.

Claims (10)

1. a kind of predepropanization front-end hydrogenation technique removes alkynes method, using the front-end hydrogenation process of predepropanization, ethylene is filled In putting the tower top effluent from predepropanization tower enter fixed bed reactors carry out selection plus hydrogen, with remove alkynes therein and Alkadienes, it is characterised in that aoxidized in adiabatic reactor reactor equipped with Fe-Co selective hydrogenation catalysts, carrier for high temperature resistant inorganic Object, active component is at least containing Fe and Co, and in terms of catalyst quality 100%, catalyst contains Fe 5~12%, preferred content 6 ~10%, Co 0.5~2.5%, preferred content are 1.0~2.2%；The specific surface of catalyst is 10~300m2/ g, preferably 90 ~170m2/ g, Kong Rongwei 0.2~0.65ml/g, wherein preferably 0.40~0.60ml/g, Fe are to be loaded with by impregnation method in load Fired on body, hydrogen atmosphere reduction is made；Reaction condition：50 DEG C~100 DEG C of reactor inlet temperature, reaction pressure 1.5~ 4.0MPa, 10000~20000h of reaction velocity-1。
2. according to claim 1 remove alkynes method, it is characterised in that use in hydrogenation catalyst, active component Fe mainly with α-Fe2O3Form exists, wherein α-Fe2O3The Fe of form will account for more than 50% Fe gross masses.
3. according to claim 1 remove alkynes method, it is characterised in that：Catalyst carrier is that aluminium oxide or alumina series carry Body, alumina series carrier refer to the complex carrier of aluminium oxide and other oxides, wherein aluminium oxide account for the 50% of carrier quality with On, can be aluminium oxide with silica, zirconium oxide, magnesia compound, preferably alumina-zirconia composite carrier, Middle alumina content is more than 60%；Aluminium oxide can be θ, α, γ type or the mixture of its a variety of crystal form, preferably α-Al2O3 Or-the Al containing α2O3Mixing crystal form aluminium oxide.
4. alkynes method is removed according to claim 1, which is characterized in that use the preparation side of Fe-Co selective hydrogenation catalysts Method：Catalyst is by preparing Fe predecessors aqueous solution, Co predecessor aqueous solutions, impregnated carrier, respectively ageing, dry, roasting respectively It burns or with its mixed solution impregnated carrier, is obtained after rear ageing, dry, roasting.
5. according to claim 4 remove alkynes method, it is characterised in that：30~60 DEG C of dipping temperature, dip time 10~ 60min, maceration extract pH value 1.5~5.0；20~60 DEG C of Aging Temperature, 30~120mi of digestion time；300 DEG C of calcination temperature~ 600 DEG C, 240~300min of roasting time, preferably 400~500 DEG C of calcination temperature.
6. according to claim 4 remove alkynes method, it is characterised in that：It is dry to be dried for temperature programming, drying temperature program It is set as：
7. according to claim 4 remove alkynes method, it is characterised in that：Temperature-programmed calcination is roasted to, calcination temperature program setting is：
8. according to claim 4 remove alkynes method, it is characterised in that catalyst is using preceding using N2+H2Gaseous mixture is in micro-positive pressure Under the conditions of restored, H2Volume content is preferably 10~50%, 200~350 DEG C of reduction temperature, preferably 250~335 DEG C, 240~360min of recovery time, 60~500h of air speed-1, 0.1~0.5MPa of reduction pressure.
9. according to claim 1 remove alkynes method, it is characterised in that：Predepropanization is come from predepropanization front-end hydrogenation technique The tower top outflow volume of material of tower, which forms, is mainly：Methane 30~40%, hydrogen 15~12%, ethane 8~15%, ethylene 30~ 45%, propane 5~10%, propylene 5~10%, allene 0.1~0.5%, acetylene 0.5~1.0%, propine 0.1~0.5%.
10. according to claim 1 remove alkynes method, it is characterised in that the adiabatic reactor reactor used is three sections of cascade reaction Device, reaction condition are：Reaction condition is：One section of 50~100 DEG C of inlet temperature, two sections of 50~100 DEG C of inlet temperatures, three sections of entrances 50~100 DEG C, 1.5~4.0MPa of reaction pressure, 10000~20000h of reaction velocity of temperature-1。
CN201611245804.3A 2016-12-29 2016-12-29 A kind of predepropanization front-end hydrogenation technique removes alkynes method Pending CN108250019A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243387A (en) * 1963-04-25 1966-03-29 Leuna Werke Veb Palladium-silver-iron oxide on alphaalumina catalyst composition for the selective hydrogenation of acetylene
GB1090787A (en) * 1963-12-11 1967-11-15 Chemetron Corp Catalyst and method for producing the same
CN102199067A (en) * 2011-04-07 2011-09-28 中国石油天然气股份有限公司 Selective hydrogenation method for C2 fraction
CN105732277A (en) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 Front-depropanization front-hydrogenation method for C2 fraction
CN105732281A (en) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 Front-depropanization front-hydrogenation method for C2 fraction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243387A (en) * 1963-04-25 1966-03-29 Leuna Werke Veb Palladium-silver-iron oxide on alphaalumina catalyst composition for the selective hydrogenation of acetylene
GB1090787A (en) * 1963-12-11 1967-11-15 Chemetron Corp Catalyst and method for producing the same
CN102199067A (en) * 2011-04-07 2011-09-28 中国石油天然气股份有限公司 Selective hydrogenation method for C2 fraction
CN105732277A (en) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 Front-depropanization front-hydrogenation method for C2 fraction
CN105732281A (en) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 Front-depropanization front-hydrogenation method for C2 fraction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
朱洪法等编著: "《催化剂制备及应用技术》", 30 June 2011 *
朱洪法等编著: "《石油化工催化剂基础知识》", 30 September 1995 *

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Application publication date: 20180706