CN106925275B - Ti-Fe-Ni selective hydrogenation catalyst, preparation method and application thereof - Google Patents

Ti-Fe-Ni selective hydrogenation catalyst, preparation method and application thereof Download PDF

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CN106925275B
CN106925275B CN201511032581.8A CN201511032581A CN106925275B CN 106925275 B CN106925275 B CN 106925275B CN 201511032581 A CN201511032581 A CN 201511032581A CN 106925275 B CN106925275 B CN 106925275B
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alumina
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CN106925275A (en
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梁玉龙
付含琦
苟尕莲
张峰
韩伟
钱颖
车春霞
景喜林
常晓昕
王涛
谢培思
王斌
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China Petroleum and Natural Gas Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
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    • 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
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Abstract

A Ti-Fe-Ni selective hydrogenation catalyst, a preparation method and an application thereof are disclosed, wherein the catalyst contains 2-15% of Fe 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 m2(ii)/g; the pore volume is 0.2-0.65 ml/g; wherein Fe is loaded on the carrier by dipping, and is prepared by roasting and hydrogen atmosphere reduction, and in the catalyst, Fe is mainly alpha-Fe2O3Exists in a form and contains a FeNi phase. The catalyst of the present invention can be used in C2～3Selective hydrogenation of acetylene, propyne (MA) and Propadiene (PD) in the cracked fraction. The catalyst has mild hydrogenation activity, excellent olefin selectivity, high olefin increment, good operation elasticity, low green oil generation amount and good long-period running performance. And the catalyst cost is far lower than that of the noble metal Pd catalyst.

Description

Ti-Fe-Ni selective hydrogenation catalyst, preparation method and application thereof
Technical Field
The invention relates to a Ti-Fe-Ni selective hydrogenation catalyst, which is used for preparing ethylene and propylene by selective hydrogenation of acetylene, propyne (MA) and Propadiene (PD) contained in a fraction cracked by carbon dioxide.
Background
Ethylene and propylene are one of the most important basic raw materials in the petrochemical industry, and are mostly prepared by steam cracking of petroleum hydrocarbons (such as ethane, propane, butane, naphtha, light diesel oil and the like) as monomers for synthesizing various polymers. Ethylene-based C obtained by this process2The fraction also contains 0.5-2.5% (mole fraction) acetylene. The presence of acetylene complicates the polymerization process of ethylene and deteriorates the polymer properties. When polyethylene is produced by a high pressure process, there is a risk of explosion due to the accumulation of acetylene; in addition, the presence of acetylene also reduces the activity of the polymerization catalyst and increases the catalyst consumption when producing polyethylene. Therefore, acetylene in ethylene must be reduced to a certain value or less to be used as a monomer for synthesizing a high polymer.
At present, noble metal Pd series hydrogenation catalysts are commonly adopted in the industry for selectively removing C2Acetylene and C in the distillate3Propyne (MA) and Propadiene (PD) in the fractions. The patent US4404124 prepares a selective hydrogenation catalyst with a palladium shell layer distribution as an active component by a step-by-step impregnation method, and can be applied to selective hydrogenation of carbon dioxide and carbon three fractions to eliminate acetylene in ethylene and propadiene in propylene. US5587348 uses alumina as carrier, regulates the action of promoter silver and palladium, and adds alkali metal and chemically bonded fluorine to prepare excellent carbon dioxide hydrogenation catalyst. The catalyst has the advantages of reducing the generation of green oil, improving the selectivity of ethylene,reducing the generation amount of oxygen-containing compounds. US5519566 discloses a process for preparing silver and palladium catalysts by wet reduction, by adding organic or inorganic reducing agents to the impregnation solution, silver and palladium bi-component selective hydrogenation catalysts are prepared.
Because of using noble metal Pd as active component, the catalyst cost is high, and because the noble metal catalyst activity is high, there are certain problems in the aspects of device start-up stability, operation flexibility and long-period operation performance of the catalyst. The development of a low-cost and excellent-performance carbon dioxide hydrogenation catalyst system is always the aim of scientific research personnel in the field.
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 Ti-Fe-Ni hydrogenation catalyst and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a Ti-Fe-Ni selective hydrogenation catalyst, a preparation method and application thereof, which are used for selective hydrogenation of alkyne and dialkene in carbon dioxide and carbon three-fraction. The catalyst of the invention can be used for selectively hydrogenating a small amount of acetylene, propyne (MA) and Propadiene (PD) contained in a cracking atmosphere to convert the acetylene, the propyne (MA) and the Propadiene (PD) into ethylene and propylene, can also be used for refining reaction of the ethylene and the propylene, and can be used for completely removing the trace amount of acetylene, the propyne (MA) and the Propadiene (PD) contained in raw materials of the ethylene and the propylene and producing polymerization-grade raw materials.
In order to achieve the purpose, the invention adopts the following technical scheme: a Ti-Fe-Ni selective hydrogenation catalyst takes a high-temperature resistant inorganic oxide as a carrier, and the catalyst contains 2-15% of Fe, preferably 4-10% of Ti, 0.2-1.5% of Ti, preferably 0.5-1% of Ni, 0.5-1.8% of Ni, preferably 0.8-1.2% of Ti, and the specific surface of the catalyst is 10-300 m in terms of 100% of the mass of the catalyst2A concentration of 30 to 170m2The pore volume is 0.2-0.65 ml/g, preferably 0.30-0.63 ml/g, wherein Fe is loaded on the carrier by a dipping mode, and is prepared by roasting at 300-700 ℃ and reducing at 200-500 ℃ in an atmosphere containing hydrogen; in the catalyst, Fe is mainly alpha-Fe2O3Exists in a form and contains a FeNi phase.
The Fe element in the catalyst can be Fe or Fe2O3、Fe3O4FeO, etc., 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 catalyst of the present invention, a FeNi phase is also present, preferably Ti is present in an oxidized state.
The carrier of the invention is a high-temperature resistant inorganic oxide, and the technical key point of the invention is that the catalyst contains Fe, and the carrier has no special requirements such as one or more of alumina, silicon oxide, zirconium oxide, magnesium oxide and the like after specific roasting and reduction processes. 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 invention also provides a preparation method of the catalyst, which comprises the following steps:
the catalyst is obtained by preparing Fe precursor aqueous solution, Ti precursor aqueous solution and Ni precursor aqueous solution, respectively impregnating the carrier, respectively aging, drying and roasting, or impregnating the carrier with the 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 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 a temperature-raising drying, and the drying temperature program is set as follows:
Figure GDA0002090183830000041
Figure GDA0002090183830000042
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:
Figure GDA0002090183830000043
Figure GDA0002090183830000044
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:
Figure GDA0002090183830000051
(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 catalyst reduction of the invention means that before the catalyst is used, the calcined catalyst is reduced by hydrogen-containing gas, H2The content is preferably 10-50%, the reduction temperature is preferably 250-500 ℃, and N is preferably used2+H2The mixed gas is under the condition of micro positive pressureReducing at 300-400 ℃, wherein the reduction time is preferably 240-360 min, and the volume airspeed is preferably 200-400 h-1The reduction pressure is preferably 0.1 to 0.5 MPa.
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 Fe element in the catalyst can be Fe or Fe2O3、Fe3O4In the invention, Ni is recommended to be added into the active composition containing iron, and a FeNi phase can be formed after activation and reduction, which is beneficial to activation of hydrogen and improvement of catalyst activity; in the present invention, it is recommended to add TiO to the iron-containing active component2The method is beneficial to the formation and dispersion of the catalyst active phase, 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 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 Ti-Fe-Ni selective hydrogenation catalyst is particularly suitable for selective hydrogenation removal of acetylene, propyne and propadiene contained in an ethylene atmosphere.
The catalyst of the invention has the following beneficial effects:
(1) the catalyst of the invention has far lower cost than noble metal Pd catalyst, the used raw materials are harmless and easy to obtain, and the preparation method is simple and is easy to realize technically.
(2) The catalyst has good hydrogenation activity and good operation elasticity, and is suitable for application in industrial devices.
(3) The catalyst of the invention has good selectivity, and the olefin increment is higher than that of a noble metal catalyst.
(4) The green oil generation amount of the catalyst is far lower than that of a noble metal catalyst, and the catalyst is suitable for long-period operation of the catalyst.
Drawings
FIG. 1 is the XRD spectrum (minus the carrier alpha-Al) of the catalyst of example 32O3Background);
FIG. 2 is the XRD spectrum (minus the carrier alpha-Al) of the catalyst of comparative example 22O3Background);
FIG. 3 is the XRD spectrum (minus the carrier alpha-Al) of the catalyst of comparative example 52O3Background);
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
Symbolic illustration in fig. 1:
● is alpha-Fe2O3■ is Fe3O4A, tangle-solidup is FeNi, and t is TiO2；
The symbols in fig. 2 illustrate:
● is alpha-Fe2O3■ is Fe3O4Tangle-solidup is FeNi, diamond-solid is anatase;
the symbols in fig. 3 illustrate:
^ is alpha-Fe, ■ is Fe3O4A t is Ti2O, wherein a is Ni;
as can be seen in FIG. 1, the Fe in the catalyst is mainly alpha-Fe2O3The form appears, the relative content is 8.10 percent, and simultaneously FeNi phase appears;
as can be seen in fig. 2, Ti in the catalyst sinters with iron oxide, an anatase crystalline phase appears, distribution and structure of active components are destroyed, and activity of the catalyst is reduced;
in FIG. 3, Fe mainly appears in the form of simple substance alpha-Fe, the relative content is 8.92%, and a small amount of Fe exists3O4And (4) forming.
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
100ml of clover-type alpha-alumina carrier with phi of 4.5 multiplied by 4.5mm is weighed and placed in a 1000ml beaker. 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 solution at 50 ℃, impregnating the surface of a carrier in an equal volume, quickly shaking the carrier for impregnation for 6min, standing for 30min until the adsorption is balanced, completely sealing the mouth of a beaker by using a preservative film, aging in a water bath at 60 ℃ for 30min, and then drying in an oven according to the following procedures:
Figure GDA0002090183830000071
transferring the catalyst into an evaporating dish, and activating the catalyst in a muffle furnace by adopting a programmed heating method, wherein the activating program comprises the following steps:
Figure GDA0002090183830000072
Figure GDA0002090183830000073
weighing nickel nitrate, impregnating according to the preparation steps, drying and activating. Then taking tetrabutyl titanate, carrying out loading according to the same method, and activating to obtain the catalyst.
The evaluation method comprises the following steps: the performance of the catalyst is evaluated on a 10ml micro-reaction device, the catalyst is crushed in a mortar, 3ml of the catalyst is sieved by a sieve of 10-20 meshes, and the sieved catalyst is diluted to 5ml by glass beads of 20 meshes and filled.
The catalyst is firstly reduced by 40 percent of hydrogen and 60 percent of nitrogen, the reduction temperature is 350 ℃, the pressure is 0.5MPa, and the reduction time is 4 hours.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas and comprises the following components:
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
Example 2
At 50 ℃, a certain amount of NaAlO is added2Solution 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 15% polyvinyl alcohol serving 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, wherein the mass ratio of alumina to zirconia in the carrier is 4: 1.
100ml of the composite carrier is weighed and placed in a 1000ml big beaker. Heating and dissolving ferric nitrate and nickel nitrate in 100ml of 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:
Figure GDA0002090183830000081
transferring the catalyst into an evaporating dish, and activating the catalyst in a muffle furnace by adopting a programmed heating method, wherein the activating program comprises the following steps:
Figure GDA0002090183830000084
taking a proper amount of tetrachloroAnd (3) carrying titanium according to the same steps, and roasting to obtain the catalyst.
The catalyst evaluation was carried out in the same manner as in example 1, and the catalyst was reduced with 30% hydrogen at a reduction temperature of 300 ℃ under a pressure of 0.5MPa for a reduction time of 4 hours.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas and comprises the following components:
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
Example 3
100ml of spherical alpha-alumina carrier with phi of 1.5mm is weighed. Dissolving ferric nitrate in 40ml of deionized water, adjusting the pH value to 3.0, adjusting the temperature of the soaking solution to 40 ℃, spraying and soaking the ferric nitrate on a carrier by a spraying pot, loading the carrier in a rotary drum for 10min to uniformly upload active components, controlling the loading process to be finished within 6min, and then, in an oven according to the following procedures:transferring the catalyst into an evaporating dish, and activating the catalyst in a muffle furnace by adopting a programmed heating method, wherein the activating program comprises the following steps:
Figure GDA0002090183830000087
Figure GDA0002090183830000088
to obtain a leached catalyst.
And (3) adopting the same method of the first step, dissolving nickel nitrate, spraying and soaking the nickel nitrate on the surface of the first-soaked catalyst, drying and roasting to obtain the final catalyst. And (3) drying procedure:
Figure GDA0002090183830000089
Figure GDA00020901838300000810
and (3) roasting procedure:
Figure GDA00020901838300000811
Figure GDA00020901838300000812
taking a proper amount of titanium tetrachloride, carrying out loading according to the same steps, and roasting to obtain the catalyst.
The catalyst was reduced with 20% hydrogen at 350 deg.C under 0.5MPa for 4h, according to the same method as in example 1. XRD analysis of the reduced catalyst is shown in figure 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas and comprises the following components:
Figure GDA0002090183830000091
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
Example 4
50ml of spherical alumina-titania support of 2.0mm diameter were weighed out and placed in a rotary evaporator. Ferric nitrate was dissolved in 15ml of deionized water and the pH was adjusted to 3.5 for further use. Opening a vacuum pumping pump of the rotary evaporator to a vacuum degree of 0.1mmHg, then slowly adding the prepared impregnation liquid from a feeding port, finishing adding after 5min, carrying out rotary evaporation under the heating of water bath at 60 ℃ until the flowing moisture on the surface of the catalyst completely disappears, finishing loading, moving the loaded catalyst out of the rotary evaporator, and carrying out the following procedures in an oven:
Figure GDA0002090183830000092
Figure GDA0002090183830000093
in a muffle furnace according to:
Figure GDA0002090183830000094
Figure GDA0002090183830000095
to obtain a leached catalyst.
And (3) taking lanthanum nitrate, impregnating according to the same method, drying, and roasting to obtain the final catalyst. And (3) drying procedure:and (3) roasting procedure:
Figure GDA0002090183830000097
Figure GDA0002090183830000098
and (3) taking tetrabutyl titanate, carrying out loading according to the same steps, and roasting to obtain the catalyst.
The catalyst was reduced with 15% hydrogen at 400 ℃ under 0.5MPa for 4 hours, using the same method as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas and comprises the following components:
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
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 500 ℃.
The catalyst is reduced by 25 percent hydrogen at 400 ℃ and under 0.5MPa for 4 h.
Evaluation was carried out in the same manner as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas (ethane balance gas) and has the following composition:
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
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 1.
The catalyst is reduced at high temperature in a tubular furnace, wherein the reducing atmosphere is 45% hydrogen, the temperature is 450 ℃, the pressure is 0.5MPa, and the reducing time is 4 h.
Evaluation was carried out in the same manner as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas (ethane is balance gas) and has the following composition:
Figure GDA0002090183830000102
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
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 120 ℃, the pressure is 0.5MPa, and the space velocity of the hydrogen is 100h-1。
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
Evaluation of feed gas composition:
Figure GDA0002090183830000111
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
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 ℃.
The catalyst is reduced by 25 percent hydrogen at 350 ℃, the pressure is 0.5MPa and the reduction time is 4 h. The XRD diffraction pattern of the reduced catalyst is shown in figure 2.
Evaluation was carried out in the same manner as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas (ethane balance gas) and has the following composition:
Figure GDA0002090183830000112
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 3
A catalyst was prepared by the same method as in example 1 by using alumina having a particle diameter of 4.0mm as a carrier, and activated at 450 ℃.
The catalyst is reduced by 35 percent hydrogen at 350 ℃, the pressure is 0.5MPa and the reduction time is 4 h.
Evaluation was carried out in the same manner as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas (ethane balance gas) and has the following composition:
Figure GDA0002090183830000113
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 4
The same catalyst as in example 1 was used, and the catalyst was activated at 450 ℃ and then directly started without reduction with hydrogen.
Evaluation was carried out in the same manner as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas (ethane balance gas) and has the following composition:
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 5
The catalyst prepared in the same manner as in example 1 was activated at 450 ℃.
The catalyst is reduced in a tubular furnace under the atmosphere of 30% hydrogen and 55% nitrogen at 600 ℃, the pressure of 0.5MPa and the reduction time of 4 h. The XRD diffraction pattern of the reduced catalyst is shown in figure 3.
Evaluation was carried out in the same manner as in example 1.
Reaction conditions are as follows: space velocity of 8000h-1The pressure is 1.5MPa, and the reaction temperature is 80 ℃.
The reaction raw material gas adopts standard gas (ethane balance gas) and has the following composition:
Figure GDA0002090183830000122
the physical properties of the catalyst are shown in Table 1, and the reaction results are shown in Table 2.
TABLE 1 Carrier and catalyst Properties
TABLE 2 catalyst pairs C2-3Selective hydrogenation of cracked material
Figure GDA0002090183830000141
Note: acetylene and ethylene are polymerized to produce n-butene, which is further polymerized to produce "green oil", and the amount of n-butene produced is generally used to characterize the amount of catalyst green oil "produced during the analysis.
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 (15)

1. A Ti-Fe-Ni selective hydrogenation catalyst takes a high-temperature resistant inorganic oxide as a carrier, and is characterized in that the catalyst contains 2-15% of Fe, 0.2-1.5% of Ti and 0.5-1.8% of Ni by 100% of the mass of the catalyst, and the specific surface area of the catalyst is 10-300 m2The pore volume is 0.2-0.65 mL/g, wherein Fe is loaded on the carrier by a dipping mode, and is prepared by roasting at 300-700 ℃ and reducing at 200-500 ℃ in an atmosphere containing hydrogen; in the catalyst, Fe is mainly alpha-Fe2O3Exists in a form and contains a FeNi phase.
2. The Ti-Fe-Ni selective hydrogenation catalyst of claim 1 wherein, in the catalyst, α -Fe2O3The Fe in the form accounts for more than 50% of the total weight of the Fe.
3. The Ti-Fe-Ni selective hydrogenation catalyst according to claim 1, wherein the carrier is an alumina or alumina-based carrier, the alumina-based carrier being a composite carrier of alumina and other oxides, wherein alumina accounts for 50% or more of the mass of the carrier; the alumina is theta, alpha, gamma or the mixture of a plurality of crystal forms.
4. The Ti-Fe-Ni selective hydrogenation catalyst of claim 1 wherein the impregnation means is an equal volume impregnation, an excess impregnation, a surface spray impregnation, a vacuum impregnation or multiple impregnations.
5. The Ti-Fe-Ni selective hydrogenation catalyst according to claim 1, wherein the catalyst contains 4 to 10% of Fe, 0.5 to 1% of Ti, 0.8 to 1.2% of Ni, and has a specific surface area of 30 to 170m, based on 100% by mass of the catalyst2The pore volume is 0.30 to 0.63 mL/g.
6. The Ti-Fe-Ni selective hydrogenation catalyst of claim 3, wherein the alumina-based support is a composite of alumina with silica, zirconia, magnesia.
7. The Ti-Fe-Ni selective hydrogenation catalyst of claim 3, wherein the composite support of alumina and other oxides is an alumina-zirconia composite support in which the alumina content is 60% or more; the alumina being alpha-Al2O3Or containing alpha-Al2O3Mixed crystal form alumina of (1).
8. A method for preparing a Ti-Fe-Ni selective hydrogenation catalyst as claimed in any one of claims 1 to 7 wherein the catalyst is prepared by a process comprising: preparing impregnation liquid containing Fe precursor water solution and Ti and Ni precursor water solution, impregnating the carrier respectively, aging, drying and roasting respectively or impregnating the carrier by using mixed solution thereof, aging, drying and roasting, and finally reducing to obtain the catalyst.
9. The preparation method of claim 8, 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.
10. The method according to claim 8, wherein the drying conditions are:
Figure FDA0002175813580000021
Figure FDA0002175813580000022
11. the method of claim 8, wherein: the roasting is temperature-raising roasting, and the roasting temperature program is set as follows:
Figure FDA0002175813580000023
Figure FDA0002175813580000024
12. the method of claim 8, wherein: catalyst reduction means that the calcined catalyst is reduced with a hydrogen-containing gas, H, before the catalyst is used2The content is 10-50%, the reduction temperature is 200-500 ℃, 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 according to claim 9, wherein the calcination temperature is 400 to 500 ℃.
14. The method of claim 12, wherein the catalyst is reduced to 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.
15. Use of the catalyst of claim 1, wherein: the Ti-Fe-Ni selective hydrogenation catalyst is used for selective hydrogenation removal of acetylene, propyne and propadiene contained in an ethylene atmosphere.
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