CN106928009B - Method for removing alkyne by hydrogenation before front deethanization - Google Patents

Method for removing alkyne by hydrogenation before front deethanization Download PDF

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CN106928009B
CN106928009B CN201511034114.9A CN201511034114A CN106928009B CN 106928009 B CN106928009 B CN 106928009B CN 201511034114 A CN201511034114 A CN 201511034114A CN 106928009 B CN106928009 B CN 106928009B
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catalyst
temperature
hydrogenation
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roasting
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CN106928009A (en
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张峰
苟尕莲
钱颖
景喜林
谷丽芬
王斌
韩伟
梁玉龙
车春霞
张忠东
胡晓丽
刘俊涛
黄德华
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Petrochina Co Ltd
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Abstract

‑1A hydrogenation alkyne-removing method before front deethanization is disclosed, wherein a hydrogenation catalyst is a Fe selective hydrogenation catalyst, a carrier is a high-temperature-resistant inorganic oxide, the catalyst contains 5-15% of Fe, preferably 8-12% of Fe and 0-2% of X, wherein X is one or more of K, La and Ce, the volume of a hydrogenation raw material is mainly 700-900 mu L/L of CO, 15-25% of hydrogen, 28-40% of methane, 0.5-1.0% of acetylene and 30-45% of ethylene, and the volume of ethane is 5-10%.

Description

Method for removing alkyne by hydrogenation before front deethanization
Technical Field
The invention relates to a method for removing acetylene by hydrogenation before front deethanization, in particular to a method for selectively hydrogenating and converting acetylene contained in a front deethanized front hydrogenated ethylene material into ethylene by using a Fe-based 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 to 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
C2H2+H2→C2H4 (1)
Side reactions
C2H4+H2→C2H6 (2)
C2H2+2H2→C2H6 (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, and the intermetallic compound is selected from the group consisting of CoAl and CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13Group (d) of (a). Among them, Fe is preferred4Al13and o-Co4Al13. The intermetallic compound is prepared by a hot melting method in solid chemistry. The hydrogenation performance of the catalyst is tested in a quartz tube furnace, the reaction temperature is 473K, and after the stable reaction is carried out for 20 hours, o-Co4Al13The catalyst has acetylene conversion rate up to 62%, ethylene selectivity up to 71%, and Fe4Al13The acetylene conversion rate on the 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 Fe-based hydrogenation catalyst and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a hydrogenation removal method before front-end deethanization. In particular to a Fe hydrogenation catalyst, which can selectively hydrogenate the acetylene contained in the tower top effluent of a front deethanizer in a front deethanizing front hydrogenation process and completely convert the acetylene into ethylene without loss of ethylene and propylene. .
The fore-deethanization fore-hydrogenation removing method of the invention is a fore-deethanization towerThe material flowing out of the tower top enters a hydrogenation reactor for selective hydrogenation to remove acetylene contained in the material, a Fe 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, preferably 8-12% of Fe and 0-2% of X, wherein the X is selected from one or more of K, La and Ce, and the preferable content of the X is 0.8-1.6%, based on 100% of the mass of the catalyst; the specific surface of the catalyst is 10-300 m2The preferred concentration is 90-170 m/g2The pore volume is 0.2-0.65 ml/g, preferably 0.40-0.60 ml/g, wherein Fe is loaded on the carrier by a dipping mode, and is prepared by roasting at 300-700 ℃ and reducing at 250-500 ℃ in an atmosphere containing hydrogen; in the catalyst, Fe is mainly alpha-Fe2O3The morphology exists. 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. 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 hydrogenation method adopts the hydrogenation catalyst, the carrier is a high-temperature-resistant inorganic oxide, the technical key point of the invention is that the catalyst contains Fe, and the catalyst is subjected to a specific roasting and reduction process, and 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 type or their mixture of multiple crystal forms, preferably alpha-Al2O3or containing alpha-Al2O3Mixed crystal form alumina of (1).
The preparation process of the Fe catalyst adopted by the alkyne removing method comprises the following steps:
The catalyst is obtained by preparing Fe precursor aqueous solution and X 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 process of the catalyst used in the present invention are:
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 400-500 ℃, and the roasting time is 180-300 min.
in the present invention, the drying is preferably temperature-programmed 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 method 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 the dried catalyst by adopting a temperature programming method, wherein the roasting temperature programming comprises the following steps: chamber
the catalyst X component is loaded by adopting the same steps, the roasting temperature is 300-700 ℃, preferably 400-500 ℃, the two components can also be prepared into a mixed solution, and the mixed solution is dipped on the surface of the carrier at one time according to the steps.
The active component of the catalyst is mainly Fe, and the catalyst can be a non-noble metal catalyst, even can not contain cobalt, nickel, 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 hydrogenation catalyst adopted by the method for removing alkyne by hydrogenation before front deethanization can be Fe or Fe2O3、Fe3O4Several forms exist in FeO, but among them, alpha-Fe2O3The Fe content in the form is higher than that in the other forms, and preferably, it is 50% or more of the total Fe mass. In the present invention, K, L is recommended to be added into the active composition containing irona. One or more Ce is beneficial to the formation and dispersion of the catalyst active phase, the stability of the active phase and the improvement of the catalyst selectivity and the coking resistance.
the activation temperature of the catalyst in the invention is related to the active composition, content and carrier of the catalyst, and alpha-Fe is formed after the activation process2O3Fe in a form, and is relatively stable, and the activation temperature cannot be too high; on the other hand, the degree of activation determines the reduction conditions of the catalyst, and the catalyst provided by the invention still uses alpha-Fe2O3fe in the form of Fe is a main component, and excessive reduction can influence the effect of the catalyst and the selectivity and is easy to coke.
The catalyst reduction of the present invention means that the calcined catalyst is reduced with a hydrogen-containing gas, H, before the catalyst is used2The volume content is preferably 10-50%, the reduction temperature is 250-500 ℃, the reduction time is 240-360 min, and the volume airspeed is 100-500 h-1The reduction pressure is 0.1-0.8 MPa; with the preferred proviso that N is used2+H2Reducing the mixed gas at the reduction temperature of 300-400 ℃ at a volume airspeed of 200-400 h-1The reduction pressure is preferably 0.1 to 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.
The hydrogenation reactor is an isothermal bed reactor or an adiabatic bed reactor, and selectively hydrogenates acetylene contained in an ethylene material to convert the acetylene into ethylene.
Because of the beneficial effects of the catalyst of the present invention, it is recommended to use two-stage or three-stage series adiabatic bed hydrogenation reactors.
When the hydrogenation reactor is a two-stage or three-stage series adiabatic bed reactor, the reaction conditions are as follows: the temperature of the first section inlet is 50-100 ℃, preferably 60-85 ℃, and the temperature of the second section inlet is 50-100 ℃, preferably 75-90 ℃; when the hydrogenation reactor is a three-section series adiabatic bed reactor, the inlet temperature of the three sections is 50-100 ℃, and preferably 80-95 ℃.
The hydrogenation material is the top effluent of a front deethanizer in the front deethanizing process, and the material composition mainly comprises: 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 shows the XRD spectrum (with the carrier background removed) of the catalyst of example 3 in which the invention is applied.
figure 3 is the XRD spectrum of the catalyst of comparative example 2 (minus the background of the support).
Figure 4 is the XRD spectrum of the catalyst of comparative example 5 (with the carrier background subtracted).
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-Fe2O3A, is Fe3O4And diamond was CeO.
The symbols in fig. 3 illustrate:
● is alpha-Fe2O3A, is Fe3O4■ is LaFeO3。
Symbolic illustration in fig. 4:
A is Fe3O4And xxx is Ce and ^ alpha-Fe.
In FIG. 2, Fe in the catalyst is mainly alpha-Fe2O3The relative content is 7.6%.
In FIG. 3, the second component La in the catalyst is mainly combined with the iron oxide to form LaFeO3The sintering of the auxiliary component and the active component destroys the distribution and the structure of the active component, and the activity of the catalyst is reduced.
FIG. 4 contains no alpha-Fe2O3And in the phase, Fe mainly appears in the form of simple substance alpha-Fe, the relative content is 8.92 percent, and the third component appears in the form of simple substance Ce.
Detailed Description
The analysis and test method comprises the following steps:
Specific surface area: GB/T-5816
Pore volume: GB/T-5816
Content of Fe oxide in different crystal forms: XRD
The content of active components in the catalyst is as follows: atomic absorption method
The conversion and selectivity in the examples were calculated according to the following formulas:
Acetylene conversion (%). 100. times. delta. acetylene/inlet acetylene content
Ethylene selectivity (%). 100 x. DELTA. ethylene/. DELTA.acetylene
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:Drying the catalyst, and then activating the catalyst by adopting a programmed heating method, wherein the activating program 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 reducing temperature of 300 ℃ and under the pressure of 0.5MPa 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 volume airspeed: 20000h-1(ii) a Operating pressure: 4.0 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.
Example 2
NaAlO is added at 50 deg.C2Solution and ZrCl4The solution is stirred and mixed, then is neutralized by nitric acid solution, is stirred for 10 hours, and is coprecipitated to generate uniform Al-Zr particles. The resultant was filtered, and Na contained therein was washed with deionized water+And Cl-and (3) ionizing, adding a proper amount of polyvinyl alcohol with the mass concentration of 15% as a pore-forming agent, and 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:Drying the catalyst, and activating the catalyst by adopting a programmed heating method, wherein the activating program 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 320 ℃, 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.
Reaction conditions are as follows: volume space velocity of 18000h-1the pressure is 3.5 MPa. The raw material composition is shown in table 2.
TABLE 2 hydrogenation feed composition
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 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:Drying the catalyst, and activating the catalyst by adopting a programmed heating method, wherein the activating program 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 340 ℃, under the pressure of 0.5MPa and for 4 hours. 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: volume airspeed 15000h-1The 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:Drying in a muffle furnace according to the following steps: chamberAnd (4) roasting. 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, reducing the catalyst in a reducing furnace by using 15 percent hydrogen at 360 ℃ under 0.5MPa for 4 h. The hydrogenation scheme shown in figure 1 was used with the catalyst packed in an adiabatic bed reactor.
Reaction conditions are as follows: volume space velocity 12000h-1The 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 380 ℃, 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: volume space velocity 10000h-1The operating pressure is as follows: 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 commercial pseudo-boehmite, silica gel, zirconium oxychloride powder and extrusion aid are mixed 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 400 ℃, the pressure is 0.5MPa, and the activation time is 4 h. The hydrogenation flow shown in the attached figure 1 is used, and the catalyst is filled in a fixed bed reaction device.
Three sections of heat insulation devices connected in series are adopted, and the reaction conditions are as follows: volume space velocity 8000h-1The operating pressure is as follows: 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.
Example 7
A catalyst was prepared in the same manner as in example 1 using alumina having a particle diameter of 4.0mm as a carrier, and activated at 450 ℃.
before the catalyst is used, the catalyst is reduced by 30 percent hydrogen in a reducing furnace, the temperature is 270 ℃, 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 the reaction device.
reaction conditions are as follows: volume airspeed 6000h-1The pressure is 3.5 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
Taking an alumina carrier with phi of 4.0mm and a specific surface of 4.5m2The pore volume was 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 volume space velocity of the hydrogen is 100h-1. The hydrogenation flow shown in the attached figure 1 adopts an isothermal tubular reactor, and the catalyst is filled in the reaction device.
The raw material composition is the same as that of example 1, and the reaction conditions are as follows: volume airspeed 16000h-1The operating pressure is as follows: 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 300 ℃, 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 the reaction device. The XRD diffraction pattern of the reduced catalyst is shown in figure 3.
The raw material composition is shown in table 2, and the reaction conditions are as follows: volume airspeed 15000h-1The operating pressure is as follows: 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 300 ℃, 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 a fixed bed reaction device.
the process adopts two sections of adiabatic reactors connected in series, the raw material composition is shown in table 1, and the reaction conditions are as follows: volume space velocity 8000h-1The operating pressure is as follows: 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 flow shown in the attached figure 1 is used, and the catalyst is filled in a fixed bed reaction device.
The three-stage series adiabatic reactor process was used, and the raw material composition is shown in table 1. Reaction conditions are as follows: volume space velocity of 18000h-1The operating pressure is as follows: 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 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 figure 1 is adopted, and an isothermal bed reactor catalyst is filled in a fixed bed reaction device. The XRD diffraction pattern of the reduced catalyst is shown in figure 4.
The composition of the raw materials is shown in table 1. Reaction conditions are as follows: volume airspeed 15000h-1The pressure is 3.6 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 catalyst preparation Using Carrier Properties
TABLE 4 Process conditions and catalyst Properties

Claims (17)

1. A front deethanization front hydrogenation alkyne removal method comprises the steps of enabling tower top effluent from a front deethanization tower to enter a hydrogenation reactor for selective hydrogenation in a front hydrogenation process ethylene device for front deethanization to remove acetylene; the method is characterized in that: a Fe selective hydrogenation catalyst is filled in a hydrogenation reactor, a carrier is a high-temperature-resistant inorganic oxide, the catalyst contains 5-15% of Fe and 0-2% of X by 100% of the mass of the catalyst, wherein the X is selected from one or more of K, La and Ce; the specific surface of the catalyst is 10-300 m2The pore volume is 0.2-0.65 mL/g, wherein Fe is loaded on the carrier in an impregnation mode; roasting at 300-700 deg.c, reducing in hydrogen-containing atmosphere at 250-500 deg.c to obtain the catalyst with Fe element of alpha-Fe2O3The form exists; 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: based on 100% of the mass of the catalyst, the catalyst contains 8-12% of Fe, and the content of X is 0.8-1.6%; the specific surface of the catalyst is 90-170 m2The pore volume is 0.40-0.60 mL/g, and the hydrogenation 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。
3. the method of claim 1, wherein: in the catalyst, alpha-Fe2O3The Fe in the form accounts for more than 50% of the total weight of the Fe.
4. The method of 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, and the other oxides can be silicon oxide, zirconium oxide, magnesium oxide or titanium oxide; the alumina is in theta, alpha and gamma type.
5. The method according to claim 4, wherein the composite support of alumina and other oxides is an alumina-zirconia composite support; the alumina is alpha-Al2O3。
6. The method according to claim 1, wherein the impregnation is an equal volume impregnation, an excess impregnation, a surface spray impregnation, a vacuum impregnation or a plurality of impregnations.
7. The method of claim 1, wherein: the catalyst is obtained by preparing Fe precursor aqueous solution and X 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.
8. The method of claim 7, wherein: the dipping temperature is 30-60 ℃, the dipping time is 10-60 min, the pH value of a dipping solution is 1.5-5.0, the aging temperature is 30-60 ℃, the aging time is 30-120 min, and the roasting temperature is 300-700 ℃; the roasting time is 180-300 min.
9. The method of claim 8, wherein: the roasting temperature is 400-500 ℃.
10. The method of claim 7, wherein: the drying is temperature programmed drying, and the drying temperature program is set as follows:
11. The method according to claim 1 or 7, characterized in that: the roasting is temperature programmed roasting, and the roasting temperature program is set as follows:
12. The method according to claim 1 or 7, characterized in that: catalyst reduction means that the calcined catalyst is reduced with a hydrogen-containing gas, H, before the catalyst is used2The volume content is 10-50%, the reduction temperature is 250-500 ℃, the reduction time is 240-360 min, and the volume airspeed is 100-500 h-1And the reduction pressure is 0.1-0.8 MPa.
13. The method of claim 12, wherein: the reduction condition is N2+H2reducing the mixed gas at the reduction temperature of 300-400 ℃ at a volume airspeed of 200-400 h-1The reduction pressure is 0.1-0.5 MPa.
14. the method of claim 1, wherein: the hydrogenation reactor is an isothermal bed reactor or an adiabatic bed reactor.
15. The method of claim 14, 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 preferred temperature is 75-90 ℃; when the hydrogenation reactor is a three-section series adiabatic bed reactor, the inlet temperature of the three sections is 50-100 ℃, and preferably 80-95 ℃.
16. The method of claim 15, wherein: the temperature of the first-section inlet is 60-85 ℃, the temperature of the second-section inlet is 75-90 ℃, and the temperature of the third-section inlet is 80-95 ℃.
17. The method of claim 1, wherein: the material for selective hydrogenation is the top effluent from the front deethanizer in the front deethanizing front hydrogenation process, and the volume composition of the raw materials 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.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1972885A (en) * 2004-06-23 2007-05-30 催化溶液公司 Catalysts and processes for selective hydrogenation of acetylene and dienes in light olefin feedstreams
CN102206130A (en) * 2011-04-07 2011-10-05 中国石油天然气股份有限公司 Process for the selective hydrogenation of a carbon-containing fraction
CN102218323A (en) * 2011-04-22 2011-10-19 西北化工研究院 Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1972885A (en) * 2004-06-23 2007-05-30 催化溶液公司 Catalysts and processes for selective hydrogenation of acetylene and dienes in light olefin feedstreams
CN102206130A (en) * 2011-04-07 2011-10-05 中国石油天然气股份有限公司 Process for the selective hydrogenation of a carbon-containing fraction
CN102218323A (en) * 2011-04-22 2011-10-19 西北化工研究院 Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof

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