CN106927994B - Acetylene removal method by front-end deethanization and front-end hydrogenation process - Google Patents

Acetylene removal method by front-end deethanization and front-end hydrogenation process Download PDF

Info

Publication number
CN106927994B
CN106927994B CN201511032474.5A CN201511032474A CN106927994B CN 106927994 B CN106927994 B CN 106927994B CN 201511032474 A CN201511032474 A CN 201511032474A CN 106927994 B CN106927994 B CN 106927994B
Authority
CN
China
Prior art keywords
catalyst
hydrogenation
temperature
removal method
carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201511032474.5A
Other languages
Chinese (zh)
Other versions
CN106927994A (en
Inventor
张峰
苟尕莲
钱颖
梁玉龙
谷丽芬
车春霞
韩伟
景喜林
何崇慧
王涛
刘俊涛
谢培思
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN201511032474.5A priority Critical patent/CN106927994B/en
Publication of CN106927994A publication Critical patent/CN106927994A/en
Application granted granted Critical
Publication of CN106927994B publication Critical patent/CN106927994B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A method for removing alkyne in a hydrogenation process before front deethanization is disclosed, wherein a hydrogenation catalyst is a Ti-Fe-Ni selective hydrogenation catalyst, a carrier is a high-temperature-resistant inorganic oxide, and the catalyst contains Fe 5-15% by 100% of the mass of the catalyst; 0.2-1.5% of Ti; 0.5 to 1.8 percent of Ni; the specific surface of the catalyst is 10-300 m 2/g; the pore volume is 0.2-0.65 ml/g; wherein Fe is loaded on a carrier by a dipping mode, and is prepared by roasting and reducing in a hydrogen atmosphere, wherein the Fe mainly exists in a form of alpha-Fe 2O3 and contains a FeNi phase. By adopting the alkyne-removing method, the catalyst has moderate reaction activity, good operation elasticity, good ethylene selectivity and far lower green oil generation amount than that of the noble metal catalyst.

Description

Acetylene removal method by front-end deethanization and front-end hydrogenation process
Technical Field
The invention relates to a method for removing alkyne in a hydrogenation process before front deethanization, in particular to a method for selectively hydrogenating and converting acetylene contained in a hydrogenation ethylene material before front deethanization into ethylene by using a Ti-Fe-Ni hydrogenation catalyst.
Background
Polymer grade ethylene production is the tap of the petrochemical industry, and polymer grade ethylene and propylene are the most basic raw materials for downstream polymerization plants. The selective hydrogenation of acetylene has very important influence on the ethylene processing industry, the selectivity of the catalyst is excellent except ensuring that the content of the acetylene at the outlet of a hydrogenation reactor reaches the standard, the ethylene can be generated into ethane as little as possible, and the catalyst has important significance for improving the ethylene yield of the whole process and the economic benefit of a device.
The cracked carbon-dioxide fraction contains acetylene with a mole fraction of 0.5-2.5%, and a small amount of acetylene in ethylene reduces the activity of a polymerization catalyst and deteriorates the physical properties of a polymer when polyethylene is produced, so that the acetylene content in ethylene must be reduced to a certain limit before the ethylene can be used as a monomer for synthesizing a high polymer. Acetylene separation and conversion is therefore one of the important processes in the ethylene plant scheme.
The catalytic selective hydrogenation in the ethylene device is divided into front hydrogenation and back hydrogenation, wherein the front hydrogenation and the back hydrogenation of acetylene refer to that the hydrogenation reactor is positioned in front of the demethanizer and is front hydrogenation, and the hydrogenation reactor is positioned behind the demethanizer and is back hydrogenation relative to the position of the demethanizer. In the current hydrogenation and alkyne removal of carbon-containing fraction, a process method adopting hydrogenation before carbon-containing is increasingly adopted, and the process method is characterized in that a hydrogenation reactor is arranged before a demethanizer. The front hydrogenation is divided into two processes of front depropanization and front deethanization. The front-end deethanization hydrogenation process is that the hydrogenation reactor is located after the deethanizer and before the demethanizer. The front-end depropanization hydrogenation process is that a hydrogenation reactor is positioned after a depropanizer and before a demethanizer. The difference of the flow path brings the difference of the composition of the two hydrogenation materials. The front deethanization hydrogenation material contains methane, hydrogen, carbon monoxide and carbon dioxide fractions (acetylene, ethylene and ethane); the front-end depropanization hydrogenation material contains methane, hydrogen, carbon monoxide, carbon two fractions (acetylene, ethylene and ethane) and carbon three fractions (propyne, allene, propylene and propane).
The front end deethanizer process has a higher hydrogen content in the hydrogenated feed than the front end deethanizer process. In order to avoid ethylene loss at higher hydrogen levels, front-end deethanization requires a catalyst with better selectivity.
the front deethanization does not have a carbon three fraction, and in the front depropanization process, partial propyne and allene are removed while acetylene is selectively removed by the catalyst, so that the carbon three fraction indirectly plays a role in regulating the activity of the catalyst in the hydrogenation process, and the possibility of temperature runaway of the device is reduced to a certain extent. In the process of front-end deethanization and hydrogenation, no adjustable process parameter is used to ensure the normal operation of the device except for avoiding temperature runaway and acetylene leakage of the device through temperature adjustment. Thus, compared to the front-end deethanization, the front-end deethanization requires higher operating flexibility and stability of the hydrogenation catalyst.
in the industrial device adopting front-end deethanization, domestic devices adopt a single-section isothermal reactor alkyne removal mode, and the industrial device adopting front-end deethanization generally adopts a three-section reactor alkyne removal process. Therefore, in the front-end deethanization process, the acetylene removal load of the catalyst is higher, and the device has higher requirements on the activity of the catalyst.
The main reactions taking place in the reactor are as follows:
Main reaction
CH+H→CH (1)
Side reactions
CH+H→CH (2)
CH+2H→CH (3)
Among these applications, reaction (1) is desirable to both remove acetylene and increase ethylene production; the reactions (2) and (3) are undesirable.
even if an isothermal bed reactor is adopted, the selectivity of the reaction can only reach 50-60%, that is, the probability of the reaction 2 is 50% or even higher than that of the reaction 1, and a part of ethylene is converted into ethane.
When an isothermal bed process is used, shell and tube reactors are used with cooling media between the shell and tube to remove the heat of reaction. For the process, methanol is generally used as a cooling medium, and the flow rate of the methanol must be accurately controlled, so that the temperature in the reactor is stabilized in a proper range, acetylene leakage is easy to occur when the temperature is too low, and the temperature is high and is easy to fly. This is particularly true in the early stages of plant start-up, where the catalyst activity is high and temperature sensitive.
patent US4484015 discloses a catalyst, which uses Pd as the main active component, alpha-alumina as the carrier, and silver as the promoter, and prepares a carbon dioxide hydrogenation catalyst with excellent performance by an impregnation method. The catalyst can effectively reduce excessive hydrogenation of ethylene and reduce the risk of temperature runaway of a bed layer.
In the patent US5587348, alumina is used as a carrier, a promoter of silver is added to react with palladium, alkali metal is added, and chemically bonded fluorine is used for preparing the carbon dioxide hydrogenation catalyst with excellent performance. The catalyst has the characteristics of reducing the generation of green oil, improving the selectivity of ethylene and reducing the generation amount of oxygen-containing compounds. US5510550 adopts a wet reduction method to prepare the catalyst, and adds a reducing agent into the impregnation liquid to reduce Pd and Ag solution when the Pd and Ag solution is not dried, so that the problem of uneven dispersion of active components caused by solvation effect is reduced, and the catalyst which has excellent selectivity and is suitable for hydrogenation process before carbon dioxide is prepared.
CN201110086048.5 forms a polymer coating layer on the surface of the carrier in a certain thickness by adsorbing a specific polymer compound on the carrier, and the compound with a functional group reacts with the polymer to enable the polymer to have the functional group capable of complexing with the active component, and the active component is ensured to be orderly and highly dispersed by the complexing reaction of the active component on the functional group on the surface of the carrier. By adopting the method, the carrier adsorbs specific high molecular compounds, and the high molecular compounds are chemically adsorbed with high molecules through the hydroxyl groups of alumina, and the amount of the high molecular compounds adsorbed by the carrier is limited by the number of the hydroxyl groups of the alumina; the functional polymer and Pd have weak complexing effect, sometimes the loading capacity of the active component can not meet the requirement, and part of the active component remains in the impregnation liquid, so that the cost of the catalyst is increased; the method for preparing the carbon dioxide hydrogenation catalyst also has the defect of complicated process flow.
CN2005800220708.2 discloses a selective hydrogenation catalyst for acetylene and diolefin in light olefin raw material, which is composed of a first component selected from copper, gold and silver and a second component selected from nickel, platinum, palladium, iron, cobalt, ruthenium and rhodium, and in addition, the catalyst also includes at least one inorganic salt and oxide selected from zirconium, lanthanide and alkaline earth metal mixture. The catalyst forms a fluorite structure after being calcined, used or regenerated. The total content of the catalyst oxide is 0.01-50%, and the preferred roasting temperature is 700-850 ℃. The addition of a third oxide, modified alumina or silica support, helps to increase catalyst selectivity and activity, selectivity after regeneration. The technology still takes copper, gold, silver, palladium and the like as active components and takes nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium and the like as auxiliary components, and the regeneration performance of the catalyst is improved by modifying the oxide of the carrier.
CN102218323A discloses a hydrogenation catalyst for unsaturated hydrocarbons, the active component is a mixture of 5-15% of nickel oxide and 1-10% of other metal oxides, the other metal oxides can be one or more of molybdenum oxide, cobalt oxide and iron oxide, and in addition, 1-10% of an auxiliary agent is also included. The technology is mainly used for hydrogenating and converting ethylene, propylene, butylene and the like in the tail gas of the coal-to-liquid industry into saturated hydrocarbon, and has good deep hydrogenation capacity. The technology is mainly used for the total hydrogenation of ethylene, propylene, butylene and the like in various industrial tail gases rich in CO and hydrogen, and is not suitable for the selective hydrogenation of alkyne and dialkene.
ZL201080011940.0 discloses an ordered cobalt-aluminum and iron-aluminum intermetallic compound as acetylene hydrogenation catalyst, the intermetallic compound is selected from the group consisting of CoAl, CoAl3, Co2Al5, Co2Al9, o-Co4Al13, h-Co4Al13, m-Co4Al13, FeAl2, Fe3Al, Fe2Al5 and Fe4Al 13. Among them, Fe4Al13 and o-Co4Al13 are preferable. The intermetallic compound is prepared by a hot melting method in solid chemistry. The catalyst hydrogenation performance test is carried out in a quartz tube furnace, the reaction temperature is 473K, after the stable reaction is carried out for 20 hours, the acetylene conversion rate of the o-Co4Al13 catalyst reaches 62%, the ethylene selectivity reaches 71%, the acetylene conversion rate on the Fe4Al13 catalyst reaches 40%, and the ethylene selectivity reaches 75%. The technology is used for preparing intermetallic compounds under the condition of high temperature, is used for selective hydrogenation of acetylene, has low acetylene conversion rate and high reaction temperature, and is not beneficial to industrial application. And the catalyst is prepared by a hot melting method, and the conditions are harsh.
In summary, the selective hydrogenation of low carbon alkynes and dienes mainly adopts noble metal catalysts, and a great deal of work is carried out on the research and development of non-noble metal catalysts, but the selective hydrogenation is far away from the industrial application. In order to solve the problem, the invention provides a novel Ti-Fe-Ni hydrogenation catalyst and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a method for removing alkyne in a front deethanization front hydrogenation process. In particular to a Ti-Fe-Ni hydrogenation catalyst which can selectively hydrogenate the acetylene contained in the tower top effluent of a front deethanizer in the front deethanization front hydrogenation process and completely convert the acetylene into ethylene without loss of ethylene and propylene.
the hydrogenation removal method before front deethanization comprises the steps of enabling a material flowing out of the top of a front deethanization tower to enter a hydrogenation reactor for selective hydrogenation to remove acetylene contained in the material, wherein a Ti-Fe-Ni selective hydrogenation catalyst is filled in the hydrogenation reactor, a carrier is a high-temperature-resistant inorganic oxide, and the catalyst contains 5-15% of Fe, preferably 7.5-12% of Ti, 0.2-1.5% of Ti, preferably 0.5-1% of Ni, and preferably 0.8-1.2% of Ni, based on 100% of the mass of the catalyst. The specific surface area of the catalyst is 10-300 m2/g, preferably 90-170 m2/g, the pore volume is 0.2-0.65 ml/g, preferably 0.40-0.60 ml/g, wherein Fe is loaded on a carrier in an impregnation mode, and the catalyst is prepared by roasting at 300-700 ℃ and reducing at 200-500 ℃ in an atmosphere containing hydrogen; in the catalyst, Fe exists mainly in a-Fe 2O3 form and contains FeNi phase. Catalytic selective hydrogenation reaction conditions: the inlet temperature of the hydrogenation reactor is 50-100 ℃, the reaction pressure is 3.0-4.5 MPa, and the reaction volume space velocity is 5000-20000 h < -1 >. Preferred hydrogenation conditions are: the inlet temperature of the hydrogenation reactor is 60-95 ℃, the reaction pressure is 2.8-3.8 MPa, and the volume space velocity is 8000-15000 h < -1 >.
The acetylene removing method adopts the hydrogenation catalyst, the carrier is a high-temperature-resistant inorganic oxide, and the technical key point of the method is that the catalyst contains Fe, and the catalyst is roasted and reduced, so that the carrier has no special requirement, such as one or more of alumina, silica, zirconia, magnesia and the like. However, alumina or alumina-based carriers, which are composite carriers of alumina and other oxides, in which alumina accounts for 50% or more of the mass of the carrier, are also preferred, and for example, alumina and oxides such as silica, zirconia, magnesia, etc., and alumina-zirconia composite carriers, in which the alumina content is 60% or more, are also preferred. The alumina can be theta, alpha, gamma or a mixture of a plurality of crystal forms, and is preferably alpha-Al 2O3 or mixed crystal form alumina containing alpha-Al 2O 3.
The preparation process of the Fe catalyst adopted by the alkyne removing method comprises the following steps:
The catalyst is obtained by preparing impregnation liquid of Fe precursor aqueous solution and Ti and Ni precursor aqueous solution, respectively impregnating the carrier, respectively aging, drying and roasting or impregnating the carrier with mixed solution thereof, then aging, drying and roasting, and finally reducing.
The preferred conditions in the preparation method of the invention are:
The dipping temperature is 30-60 ℃, the loading time is 10-60 min, the pH value of the dipping solution is 1.5-5.0, the aging time is 30-120 min, the roasting temperature is 400-500 ℃, and the roasting time is 180-300 min.
in the present invention, the drying is preferably a temperature-raising drying, and the drying temperature program is set as follows:
In the present invention, the calcination, i.e. the activation process, is preferably temperature programmed calcination, and the calcination temperature program is set as follows:
The catalyst can be prepared by adopting any one impregnation mode of isometric impregnation, excessive impregnation, surface spray impregnation, vacuum impregnation and multiple impregnation.
The preparation method of the catalyst provided by the invention comprises the following specific steps:
(1) And measuring the water absorption of the carrier and then weighing the carrier.
(2) Accurately weighing a certain amount of Fe precursor (recommending soluble nitrate, chloride or sulfate) according to the load, preparing an impregnation solution according to the water absorption rate of the carrier and an impregnation method, adjusting the pH value of the impregnation solution to 1.5-5.0 according to requirements, and heating the solution to 30-60 ℃ for later use.
(3) When an isometric immersion or spray immersion method is adopted, the weighed carrier can be placed into a rotary drum, the rotating speed of the rotary drum is adjusted to be 25-30 r/min, the carrier is completely turned over, the prepared immersion liquid at the temperature of 30-60 ℃ is poured or sprayed onto the carrier at a certain speed, and the carrier is loaded for 5-10 min.
When an excessive impregnation method is adopted, the weighed carrier is placed in a container, then the prepared impregnation solution with the temperature of 30-60 ℃ is added, the container is quickly shaken, so that heat emitted in the adsorption process is quickly released, the active component is uniformly loaded on the carrier, and standing is carried out for 5-10 min so that the surface active component and the active component in the solution compete for adsorption balance.
When a vacuum impregnation method is adopted, the weighed carrier is placed in a cyclone evaporator, the vacuum is pumped, impregnation liquid with the temperature of 30-60 ℃ is added for impregnation for 5-10 min, and the carrier is heated in a water bath until the surface of the carrier is completely dried.
(4) Transferring the impregnated catalyst into a container, and aging the catalyst for 30-120 min at 25-60 ℃.
(5) Filtering out excessive solution after impregnation, and then drying in an oven by adopting a temperature programming method, wherein the drying temperature programming is as follows:
(6) Roasting and activating the dried catalyst in a muffle furnace or a tubular furnace, wherein the roasting temperature-rising program comprises the following steps:
The Ni component of the catalyst can be singly soaked by adopting the steps or can be prepared into a mixed solution with Fe and then is soaked together according to the steps; the Ti component is loaded by adopting the same steps, and the roasting temperature is 300-700 ℃, preferably 400-500 ℃.
The Fe element in the catalyst can exist in various forms of Fe, Fe2O3, Fe3O4 and FeO, but the content of the Fe in the alpha-Fe 2O3 form is higher than that of the Fe in other forms, and the Fe accounts for more than 50% of the total weight of the Fe. In the invention, Ni is recommended to be added into the active composition containing iron, and a FeNi phase is formed by roasting and reduction, which is beneficial to the activation of hydrogen and improves the activity of the catalyst; in the invention, TiO2 is recommended to be added into the active composition containing iron, which is beneficial to the formation and dispersion of the active phase of the catalyst, and is beneficial to the stability of the active phase, and the selectivity and the coking resistance of the catalyst are improved.
The activation temperature of the catalyst is related to the active composition, content and carrier of the catalyst, and the alpha-Fe 2O 3-form Fe is formed after the activation process, so that the catalyst is stable and the activation temperature cannot be too high; on the other hand, the activation degree determines the reduction condition of the catalyst, and the excessive reduction of the catalyst provided by the invention, which still takes the Fe in the form of alpha-Fe 2O3 as the main component, can influence the effect of the catalyst, influence the selectivity and is easy to coke.
The active component of the catalyst is mainly Fe, and the catalyst can be a non-noble metal catalyst, even can not contain cobalt, molybdenum and tungsten, so that the cost is greatly reduced, and the cost of the catalyst is far lower than that of a noble metal Pd catalyst.
The catalyst reduction is that before the catalyst is used, the calcined catalyst is reduced by using hydrogen-containing gas, the H2 volume content is preferably 10-50%, the reduction temperature is 200-500 ℃, the reduction time is 240-360 min, the volume space velocity is 100-500H < -1 >, and the reduction pressure is 0.1-0.8 MPa; the preferable conditions are that mixed gas of N2 and H2 is used for reduction, the reduction temperature is 300-400 ℃, the volume space velocity is 200-400H < -1 >, and the reduction pressure is preferably 0.1-0.5 MPa. The process is usually carried out before the selective hydrogenation reaction, and is preferably carried out outside the reactor, i.e., outside the selective hydrogenation reaction apparatus.
According to the fore-deethanization fore-hydrogenation removal method, the hydrogenation reactor can be an isothermal bed reactor or an adiabatic bed reactor, and acetylene contained in the ethylene material is selectively hydrogenated and converted into ethylene.
Due to the beneficial effect of the catalyst, when the adiabatic bed reactor is adopted, a two-section or three-section series adiabatic bed hydrogenation reactor can be adopted. The hydrogenation reactor is a two-section or three-section series adiabatic bed reactor, and the reaction conditions are as follows: the inlet temperature of the first section is 50-100 ℃, preferably 60-85 ℃, the inlet temperature of the second section is 50-100 ℃, preferably 75-90 ℃, and the inlet temperature of the hydrogenation reactor is 50-100 ℃ of the inlet temperature of the third section when the hydrogenation reactor is a three-section series adiabatic reactor, preferably 80-95 ℃.
The hydrogenation raw material for selective hydrogenation is from the tower top effluent of a front deethanizer in a front deethanizing front hydrogenation process, and the volume composition of the hydrogenation raw material is as follows: 700-900 mu L/L of CO, 15-25% of hydrogen, 28-40% of methane, 0.5-1.0% of acetylene, 30-45% of ethylene and 5-10% of ethane.
by adopting the alkyne-removing method, the catalyst has moderate reaction activity, good operation elasticity, good ethylene selectivity and far lower green oil generation amount than that of the noble metal catalyst.
Drawings
FIG. 1 is a flow diagram of a carbon-dioxide hydrogenation process employing a front end deethanization process. 1-oil wash column; 2-water washing tower; 3-alkaline washing tower; 4-drying tower; 5-front deethanizer; 6-a carbon two hydrogenation reactor; 7-demethanizer.
FIG. 2 is the XRD spectrum of the catalyst of example 3 (minus the background of the support α -Al2O 3).
FIG. 3 is the XRD spectrum of the catalyst of comparative example 2 (minus the background of the support α -Al2O 3).
FIG. 4 is the XRD pattern (with background of α -Al2O3 removed) of the catalyst of comparative example 5 after reduction.
XRD measurement conditions:
german Bruker D8ADVANCE X-ray diffractometer
tube voltage: 40kV current 40mA
Scanning: step size of 0.02 degree, frequency of 0.5s, scanning range of 4-120 degree, temperature of 25 degree C
Cu Ka 1 wavelength, diffraction angle 2 theta on abscissa and diffraction intensity on ordinate
The symbols in fig. 2 illustrate:
● is alpha-Fe 2O3, a-solidup is FeNi, and a xxx is Ti 2O.
The symbols in fig. 3 illustrate:
● is alpha-Fe 2O3, tangle-solidup is FeNi, diamond-solid is anatase.
Symbolic illustration in fig. 4:
Duct | -, is alpha-Fe, ■ is Fe3O4, t is Ti2O, and a-solidup is Ni.
It can be seen in fig. 2 that Fe in the catalyst occurs mainly in the form of α -Fe2O3 with a relative content of 8.10% and a FeNi phase.
As can be seen in fig. 3, Ti in the catalyst sinters with iron oxide, an anatase crystal phase appears, distribution and structure of active components are destroyed, and the catalyst activity decreases.
In FIG. 4, Fe mainly appears in the form of elemental alpha-Fe, with a relative content of 8.92%, and a small amount of Fe3O4 is formed.
Detailed Description
The analysis and test method comprises the following steps:
Comparison table: GB/T-5816
Pore volume: GB/T-5816
Content of Fe oxide in different crystal forms: XRD
The content of active components of the catalyst is as follows: GB/T1537-94
The selective calculation method comprises the following steps:
Selectivity to ethylene, S ═ 1-Delta ethane/. DELTA.acetylene
Propylene selectivity S ═ 1- < delta > propane/< delta > (propyne + propadiene)
Example 1
Weighing cloverleaf clover type alumina carrier with phi of 4.5 multiplied by 4.5 mm. Taking ferric nitrate, heating and dissolving in 60ml of deionized water, adjusting the pH value to be 2.5, keeping the temperature of an impregnation liquid at 50 ℃, impregnating the surface of a carrier in an equal volume, rapidly turning over the carrier for impregnation for 6min, standing for 30min until adsorption is balanced, aging at 60 ℃ for 30min, and then placing in an oven according to the following procedures: then activating the catalyst by adopting a programmed heating method, wherein the activating procedure comprises the following steps: weighing lanthanum nitrate, and impregnating according to the preparation steps.
Before the catalyst is used, reducing the catalyst in a reducing furnace by using 40 percent of hydrogen and 60 percent of nitrogen at the reduction temperature of 450 ℃, under the pressure of 0.5MPa and for 4 hours. The hydrogenation flow shown in the attached figure 1 is adopted, and the catalyst is filled in an isothermal bed reaction device. The reaction mass composition is shown in table 1:
Table 1 hydrogenation feed composition is shown in the table below
Reaction conditions are as follows: material airspeed: 20000 h-1; operating pressure: 4.0 MPa.
the reaction results are shown in Table 3, and the catalyst and carrier properties are shown in Table 4.
Example 2
Stirring and mixing a certain amount of NaAlO2 solution and ZrCl4 solution at 50 ℃, then neutralizing with nitric acid solution, stirring for 10h, and coprecipitating to generate uniform Al-Zr particles. The resultant was filtered, and Na + and Cl-ions were washed with deionized water, and then polyvinyl alcohol having a mass concentration of 15% was added as a pore-forming agent, followed by kneading and molding. Drying at 130 ℃ for 2h, and roasting at 650 ℃ for 4h to obtain the Zr-Al composite carrier. The mass ratio of alumina to zirconia in the carrier was 4: 1.
The catalyst is prepared by alumina-zirconia composite carrier. Heating and dissolving ferric chloride and potassium chloride in deionized water, adjusting the pH value to be 2.0, soaking the carrier in excess at the temperature of 80 ℃, shaking a beaker for soaking for 10min, filtering out excessive soaking liquid, aging the catalyst in a water bath at the temperature of 60 ℃ for 50min, and then drying in an oven according to the following procedures: activating the catalyst by adopting a programmed heating method, wherein the activating procedure comprises the following steps:
Before the catalyst is used, reducing the catalyst in a reducing furnace by using 30 percent of hydrogen and 60 percent of nitrogen at the reducing temperature of 550 ℃, under the pressure of 0.5MPa and for 4 hours. The hydrogenation flow shown in the attached figure 1 is adopted, and the catalyst is filled in an isothermal bed reaction device. The raw material composition is shown in table 2.
TABLE 2 hydrogenation feed composition
The reaction results are shown in Table 3, and the catalyst and carrier properties are shown in Table 4.
Example 3
Spherical alumina with phi of 1.5mm is weighed to prepare the catalyst. Dissolving ferric nitrate in deionized water, adjusting the pH value to 3.0, keeping the temperature of the impregnation liquid at 40 ℃, spraying the carrier by a spraying pot, loading for 10min to uniformly load the active components, and then, in an oven, according to the following procedures: activating the catalyst by adopting a programmed heating method, wherein the activating procedure comprises the following steps: to obtain a leached catalyst.
And (3) dissolving cerium nitrate, spraying and soaking the dissolved cerium nitrate on the surface of the first-soaked catalyst, drying and roasting to obtain the final catalyst by adopting the same method in the first step. And (3) drying procedure: and (3) roasting procedure:
Before the catalyst is used, reducing the catalyst in a reducing furnace by using 20 percent hydrogen at the reducing temperature of 400 ℃ and under the pressure of 0.5MPa for 4 h. XRD analysis of the reduced catalyst is shown in figure 2. The hydrogenation flow shown in the attached figure 1 is adopted, and the catalyst is filled in an isothermal bed reaction device.
Reaction conditions are as follows: the space velocity is 15000h < -1 > and the operating pressure is 3.0 MPa.
the raw material composition is shown in table 2. The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
example 4
The spherical alumina-titania carrier with phi of 2.0mm is weighed and placed in a vacuum impregnation device. Dissolving ferric nitrate in deionized water, and adjusting the pH value to 3.5 for later use. Opening a vacuum pumping pump of a vacuum impregnation device until the vacuum degree is 0.1mmHg, then slowly adding the prepared impregnation liquid from a feeding port, finishing the addition for 5min, evaporating at 60 ℃ until the flowing moisture on the surface of the catalyst completely disappears, finishing the loading, and putting the loaded catalyst in an oven according to the following procedures: in a muffle furnace according to: to obtain a leached catalyst.
And (3) taking cerium nitrate, impregnating according to the same method, drying, and roasting to obtain the final catalyst. And (3) drying procedure: and (3) roasting procedure:
Before the catalyst is used, the catalyst is reduced by 15 percent hydrogen in a reducing furnace, the reducing temperature is 500 ℃, the pressure is 0.5MPa, and the reducing time is 4 hours. The hydrogenation scheme shown in figure 1 was used with the catalyst packed in an adiabatic bed reactor.
Reaction conditions are as follows: the space velocity is 12000h-1, and the operating pressure is 4.5 MPa. The raw material composition is shown in table 1. The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
Example 5
A catalyst was prepared by weighing 100ml of an alumina carrier having a diameter of 4.0mm by the same method as in example 3. The activation temperature was 650 ℃.
before the catalyst is used, the catalyst is reduced by 25 percent hydrogen in a reducing furnace, the temperature is 700 ℃, the pressure is 0.5MPa, and the reduction time is 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
The raw material composition is shown in table 2. Reaction conditions are as follows: space velocity 10000h-1, operating pressure: 3.2 MPa.
the physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
Example 6
The method comprises the following steps of mixing commercially available pseudo-boehmite, silica gel, zirconium oxychloride powder and extrusion aid according to the weight ratio of alumina: silicon oxide: uniformly mixing zirconium oxide in a ratio of 8:1:3, extruding the mixture on a strip extruding machine for forming, drying the mixture at 120 ℃, and roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the Zr-Si-Al composite oxide carrier. The catalyst was prepared by the same method as in example 4.
Before the catalyst is used, 45% hydrogen and 55% nitrogen are used in a reducing furnace, the temperature is 450 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
Three sections of heat insulation devices connected in series are adopted, and the reaction conditions are as follows: space velocity 8000h-1, operating pressure: 4.0 MPa. The composition of the reaction raw materials is shown in table 1. The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
Comparative example 1
The alumina carrier with phi of 4.0mm is taken, the specific surface is 4.5m2/g, and the pore volume is 0.32 ml/g. The method comprises the steps of adopting an isometric impregnation method, impregnating a silver nitrate solution onto a carrier in an isometric manner, aging, drying and roasting to obtain a primary impregnated catalyst, then dissolving palladium chloride, impregnating in an isometric manner, aging, drying and roasting to obtain a final catalyst (PAH-01 hydrogenation catalyst of petrochemical research institute). The catalyst has Pd content of 0.050% and Ag content of 0.20%.
The catalyst is reduced by hydrogen for 160min at 100 ℃, the pressure is 0.5MPa, and the space velocity of the hydrogen is 100h < -1 >. The hydrogenation flow shown in the attached figure 1 is adopted, an isothermal bed reactor is adopted, and a catalyst is filled in a tubular bed reaction device.
The raw material composition is the same as that of example 1, and the reaction conditions are as follows: space velocity 16000h-1, operating pressure: 3.5 MPa.
The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
Comparative example 2
The catalyst was prepared in the same manner as in example 1 using alumina of Φ 4.0mm as a carrier, and the catalyst activation temperature was 850 ℃.
Before the catalyst is used, the catalyst is reduced by 25 percent hydrogen in a reducing furnace, the temperature is 450 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation flow shown in the attached figure 1 adopts an isothermal tubular reactor, and the catalyst is filled in an isothermal bed reactor. The XRD diffraction pattern of the reduced catalyst is shown in figure 3.
Evaluation was carried out by the same procedure as in example 1. The raw material composition is the same as that of example 2, and the reaction conditions are as follows: space velocity 15000h-1, operating pressure: 3.0 MPa.
The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
comparative example 3
Alumina of phi 4.0mm was weighed as a carrier, and the catalyst with low iron content was prepared by the same method as in example 1, and activated at 450 ℃.
Before the catalyst is used, the catalyst is reduced by 45 percent hydrogen in a reducing furnace, the temperature is 450 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation process shown in figure 1 adopts two-stage series adiabatic reactor process, and the catalyst is filled in adiabatic bed reactor.
The evaluation was carried out using two adiabatic reactors connected in series, the composition of the starting materials being the same as in example 1, the reaction conditions being: space velocity 8000h-1, operating pressure: 3.0 MPa.
The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
Comparative example 4
The catalyst was prepared in the same manner as in example 1, and was directly started after activation at 450 ℃ without reduction with hydrogen. The hydrogenation scheme shown in figure 1 was used, and the catalyst was packed in an adiabatic bed reactor.
Three sections of adiabatic reactors in series were used for evaluation, the raw material composition was the same as in example 1, and the reaction conditions were: space velocity 18000h-1, operating pressure: 3.5MPa, single-stage catalyst loading: 50 ml.
The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
Comparative example 5
The catalyst was prepared by the same method as in example 1 and activated at 450 ℃.
The catalyst is reduced in a tubular furnace under the atmosphere of 30% hydrogen and 55% nitrogen at 850 ℃, the pressure of 0.5MPa and the activation time of 4 h. The hydrogenation flow shown in the attached figure 1 is adopted, and an isothermal bed reactor is adopted. The XRD diffraction pattern of the reduced catalyst is shown in figure 4.
The evaluation was carried out using an isothermal bed reactor, the composition of the starting materials being the same as in example 1, and the reaction conditions: space velocity 15000h-1, operating pressure: 3.2 MPa.
The physical properties of the carrier used for the catalyst preparation are shown in Table 3, and the reaction results are shown in Table 4.
TABLE 3 Process conditions and catalyst Properties
TABLE 4 catalyst Properties of the examples and comparative examples
the present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (17)

1. A front-end deethanization front-end hydrogenation process alkyne removal method is characterized in that in a front-end deethanization front-end hydrogenation process ethylene device, tower top effluent from a front-end deethanization tower enters a hydrogenation reactor for selective hydrogenation to remove acetylene, a Ti-Fe-Ni selective hydrogenation catalyst is filled in the hydrogenation reactor, a carrier is a high-temperature-resistant inorganic oxide, the catalyst contains 5-15% of Fe, 0.2-1.5% of Ti and 0.5-1.8% of Ni based on 100% of the mass of the catalyst, the specific surface area of the catalyst is 10-300 m2/g, and the pore volume is 0.2-0.65 mL/g, wherein Fe is loaded on the carrier in an impregnation mode and is roasted at 300-700 ℃, and is prepared by reduction in an atmosphere containing hydrogen at the temperature of 200-500 ℃; in the catalyst, Fe mainly exists in a-Fe 2O3 form and contains FeNi phase; selecting the hydrogenation reaction conditions: the inlet temperature of the hydrogenation reactor is 50-100 ℃, the reaction pressure is 3.0-4.5 MPa, and the reaction volume space velocity is 5000-20000 h < -1 >.
2. The method of claim 1, wherein the amount of Fe present in the form of α -Fe2O3 is greater than 50% by weight of the total Fe present in the catalyst.
3. The alkyne removal method as claimed in claim 1, wherein the carrier of the catalyst is alumina or a composite carrier of alumina and other oxides, the alumina accounts for more than 50% of the mass of the carrier in the composite carrier of alumina and other oxides, and the other oxides are silica, zirconia, magnesia or titania; the alumina is of the theta, alpha or gamma type.
4. the method of claim 1, wherein the impregnation is an equal volume impregnation, an excess impregnation, a surface spray impregnation, a vacuum impregnation or multiple impregnations.
5. The alkyne removal method as claimed in claim 1, wherein the catalyst is obtained by preparing an aqueous solution of a Fe-containing precursor, an aqueous solution of a Ni precursor, and an aqueous solution of a Ti precursor, impregnating the carriers respectively, aging respectively, drying, calcining or impregnating the carriers with a mixed solution thereof, aging, drying, calcining, and finally reducing.
6. The alkyne removal method of claim 5, wherein: the dipping temperature is 30-60 ℃, the dipping time is 10-60 min, the pH value of the dipping solution is 1.5-5.0, the aging temperature is 30-60 ℃, the aging time is 30-120 min, the roasting temperature is 300-700 ℃, and the roasting time is 180-300 min.
7. The alkyne removal method of claim 5, wherein: the drying conditions were:
8. The alkyne removal method of claim 1 or 5, wherein: the roasting is temperature programmed roasting, and the roasting temperature program is set as follows:
9. The alkyne removal method of claim 1 or 5, wherein: the catalyst reduction means that the calcined catalyst is reduced by using a hydrogen-containing gas before the catalyst is used, the volume content of H2 is 10-50%, the reduction temperature is 200-500 ℃, the reduction time is 240-360 min, the volume space velocity is 100-500H < -1 >, and the reduction pressure is 0.1-0.8 MPa.
10. The alkyne removal method of claim 1, wherein: the hydrogenation reactor is an isothermal bed reactor or an adiabatic bed reactor.
11. The alkyne removal method of claim 1, wherein: the hydrogenation reactor is a two-section or three-section series adiabatic bed reactor, and the reaction conditions are as follows: the inlet temperature of the first section is 50-100 ℃, the inlet temperature of the second section is 50-100 ℃, and the inlet temperature of the hydrogenation reactor is 50-100 ℃ when the hydrogenation reactor is a three-section series adiabatic reactor.
12. The alkyne removal method of claim 1, wherein the hydrogenation raw material for selective hydrogenation comes from the overhead of a front deethanizer in a front deethanizing front hydrogenation process, and the volume of the hydrogenation raw material is as follows: 700-900 mu L/L of CO, 15-25% of hydrogen, 28-40% of methane, 0.5-1.0% of acetylene, 30-45% of ethylene and 5-10% of ethane.
13. The alkyne removal method as claimed in claim 1, wherein the catalyst contains 7.5-12% of Fe, 0.5-1% of Ti and 0.8-1.2% of Ni based on 100% of the mass of the catalyst, the specific surface area of the catalyst is 90-170 m2/g, and the pore volume is 0.40-0.60 mL/g; the selective hydrogenation reaction conditions are as follows: the inlet temperature of the hydrogenation reactor is 60-95 ℃, the reaction pressure is 2.8-3.8 MPa, and the volume space velocity is 8000-15000 h < -1 >.
14. The alkyne removal method as claimed in claim 3, wherein the composite support of alumina and other oxides is an alumina-zirconia composite support; the alumina is alpha-Al 2O 3.
15. the alkyne removal method as claimed in claim 6, wherein the roasting temperature is 400-500 ℃.
16. The alkyne removal method as claimed in claim 9, wherein the reduction conditions are N2+ H2 mixed gas for reduction, the reduction temperature is 300-400 ℃, the volume space velocity is 200-400H < -1 >, and the reduction pressure is 0.1-0.5 MPa.
17. The alkyne removal method of claim 11, wherein the reaction conditions are: the temperature of the first-stage inlet is 60-85 ℃, the temperature of the second-stage inlet is 75-90 ℃, and the temperature of the third-stage inlet is 80-95 ℃ when the hydrogenation reactor is a three-stage series adiabatic reactor.
CN201511032474.5A 2015-12-31 2015-12-31 Acetylene removal method by front-end deethanization and front-end hydrogenation process Active CN106927994B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511032474.5A CN106927994B (en) 2015-12-31 2015-12-31 Acetylene removal method by front-end deethanization and front-end hydrogenation process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511032474.5A CN106927994B (en) 2015-12-31 2015-12-31 Acetylene removal method by front-end deethanization and front-end hydrogenation process

Publications (2)

Publication Number Publication Date
CN106927994A CN106927994A (en) 2017-07-07
CN106927994B true CN106927994B (en) 2019-12-06

Family

ID=59443766

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201511032474.5A Active CN106927994B (en) 2015-12-31 2015-12-31 Acetylene removal method by front-end deethanization and front-end hydrogenation process

Country Status (1)

Country Link
CN (1) CN106927994B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547615A (en) * 1983-06-16 1985-10-15 Nippon Zeon Co. Ltd. Process for producing conjugated diolefins
CN101821219A (en) * 2007-09-19 2010-09-01 马克斯-普郎克科学促进学会 Use of mixture of an ordered intermetallic compound and an inert material as a catalyst and corresponding hydrogenation processes
CN104245112A (en) * 2012-04-18 2014-12-24 帝斯曼知识产权资产管理有限公司 Device useful for hydrogenation reactions (III)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547615A (en) * 1983-06-16 1985-10-15 Nippon Zeon Co. Ltd. Process for producing conjugated diolefins
CN101821219A (en) * 2007-09-19 2010-09-01 马克斯-普郎克科学促进学会 Use of mixture of an ordered intermetallic compound and an inert material as a catalyst and corresponding hydrogenation processes
CN104245112A (en) * 2012-04-18 2014-12-24 帝斯曼知识产权资产管理有限公司 Device useful for hydrogenation reactions (III)

Also Published As

Publication number Publication date
CN106927994A (en) 2017-07-07

Similar Documents

Publication Publication Date Title
JP2019501767A (en) Palladium-based supported hydrogenation catalyst, production method thereof, and use thereof
CN106928011B (en) Hydrogenation alkyne-removing method for ethylene material of methanol-to-olefin device
CN106928012B (en) Acetylene removal method by using carbon dioxide post-hydrogenation process
CN106928007B (en) Hydrogenation alkyne-removing method for methanol-to-olefin product
CN106927994B (en) Acetylene removal method by front-end deethanization and front-end hydrogenation process
CN108250017A (en) Method for selective hydrogenation of carbon three-fraction
CN106925279B (en) Fe-based selective hydrogenation catalyst, preparation method and application thereof
CN106928002B (en) Method for removing alkyne by hydrogenation after carbon dioxide
CN106928009B (en) Method for removing alkyne by hydrogenation before front deethanization
CN106927992B (en) Method for preparing polymerization-grade ethylene by removing alkyne through hydrogenation
CN108250018A (en) Refining method for removing alkyne by hydrogenation of ethylene material
CN106928005B (en) Alkyne removing method by pre-depropanization and pre-hydrogenation process
CN112675871B (en) Preparation method of hydrogenation catalyst before deethanization before carbon dioxide fraction
CN106928006B (en) Method for preparing polymer-grade ethylene by hydrogenation
CN106928004A (en) Carbon three-fraction selective hydrogenation method
CN106927995B (en) Method for removing alkyne by hydrogenation before pre-depropanization
CN106928014B (en) Alkyne removing method for preparing low-carbon olefin from methanol
CN106928003B (en) Alkyne removing method of carbon dioxide post-hydrogenation process
CN106928001B (en) Method for preparing polymer-grade ethylene by selective hydrogenation
CN106928013B (en) Hydrogenation alkyne removal method for ethylene material in methanol-to-olefin process
CN106928008B (en) Pre-hydrogenation alkyne removal method for methanol-to-olefin product
CN108250023A (en) Method for removing alkyne by hydrogenation in pre-deethanization and pre-hydrogenation process
CN112675872B (en) Hydrogenation catalyst before deethanization before carbon dioxide fraction
CN106927999B (en) Alkyne removing method for pre-depropanization and pre-hydrogenation process
CN108250011A (en) Ethylene refining method by selective hydrogenation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant