CN106475094B - Alkyne selective hydrogenation catalyst, preparation method and application thereof, and method for removing alkyne from carbon-containing fraction - Google Patents
Alkyne selective hydrogenation catalyst, preparation method and application thereof, and method for removing alkyne from carbon-containing fraction Download PDFInfo
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Abstract
The invention relates to the field of catalysts, and discloses an alkyne selective hydrogenation catalyst, a preparation method of the catalyst, and a method for removing alkyne by selective hydrogenation of carbon-containing fraction by using the alkyne selective hydrogenation catalyst. The alkyne selective hydrogenation catalyst contains a carrier, a main active component and an optional auxiliary active component, wherein the main active component and the optional auxiliary active component are loaded on the carrier, the alkyne selective hydrogenation catalyst is characterized in that the carrier is a carbon carrier, the carbon carrier is selected from one or more of graphite, coal-based carbon, carbon black, coconut shell carbon, a high-molecular carbonized material and a carbon molecular sieve, and the main active component is palladium. The alkyne selective hydrogenation catalyst has high activity and good selectivity when being applied to the selective hydrogenation and alkyne removal process of carbon-enriched fraction, and can effectively inhibit the problems of easy temperature runaway and green oil generation.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an alkyne selective hydrogenation catalyst, a preparation method of the catalyst and a method for removing alkyne by selective hydrogenation of carbon dioxide fraction by using the alkyne selective hydrogenation catalyst.
Background
The acetylene content in the carbon-reduced fraction in the process of preparing ethylene by steam cracking of petroleum hydrocarbon is usually 0.5-3%, and the acetylene content in the carbon-reduced fraction in the process of preparing olefin from coal is 5-200 ppm. Ethylene is an important monomer for the production of polyethylene. In the production of polyethylene, a small amount of acetylene in ethylene reduces the activity of a polymerization catalyst and deteriorates the physical properties of a polymer, so that the acetylene content in ethylene must be reduced below a certain value to be used as a monomer for synthesizing a high polymer. In order to meet the requirements of the polymerization grade, the carbon-dioxide fraction needs to be subjected to alkyne removal treatment. The acetylenes in the carbon-dioxide fraction are generally removed by selective hydrogenation, a relatively economical process. The acetylene in the carbon-dioxide fraction is converted into ethylene by hydrogenation reaction by using a selective hydrogenation catalyst, and the method not only can effectively remove the acetylene, but also can increase the yield of the ethylene.
At present, the industry is divided into a pre-hydrogenation technology and a post-hydrogenation technology according to different positions and material compositions in a separation process in a hydrogenation process, wherein the pre-hydrogenation technology for carbon dioxide has the characteristics of simplified separation process, less equipment investment and low operation energy consumption and is widely applied. However, in the hydrogenation technology before carbon dioxide, the hydrogen contained in the carbon dioxide fraction is greatly excessive, the quality of the product at the outlet of the reactor can only be controlled by adjusting the inlet temperature of the reactor, the adjusting and controlling means is single, the activity of the catalyst is low when the inlet temperature is too low, the alkyne of the material cannot be removed, and the excessive hydrogenation reaction is easy to occur when the inlet temperature is too high, so that the temperature stability requirement of the catalyst is high, and the stable operation of the system can be ensured. In addition, in the selective hydrogenation acetylene removal reaction, acetylene adsorbed on the surface of the carrier is easily subjected to hydrodimerization reaction to generate unsaturated C4 hydrocarbons such as 1, 3-butadiene, and the unsaturated C4 hydrocarbons such as 1, 3-butadiene are further reacted with acetylene, ethylene or other unsaturated hydrocarbons to generate C4-C24 oligomers, and the C4-C24 oligomers are commonly referred to as green oils. In the reaction process, the catalyst is inevitably adhered to the alkyne selective hydrogenation catalyst, so that the hydrogenation activity and selectivity of the catalyst are gradually reduced, the service cycle is shortened, the catalyst is promoted to be frequently regenerated, the service life of the catalyst is influenced, and the production cost is improved.
Patent CN102989453A discloses a palladium-silver-carbon pre-hydrogenation catalyst of alumina-titania composite carrier, which improves the catalyst activity by preparing alumina-titania composite carrier with bimodal distribution, patent US7453017B1 discloses a palladium catalyst with silica as carrier, and improves the catalyst activity and selectivity by adding Ti, L a and Nb.
The hydrogenation catalyst before selection of the carbon dioxide fraction for industrial application mostly takes alumina or silica as a carrier and palladium as an active component, and the activity of the catalyst is improved by adding different cocatalyst components or modifying the carrier. However, it has been found that the surface of the carrier has a certain acidic center, so that unsaturated hydrocarbons are easily polymerized to produce a green oil byproduct, thereby reducing the selectivity and activity of the catalyst. In actual production, the suppression of green oil generation is often achieved by lowering the acidity of the alumina carrier by raising the calcination temperature of the carrier, but the consequence of raising the calcination temperature is not only the reduction of the specific surface of the alumina carrier but also the limitation of the crystalline phase of the alumina. Therefore, the development of a novel low-green oil and stable catalyst which is not easy to run away from temperature becomes a problem to be solved by the current carbon dioxide fraction pre-hydrogenation catalyst.
Disclosure of Invention
The invention aims to overcome the defects that the prior alkyne selective hydrogenation catalyst is easy to generate temperature runaway and/or generate a large amount of green oil during the hydrogenation treatment before the carbon dioxide fraction is carried out, and provides an alkyne selective hydrogenation catalyst, a preparation method of the catalyst and a method for carrying out selective hydrogenation and alkyne removal on the carbon dioxide fraction by using the alkyne selective hydrogenation catalyst. The alkyne selective hydrogenation catalyst provided by the invention is high in activity and good in selectivity when being applied to a selective hydrogenation alkyne removal process of carbon-dioxide fraction, and can effectively inhibit the problems of easiness in temperature runaway and green oil generation.
The invention provides an alkyne selective hydrogenation catalyst, which comprises a carrier, a main active component and an optional auxiliary active component, wherein the main active component and the optional auxiliary active component are loaded on the carrier, the carrier is a carbon carrier, the carbon carrier is selected from one or more of graphite, coal-based carbon, carbon black, coconut shell carbon, a high-molecular carbonized material and a carbon molecular sieve, and the main active component is palladium.
The present invention also provides a method for preparing the above catalyst for selective hydrogenation of alkynes, which comprises supporting a palladium precursor and a co-active component precursor on a carbon support using a dipping method or a spraying method, and performing a reduction treatment using an ionizing radiation method after supporting the palladium precursor.
The invention also provides the alkyne selective hydrogenation catalyst prepared by the preparation method.
The invention also provides the application of the alkyne selective hydrogenation catalyst in the selective hydrogenation alkyne removal process of carbon-containing fraction.
The invention also provides a method for selective hydrogenation and alkyne removal of a carbon-reduced fraction, which comprises the step of carrying out pre-hydrogenation treatment on the carbon-reduced fraction in the presence of the alkyne selective hydrogenation catalyst.
The inventors of the present invention have unexpectedly found, in the course of their intensive studies, that the use of a carbon support instead of the alumina and/or silica support commonly used in the prior art and metallic palladium as an active component can effectively suppress the problems of warm-over and green oil, the principle of which may be: the carbon carrier has the characteristics of high temperature resistance and corrosion resistance, and has weak acidity, so that the occurrence of a plurality of side reactions can be reduced.
Compared with the prior art, the alkyne selective hydrogenation catalyst has the main advantages that:
(1) the catalyst has wide operation temperature range, good stability and difficult temperature runaway;
(2) the catalyst carrier is a carbon material, so that acidic oxides in the catalyst are obviously reduced, and the generation of green oil is avoided;
(3) the loss of noble metal active components and the introduction of impurities in the reducing process of the reducing agent are avoided by adopting an ionization irradiation reduction method;
(4) the noble metal component in the catalyst is easy to recover, and the cost of the catalyst is reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an SEM photograph of the alkyne selective hydrogenation catalyst A prepared in example 1.
Fig. 2 is an SEM photograph of the alkyne selective hydrogenation catalyst F prepared in comparative example 2.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides an alkyne selective hydrogenation catalyst, which comprises a carrier, a main active component and an optional auxiliary active component, wherein the main active component and the optional auxiliary active component are loaded on the carrier, the carrier is a carbon carrier, the carbon carrier is selected from one or more of graphite, coal-based carbon, carbon black, coconut shell carbon, a high-molecular carbonized material and a carbon molecular sieve, and the main active component is palladium.
The inventors of the present invention have found that a carbon support is particularly suitable for use in a process for selective hydrogenation of acetylene in a carbon-containing fraction due to its weak acidity, and can effectively suppress the problems of warm-over and green oil. Since the weak acidity is a general property of the carbon support, the carbon support is not particularly limited and may be selected from various commercially available or self-made carbon supports, for example, one or more selected from graphite, coal-based carbon, carbon black, coconut shell carbon, a polymeric carbonized material, and a carbon molecular sieve.
In the present invention, the content of each component in the catalyst may be a content conventional in the art, for example, the content of the carbon support is 90 to 99.999 wt%, the content of the main active component palladium is 0.001 to 5 wt%, and the content of the auxiliary active component is 0 to 5 wt% with respect to the total weight of the alkyne selective hydrogenation catalyst; preferably, the content of the carbon support is 96.7-99.98 wt%, the content of the main active component palladium is 0.01-0.3 wt%, and the content of the auxiliary active component is 0.01-3 wt%, relative to the total weight of the alkyne selective hydrogenation catalyst; more preferably, the content of the carbon support is 99.41 to 99.96 wt%, the content of the main active component palladium is 0.02 to 0.09 wt%, and the content of the auxiliary active component is 0.02 to 0.5 wt%, relative to the total weight of the alkyne selective hydrogenation catalyst; further preferably, the content of the carbon support is 99.84 to 99.94 wt%, the content of the main active component palladium is 0.04 to 0.08 wt%, and the content of the auxiliary active component is 0.02 to 0.08 wt%, relative to the total weight of the alkyne selective hydrogenation catalyst.
In the present invention, the Co-active component is selected from one or more of Bi, Sb, Pb, In, group IB elements, rare earth elements, alkali metal elements, alkaline earth metal elements, and group VIII elements other than palladium, preferably one or more of Sb, Bi, Ag, K, Ni, Co, and L a.
In the invention, the alkyne selective hydrogenation catalyst further comprises a surfactant, wherein the surfactant can be an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and a nonionic surfactant, preferably the anionic surfactant, and the anionic surfactant is preferably one or more selected from polyoxyethylene lauryl ether, potassium dodecyl polyoxyethylene ether phosphate, sodium dodecyl benzene sulfonate, sodium alkyl polyoxyethylene ether sulfate and sodium methylene dinaphthalene sulfonate. The amount of the surfactant is not particularly limited, and for example, the content of the surfactant is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 0.14 to 3% by weight, relative to the total weight of the alkyne selective hydrogenation catalyst.
The present invention also provides a method for preparing the alkyne selective hydrogenation catalyst of the present invention, which comprises supporting a palladium precursor and a co-active component precursor on a carbon support using a dipping method or a spraying method, and performing a reduction treatment after supporting the palladium precursor, the reduction treatment being performed by a method of ionizing radiation.
In the present invention, the carbon support is preferably a carbon support having a solid form of a block, such as coal-based carbon, coconut shell carbon, a high molecular carbonized material and a carbon molecular sieve, and when the carbon support is in a powder form (such as graphite and carbon black), it may be molded first by any means (such as tableting) and then used.
In the present invention, the palladium precursor and the co-active component precursor may be supported on the carbon support by a spray method or an impregnation method, preferably by an impregnation method; the impregnation method can be a co-impregnation method, can also be a step impregnation method, and is preferably a step impregnation method. When the co-impregnation method is adopted, the components (including the main active component palladium precursor and the auxiliary active component precursor) may be prepared as a mixed solution and then co-impregnated on the carbon support. When a stepwise impregnation method is used, the support may be impregnated with one of the active components and dried, followed by sequential impregnation with the other active components. That is, in the present invention, the co-active component precursor may be supported on the carbon support by a spraying method or an impregnation method before, after, or after the carbon support is supported with the palladium precursor by ionizing radiation reduction. The time for the impregnation is not particularly limited, and may be, for example, 1 to 20 hours, and the drying may be, for example, drying at 100 ℃ and 150 ℃ for 8 to 16 hours.
In the present invention, the concentration of the palladium precursor in the solution for spraying or dipping is not particularly limited, and may be, for example, 0.5 to 2mg/m L, preferably 1 to 1.5mg/m L in terms of palladium atom, and the concentration of the co-active component precursor is also not particularly limited, and may be, for example, 0.5 to 2mg/m L, preferably 1 to 1.5mg/m L in terms of co-active component element atom.
In the invention, the main active component palladium precursor is a palladium compound, which can be selected from one or more of palladium chloride, palladium nitrate and palladium acetate, preferably palladium nitrate; the auxiliary active component precursor is a compound corresponding to the auxiliary active component, and can be selected from one or more of halide salt, nitrate, oxalate, sulfate, oxide, hydroxide and metal organic compound corresponding to the auxiliary active component precursor, and is preferably one or more of nitrate, oxalate and hydroxide.
In the present invention, the method further comprises supporting a surfactant on the carbon support, the surfactant may be supported on the carbon support by being formulated in the form of a mixed gel with the palladium precursor and by a spraying method or an impregnation method.
The inventor of the present invention finds that a reducing agent reduction method or a hydrogen reduction method is usually adopted when reduction treatment is carried out in the existing catalyst preparation process, however, the catalysts reduced by the methods often have the problems of large particle size of main active components, poor dispersibility and more impurities, and therefore, the inventor of the present invention has conducted intensive research and finds that if ionizing radiation reduction is adopted to replace the traditional reduction method, loss of precious metal active components caused by soaking and washing in the reducing agent reduction process can be avoided, and introduction of impurities is avoided, so that improvement of catalyst activity is facilitated. In the present invention, the ionizing radiation reduction process includes wetting the carbon support loaded with the palladium precursor with an aqueous solution of a radical scavenger and then applying ionizing radiation to reduce palladium particles, thereby producing a supported palladium catalyst having a smaller particle size, a higher degree of dispersion, and less impurities.
In the present invention, the type of ionizing radiation may be gamma rays, x rays or electron beams, and the source of the radiation may be selected from the group consisting of60Co (gamma source),137Cs (gamma source), x-ray source or electron accelerator (electron beam), more preferably selected from60Co, x-ray source or electron accelerator, more preferably60The ionizing radiation used for the ionizing radiation irradiation may have an absorption dose rate of 1 to 1 × 107Gy/min, preferably 10-1 × 104Gy/min, more preferably 20-100Gy/min, and ionizing radiation absorbed dose of 0.01-1 × 105kGy, preferably 5-100 kGy; the ionizing radiation may be carried out for a period of time ranging from 10 to 20 hours, preferably from 12 to 18 hours. The ionizing radiation irradiation process is preferably carried out in an inert atmosphere and vacuum; the ionizing radiation irradiation process may be carried out at various temperatures, preferably at room temperature (generally 10 to 30 ℃).
In the present invention, the radical scavenger is one or more of alcohols and formic acid, preferably one or more selected from isopropanol, methanol, ethanol, ethylene glycol and formic acid, more preferably isopropanol and/or ethanol. The content of the radical scavenger in the system of water and radical scavenger is 10 to 90 wt.%, preferably 10 to 50 wt.%, more preferably 10 to 30 wt.%.
The invention also provides the alkyne selective hydrogenation catalyst prepared by the preparation method, the alkyne selective hydrogenation catalyst has higher activity and longer service life, and has the characteristic of easy recovery of noble metals compared with the traditional noble metal catalyst, namely, the noble metals can be recovered from the waste catalyst by burning the carbon carrier, thereby reducing the catalyst recovery cost.
The invention also provides the application of the alkyne selective hydrogenation catalyst in the selective hydrogenation alkyne removal process of carbon-dioxide fraction. When the alkyne selective hydrogenation catalyst is applied to the selective hydrogenation and alkyne removal process of carbon-containing distillate, the catalyst can be stably operated at the reaction temperature of more than 80 ℃ without temperature runaway, and the generation of green oil is obviously reduced.
The present invention further provides a process for the selective hydrogenation removal of alkynes from a carbon-reduced fraction, which comprises subjecting the carbon-reduced fraction to a pre-hydrogenation treatment in the presence of the alkyne selective hydrogenation catalyst of the present invention.
In the present invention, the selective hydrogenation of acetylene in the carbon-dioxide fraction is preferably carried out in a fixed bed reactor, and the reaction conditions may include, for example: the inlet temperature is 40-200 ℃, preferably 50-150 ℃, the reaction pressure is 1-5MPa, preferably 1-3 ℃, and the gas phase space velocity of the raw material of the carbon dioxide fraction is 5000--1Preferably 6000-15000h-1。
In the present invention, the carbon dioxide cut material may be a conventional carbon dioxide cut material, typically containing methane, ethane, ethylene, acetylene, propylene, propane, propyne, propadiene, carbon monoxide, hydrogen and nitrogen, and the composition of each component is, for example: 10 to 20 mol% of hydrogen, 0.09 to 0.15 mol% of acetylene, 30 to 40 mol% of ethylene, 1 to 10 mol% of ethane, 0 to 0.1 mol% of propyne, 10 to 15 mol% of propylene, 0 to 0.1 mol% of carbon monoxide, 0 to 0.2 mol% of propadiene, 0 to 2 mol% of propane, and 12.45 to 48.91 mol% of methane.
The following examples are intended to illustrate specific embodiments of the present invention in further detail, but the scope of the present invention is not limited thereto.
Example 1
50ml of palladium nitrate solution (Pd content of 1.2mg/ml) and 10ml of dodecyl polyoxyethylene ether phosphate potassium salt glue solution (content of 15 wt%) are uniformly mixed to obtain mixed glue solution, and then 100g of coconut shell carbon (Shanghai Xizhou Baojiu Co., Ltd., HC-GS01) is soaked in the mixed glue solution for 12 hours and dried at 120 ℃ for 12 hours. The dried carbon support was then wetted with an aqueous isopropanol solution (10% by weight) and then dried60Co (gamma source) is irradiated for 15 hours at room temperature in inert atmosphere, and the absorption dose rate is 30 Gy/min. And drying the irradiated sample at 120 ℃ for 12 hours to obtain the catalyst A.
The obtained catalyst a was subjected to SEM observation, and the obtained SEM scanning photograph is shown in fig. 1, in which black areas are carbon supports and white bright spots are active ingredient palladium. As can be seen from fig. 1, the palladium is dispersed on the carbon support more uniformly without significant agglomeration.
Example 2
50ml of palladium chloride solution (palladium element content is 1.0mg/ml) and 5ml of sodium dodecyl benzene sulfonate glue solution (content is 5 wt%) are mixed uniformly to obtain mixed glue solution, then 100g of coal-based carbon (Shanghai Xichu carbon environmental protection technology Co., Ltd., HC-MQ001) is soaked in the mixed glue solution for 15h and dried at 150 ℃ for 10 h. The resulting carbon support was then impregnated with 50ml of silver nitrate solution (Ag element content 1.2mg/ml) and dried for 16 hours and at 150 ℃ for 10 hours. The resulting carbon support was then wetted with an aqueous isopropanol solution (content 15% by weight) and washed with60Co (gamma source) is irradiated for 12 hours at room temperature in inert atmosphere, and the absorption dose rate is 40 Gy/min. After irradiation, the sample is dried at 120 ℃ for 12 hours to obtain the catalyst B.
Example 3
50ml of palladium acetate solution (Pd content of 1.5mg/ml) and 10ml of lauryl alcohol polyoxyethylene ether glue solution (content of 5 wt%) are mixed uniformly to obtain mixed glue solution, then 100g of coconut shell carbon (Shanghai Xichun environmental protection technology Co., Ltd., HC-GS01) is soaked in the mixed glue solution for 18h and dried at 110 ℃ for 14 h. Then placing the dried carbon carrier into an aqueous solution (with the content of 20 wt%) of ethanol for use60Co (gamma source) is irradiated for 10 hours at room temperature in inert atmosphere, and the absorption dose rate is 45 Gy/min. And drying the irradiated sample at 110 ℃ for 14 hours to obtain the catalyst C.
Example 4
30ml of palladium nitrate solution (Pd content of 1.5mg/ml), 20ml of bismuth nitrate solution (Bi content of 1.2mg/ml) and 10ml of dodecyl polyoxyethylene ether phosphate potassium salt glue solution (content of 10 wt%) were mixed uniformly to obtain a mixed solution, and then 100g of a carbon molecular sieve (CSM-200, Strong carbon industries, Ltd. of Huzhou, China) was immersed in the mixed glue solution for 20 hours and dried at 120 ℃ for 12 hours. The resulting carbon support was dried and dried at 120 ℃ for 8 hours. And then irradiating the dried carbon carrier with an ethanol aqueous solution (the content is 15 weight percent) for 15 hours at room temperature in an inert atmosphere by using an electron accelerator, wherein the absorption dose rate is 30 Gy/min. After irradiation, the sample was dried at 120 ℃ for 12 hours to obtain catalyst D.
Comparative example 1
The procedure is as in example 1, except that coconut shell carbon is replaced by an alumina support (catalpo synthesis chemical Co., Ltd., YH-010), to give catalyst E.
Comparative example 2
The procedure of example 1 was followed, except that the reduction by ionizing radiation was not carried out, but the dried carbon carrier was immersed in an aqueous solution of sodium formate (content: 10% by weight) at 80 ℃ for 3 hours in such an amount that the carbon carrier was just immersed in the aqueous solution of sodium formate, then the carbon carrier was washed with deionized water several times to neutrality, and the sample reduced with the reducing agent was dried at 120 ℃ for 12 hours to obtain catalyst F.
The obtained catalyst F was observed by SEM, and the obtained SEM scanning photograph is shown in fig. 2, in which black areas are carbon carriers and white areas are active ingredient palladium. As can be seen from fig. 2, the palladium was significantly agglomerated on the carbon support.
Examples 5 to 8 and comparative examples 3 to 4
Examples 5 to 8 and comparative examples 3 to 4 are intended to illustrate the use of the alkyne selective hydrogenation catalyst of the present invention in the selective hydrogenation removal of alkynes from a carbon-containing fraction and the process for the selective hydrogenation removal of alkynes from a carbon-containing fraction.
The results of calculation of acetylene conversion (calculation formula 1) and ethylene selectivity (calculation formula 2) obtained by subjecting the carbon-reduced fraction to the pre-hydrogenation and acetylene removal treatment in the fixed bed reactor in the presence of the catalysts A, B, C, D, E and F prepared in examples 1 to 4 and comparative examples 1 to 2 (corresponding to examples 5 to 8 and comparative examples 3 to 4, respectively) are shown in Table 2, and the formation of green oil, i.e., the adhesion of oil to the hydrogenation catalyst, was observed during the experiment and are shown in Table 2.
Acetylene conversion% (% of moles of acetylene at inlet port-moles of acetylene at outlet port)/moles of acetylene at inlet port × 100 (formula I)
Ethylene selectivity (%)% × 100 (formula II) (outlet ethylene molar-inlet ethylene molar)/(inlet acetylene molar-outlet acetylene molar) 100%
The experimental conditions were controlled as follows: the loading of the catalyst in the fixed bed reactor is 2ml, the reaction pressure is 1.2MPa, and the gas phase space velocity of the carbon dioxide fraction raw material is 12000h-1The reaction temperatures were set at 80 deg.C, 90 deg.C and 100 deg.C (corresponding to groups I, II and III, respectively, and described as example 5I, example 5II and example 5III, respectively, taking example 5 as an example), respectively, and the compositions of the carbon fractions are shown in Table 1.
TABLE 1
| Components | Raw material content (mol%) | Components | Raw material content (mol%) |
| Hydrogen gas | 15.7 | Propylene (PA) | 13.4 |
| Carbon monoxide | 0.0947 | Ethylene | 34.0 |
| Acetylene | 0.0922 | Ethane (III) | 4.41 |
| Propyne | 0.0947 | Methane | 30.7 |
| Propane | 1.53 |
TABLE 2
As can be seen from Table 2, the catalyst of the present invention can maintain a high conversion at 80-100 ℃ with a much lower decrease in selectivity than catalyst E of comparative example 1, the catalyst of the present invention has a higher stability to temperature changes than comparative example, and catalyst E has a severe temperature runaway at 90 ℃ with a greater ethylene loss. Meanwhile, the active component palladium on the catalyst is more highly dispersed on the carrier due to the adoption of the ionizing radiation reduction mode in the preparation process, so that the agglomeration phenomenon is reduced (see figure 1 in detail), the catalyst activity is improved, and the conversion rate of the catalyst F in the comparative example 2 is obviously lower than that of the catalyst in the example as shown in the table 2. And as can also be seen from table 2, the green oil production amount of the comparative example is significantly greater than that of the example, so that the catalyst of the present invention effectively suppresses the production of green oil.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A process for the selective hydrogenation removal of alkynes from a carbon-reduced fraction, which comprises subjecting the carbon-reduced fraction to a pre-hydrogenation treatment in the presence of an alkyne selective hydrogenation catalyst; the alkyne selective hydrogenation catalyst contains a carrier, a main active component and an optional auxiliary active component, wherein the main active component and the optional auxiliary active component are loaded on the carrier, the alkyne selective hydrogenation catalyst is characterized in that the carrier is a carbon carrier, the carbon carrier is selected from one or more of graphite, coal-based carbon, carbon black, coconut shell carbon and a carbon molecular sieve, and the main active component is palladium; the content of the carbon carrier is 96.7-99.98 wt%, the content of the main active component palladium is 0.01-0.3 wt%, and the content of the auxiliary active component is 0-3 wt% relative to the total weight of the alkyne selective hydrogenation catalyst;
wherein the gas phase space velocity of the carbon dioxide fraction is 5000--1The reaction temperature is 80-100 ℃.
2. The method of claim 1, wherein the co-active component is selected from Bi and/or Ag.
3. The method according to claim 1 or 2, wherein the alkyne selective hydrogenation catalyst is prepared by a method comprising supporting a palladium precursor and a co-active component precursor on a carbon support using a dipping method or a spraying method, and carrying out a reduction treatment using an ionizing radiation method after supporting the palladium precursor.
4. The method of claim 3, wherein the ionizing radiation is absorbed in a dose of 5-100 kGy.
5. The method of claim 4, wherein theThe absorption dose rate of electric power radiation used for ionizing radiation is 10-1 × 104Gy/min。
6. The method of claim 5, wherein the ionizing radiation is provided by a source selected from the group consisting of60Co、137Cs, x-ray source, or electron accelerator.
7. The method of claim 6, wherein the ionizing radiation irradiation process is performed in an inert atmosphere or vacuum.
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