Carbon carrier, catalyst and preparation method thereof, and selective hydrogenation purification method

Abstract

The invention relates to the technical field of selective hydrogenation purification of olefin gas, and discloses a carbon carrier, a catalyst, a preparation method of the catalyst and a selective hydrogenation purification method. The preparation method of the carbon carrier comprises the following steps: mixing artificial synthetic resin and a solvent into a group, forming and granulating, and sequentially curing, carbonizing and activating particles to obtain the carbon carrier, the activation condition comprises the step of activating the carbonized particles for 1-10 hours at the temperature of 600-1000 DEG C under the condition that the flow rate of water vapor is 0.01-0.2 g / min in a protective atmosphere. The catalyst prepared from the carbon carrier not only has relatively high strength, specific surface area, pore volume and other physical properties, but also can be directly used for acetylene hydrogenation purification in a front-end deethanization front-end hydrogenation process, and the selectivity of ethylene is improved on the basis of relatively high acetylene conversion rate.

Description

Technical Field

[0001] The present invention relates to the technical field of selective hydrogenation purification of olefin gas, and more particularly to a carbon carrier, a catalyst and a preparation method thereof, and a selective hydrogenation purification method. Background Art

[0002] Polyolefin is a widely used material. The current production route is to obtain it through polymerization using low-carbon olefins such as ethylene and propylene as raw materials. Therefore, the production of polyolefin occupies an important position in the modern chemical industry. Ethylene and propylene usually rely on raw materials such as naphtha and low-carbon alkanes through steam cracking technology, which absorbs heat at high temperatures to induce free radical cracking to achieve efficient production of ethylene and propylene. Although thermal cracking reactions can obtain high ethylene and propylene yields, the reaction products are difficult to control. The products often contain trace amounts of over-cracked products such as acetylene and propadiene, which are harmful to downstream olefin polymerization and even the safe operation of the device itself. Common impurity removal and purification methods include solvent extraction and catalytic hydrogenation. At present, the main treatment method used in general industrial production is to eliminate alkynes and dienes entrained in the cracking gas through catalytic hydrogenation reactions, while increasing the production of ethylene and propylene and improving resource utilization.

[0003] The traditional production process adopts a sequential separation process to separate the hydrogen, C2 fraction, C3 fraction and other components in the cracking product in turn, and then hydrogenate and purify the acetylene and propadiene in the fraction. In recent years, the application of pre-hydrogenation separation process has increased, that is, acetylene and propadiene and other by-products are first hydrogenated and purified, and then further separated. The hydrogen content of this process is affected by the upstream cracking furnace feed, up to more than 10%, and the reaction space velocity is as high as 12000h -1 Under the above conditions, the catalyst is not only required to meet the requirements of acetylene and propadiene purification, but also needs to have high selectivity to reduce the olefin loss caused by excessive hydrogenation under high hydrogen partial pressure.

[0004] Most of the hydrogenation purification catalysts used in industry are supported metal catalysts, which are generally composed of a carrier and an active component. Common carriers are aluminum oxide, silicon oxide, molecular sieves, activated carbon, magnesium oxide, titanium oxide, diatomaceous earth, etc.; the active component is a metal element with hydrogenation catalytic activity, usually a Group VIII element, such as Pd, Pt, Ni, etc., among which Pd is a commonly used active component in this reaction. The hydrogenation purification catalysts currently used in industry have met the requirements of polymerization-grade olefins in terms of conversion rate, but their selectivity still needs to be improved.

[0005] In recent years, with the continuous deepening of research on carbon-based catalytic materials, researchers have prepared a variety of different carbon-based hydrogenation purification catalysts to achieve the selective hydrogenation of unsaturated alkynes. Bychko et al. used multi-walled carbon nanotubes as catalysts to achieve 90% acetylene conversion and 85% ethylene selectivity at 350°C (10.1002 / cctc.201701234); Dai et al. used nitrogen-doped carbon composite carriers to prepare single-atom Ni catalysts, achieving >90% acetylene conversion and ethylene selectivity at 200°C (10.1039 / c7cc04820c); Huang et al. used graphene-coated nanodiamonds as carriers to prepare Pd single-atom catalysts, which achieved >90% acetylene conversion and ethylene selectivity at 60,000 h. -1 100% acetylene conversion and 90% ethylene selectivity were achieved at a low space velocity, but again, the reaction temperature was as high as 180°C ( / 10.1021 / jacs.8b07476).

[0006] These catalytic systems can achieve efficient conversion of alkynes under laboratory conditions. However, these catalysts are expensive and in powder form with low strength. There is a large gap between these catalysts and actual industrial application conditions and they cannot meet the actual needs of factories. Summary of the invention

[0007] In order to solve the problems in the prior art, the present invention proposes a carbon carrier, a catalyst and a preparation method thereof and a method for selective hydrogenation purification. The present invention first adopts a new method to prepare a carbon-based catalyst, which is an artificial synthetic resin-based carbon, and adopts a specific activation method to obtain a new carbon carrier. The catalyst obtained from the carbon carrier not only has high strength, physical properties such as specific surface area and pore volume, but also the obtained catalyst can be directly used for acetylene hydrogenation purification in the pre-deethanization pre-hydrogenation process, and the selectivity of ethylene is improved on the basis of having a high conversion rate of acetylene.

[0008] The first aspect of the present invention is to provide a method for preparing a carbon carrier, comprising mixing a synthetic resin and a solvent into agglomerates, forming and granulating the particles, and then sequentially solidifying, carbonizing and activating the particles to obtain the carbon carrier;

[0009] The activation conditions include: activating the carbonized particles at 600-1000° C. for 1-10 hours under a protective atmosphere and a water vapor flow rate of 0.01-0.2 g / min.

[0010] In the present invention, the water vapor flow rate is controlled by entraining water vapor in the protective atmosphere.

[0011] In a preferred embodiment of the present invention, the activation conditions include: a water vapor flow rate of 0.06-0.1 g / min; and / or an activation temperature of 700-800° C.; and / or an activation time of 1-4 h.

[0012] In a preferred embodiment of the present invention, the artificial synthetic resin is at least one selected from phenolic resin, melamine formaldehyde resin, furan resin, and benzoxazine resin.

[0013] The present invention selects the above-mentioned artificial synthetic resin as raw material to prepare a carbon carrier with higher strength, which is not a conventional technical adjustment in the field.

[0014] Regarding carbon carriers, "coal tar, asphalt, starch, hydroxymethyl cellulose" and the like are also carbon raw materials, but the above raw materials are not suitable for the preparation method of the present invention. That is, using the above raw materials to replace the artificial synthetic resin in the present invention cannot obtain a carbon carrier that meets the application requirements.

[0015] The inventors of the present invention have studied and confirmed that:

[0016] Coal tar and asphalt are carbon materials. The materials prepared by bonding coal tar and asphalt have extremely high strength and methylene and iodine adsorption values, and are suitable for use as adsorbents. However, when coal tar and asphalt are used to prepare carriers and then catalysts, the catalytic performance of the obtained catalysts is unstable and has a bad effect on the life of the catalysts. It may be that these two materials are mixtures and contain impurities. The effects of these impurities on the performance of the catalysts are complicated, and the different element contents of each batch of materials will lead to fluctuations in material performance.

[0017] A series of natural polymer materials represented by starch and hydroxymethyl cellulose are commonly used carbon materials in catalyst carrier molding. However, when starch and hydroxymethyl cellulose are used to prepare carriers respectively, it is found that the strength of the obtained carriers decreases rapidly with the increase of treatment temperature, and a carrier with higher strength cannot be obtained.

[0018] From the known comparison, it can be seen that the present invention adopts artificial synthetic resin, preferably at least one of phenolic resin, melamine formaldehyde resin, furan resin and benzoxazine resin. The obtained carbon carrier not only prepares a catalyst with higher strength, but also the obtained catalyst has higher selectivity, achieving unexpected technical effects.

[0019] In a preferred embodiment of the present invention, the solvent is selected from at least one of water, ethanol, acetonitrile and hexane.

[0020] In a preferred embodiment of the present invention, the molding method is selected from at least one of compression molding, extrusion molding, spray drying molding, oil molding, spray granulation molding, cooling granulation molding, and fibrous carrier molding.

[0021] In a preferred embodiment of the present invention, the curing method comprises:

[0022] The formed particles are cured at 50-250°C for 1-24 hours, preferably at 100°C-200°C for 1-16 hours under a protective atmosphere. Preferably, the formed particles are placed in a tubular heating furnace and cured at 100°C-200°C for 8-16 hours under a nitrogen atmosphere.

[0023] In a preferred embodiment of the present invention, the carbonization conditions include:

[0024] The solidified particles are carbonized under a protective atmosphere selected from nitrogen and / or an inert atmosphere at 700-1000° C. for 1-8 hours, preferably under a protective atmosphere at 800-1000° C. for 1-6 hours.

[0025] The molding process of the composite carrier adopts the existing conventional molding process, such as compression molding, extrusion molding, spray drying molding, oil molding, spray granulation molding, cooling granulation molding and fibrous carrier molding, etc.

[0026] The composite carrier uses a carrier in the shape of at least one of spherical, columnar, sheet, toothed ball, strip, three-leaf clover or four-leaf clover.

[0027] As an example, the preparation method of the carbon carrier includes: fully kneading the resin, cooling and granulating it, and then curing it, the curing temperature is 150°C, the curing time is 12 hours, and after cooling, the particles are carbonized at 800°C, the carbonization time is 4 hours, and after natural cooling, the particles are activated in a 700°C water vapor atmosphere for 1 hour, the water vapor flow rate is 0.01-0.2g / min, and the granular carbon carrier is obtained after natural cooling.

[0028] In the present invention, the protective atmosphere is selected from nitrogen and / or an inert gas. The inert gas includes but is not limited to argon.

[0029] The second aspect of the present invention is to provide a carbon carrier, which is prepared by the preparation method described in the first aspect.

[0030] In a preferred embodiment of the present invention, the carbon carrier has at least one of the following characteristics:

[0031] The lateral pressure strength is above 40N, preferably 40-120N, more preferably 50-120N, and even more preferably 60-100N.

[0032] The specific surface area is 150m 2 / g or more, preferably 150-1000m 2 / g; more preferably 100-800m 2 / g;

[0033] The pore volume is 0.1 cm 3 / g or more, preferably 0.1-0.6cm 3 / g, more preferably 0.1-0.4cm 3 / g.

[0034] The oxygen-containing group of the carbon carrier is at least one of a carbonyl group, a carboxyl group, an ether group and a phenolic hydroxyl group. Preferably, the carbon carrier has a carboxyl content of 0.1-1 mmol / g; and / or; the carbon carrier has a phenolic hydroxyl content of 0.1-1 mmol / g.

[0035] The third aspect of the present invention is to provide a catalyst, which includes a carbon carrier and an active component loaded on the carbon carrier; the active component is at least one of the Group VIIIB noble metal elements; the carbon carrier is selected from the carbon carrier prepared by the preparation method described in the first aspect or the carbon carrier described in the second aspect.

[0036] In a preferred embodiment of the present invention, based on the total weight of the catalyst as 100wt%, the content of the active component is 0.001-10wt%; the content of the carbon carrier is 90-99.999wt%; more preferably, based on the total weight of the catalyst as 100wt%, the content of the active component is 0.01-2wt%, and the content of the carbon carrier is 98-99.99wt%.

[0037] In a preferred embodiment of the present invention, the active component includes palladium element.

[0038] The fourth aspect of the present invention is to provide a method for preparing the catalyst of the third aspect, wherein a precursor compound containing the active component is loaded onto the carbon carrier, and the catalyst is obtained through post-treatment; preferably, the loading method is an impregnation method.

[0039] In a preferred embodiment of the present invention, the preparation method comprises:

[0040] The vacuum-treated carbon support is mixed with a solution of a precursor compound containing the active component, impregnated, optionally washed, and dried to obtain the catalyst; more preferably,

[0041] Based on the sum of the mass of the metal element in the precursor compound of the active component and the mass of the carbon carrier being 100 wt %, the content of the metal element in the precursor compound of the active component is 0.001-10 wt %, preferably 0.01-2 wt %.

[0042] In a preferred embodiment of the present invention, the precursor compound of the main active component is selected from a palladium salt. Preferably, the palladium salt is selected from at least one of an inorganic palladium salt and an organic palladium salt; more preferably, the inorganic palladium salt is selected from at least one of palladium chloride, palladium nitrate, and palladium sulfate, and / or the organic palladium salt is selected from at least one of palladium acetate and palladium acetylacetonate.

[0043] In a preferred embodiment of the present invention, the impregnation conditions include: the impregnation temperature is 35-55° C., and / or the impregnation time is 0.5-2 h.

[0044] In a preferred embodiment of the present invention, the solvent used for the solution of the precursor compound containing the active component includes an inorganic solvent and / or an organic solvent. Preferably, the inorganic solvent is selected from at least one of water, hydrochloric acid, and nitric acid, and / or the organic solvent is selected from at least one of acetic acid and ethanol.

[0045] In a preferred embodiment of the present invention, the conditions for the drying treatment include: a drying treatment temperature of 80-120° C., and / or a drying treatment time of 5-24 h.

[0046] For example, when the inorganic solvent is selected from aqueous hydrochloric acid, the molar concentration of the aqueous hydrochloric acid is 0.001-0.1; and / or, when the inorganic solvent is selected from aqueous nitric acid, the molar concentration of the aqueous nitric acid is 0.001-0.1; and / or, the drying temperature in the post-treatment is 80-120° C.; and / or,

[0047] The drying time in the post-treatment is 5-24 hours; in the preparation method of the present invention, the drying can be carried out in an air atmosphere or in a vacuum.

[0048] In the preparation method of the present invention, the active component precursor can be loaded onto the carrier using the impregnation method used in catalyst preparation, such as equal volume impregnation, supersaturated impregnation, etc. When the supersaturated impregnation method is used, if the active component precursor in the impregnation solution cannot be completely adsorbed by the carrier, the volume of the impregnation solution and the active component concentration should be determined according to the adsorption ratio to ensure that the active component loaded onto the carrier meets the predetermined requirements.

[0049] As an example, the preparation method of the selective hydrogenation purification catalyst includes:

[0050] A certain amount of carbon carrier (the granular carbon carrier prepared in Preparation Example 1) was evacuated for 10 minutes. A palladium impregnation solution was prepared and weighed and diluted to 50 mL with distilled water. The impregnation solution was added to the carrier, impregnated and stirred at 60°C for 1 hour, and then the solvent was removed under reduced pressure on a rotary evaporator, and the obtained catalyst was dried in an oven at 60°C for 12 hours to obtain a selective hydrogenation purification catalyst.

[0051] The fifth aspect of the present invention is to provide a method for selective hydrogenation purification, comprising subjecting a raw gas containing acetylene and hydrogen to a selective hydrogenation reaction under the action of a catalyst;

[0052] Wherein, the catalyst is the catalyst described in the third aspect or the catalyst prepared by the preparation method described in the fourth aspect.

[0053] In a preferred embodiment of the present invention, the molar fraction of acetylene in the raw gas is 0.1-10.0%, preferably 0.1-6.0%, and / or the molar fraction of hydrogen is 1.0-30.0%, preferably 5.0-25.0%. Preferably, the raw gas is derived from the raw gas containing acetylene in the pre-deethanization pre-hydrogenation process.

[0054] In a preferred embodiment of the present invention, the conditions of the selective hydrogenation reaction include: a temperature of 10-180°C, and / or a volume space velocity of 1000-20000h -1 .

[0055] In a more preferred embodiment of the present invention, the reaction temperature of the selective hydrogenation purification is 20-120°C; more preferably 50-120°C; and more preferably 60-120°C; and / or the volume space velocity of the selective hydrogenation purification is 5000-12000h -1 .

[0056] As an example, in the selective hydrogenation purification method of the present invention, preferably, the step of the pre-hydrogenation reaction includes:

[0057] (A) loading the above catalyst into a reactor;

[0058] (B) Feeding the acetylene-containing raw gas into a reactor for selective hydrogenation and purification of acetylene.

[0059] In the present invention, the reactor is a conventional hydrogenation reactor in the art.

[0060] Compared with the prior art, the present invention has at least the following advantages:

[0061] The carbon catalyst prepared by the present invention uses a cheap resin and has high catalytic activity. The catalyst prepared by the present invention is used in the acetylene selective hydrogenation purification reaction. On the basis of having a higher acetylene conversion rate, the ethylene selectivity is improved.

[0062] The catalyst of the present invention uses a carbon-based material as a carrier, has high strength, can be directly applied to the acetylene pre-hydrogenation reaction, and is easy to prepare, has a good catalytic effect at low temperatures, and is more suitable for industrial production. DETAILED DESCRIPTION

[0063] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0064] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0065] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0066] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0067] In the following embodiments,

[0068] The method for testing the lateral pressure strength is to randomly select 30 carbon carriers, place them flat on a universal strength testing machine for testing, and the average value after deleting the maximum and minimum values ​​is recorded as the lateral pressure strength of the carbon carrier;

[0069] The specific surface area was measured by random sampling and testing the low-temperature nitrogen physical adsorption curve using BET.

[0070] The pore volume was measured by random sampling and testing the low-temperature nitrogen physical adsorption curve using BJH.

[0071] The types of surface functional groups were detected by infrared spectroscopy;

[0072] The surface functional group content was determined by Boehm titration.

[0073] The selective hydrogenation purification catalyst of the present invention can be analyzed using X-ray photoelectron spectroscopy (XPS) to confirm the chemical valence state of the active components of the catalyst; the particle size and particle size distribution of the active component particles can be observed using a transmission electron microscope (TEM); and the distribution of the active components on the surface and cross-section of the carrier can be observed using a scanning electron microscope (SEM).

[0074] Example 1

[0075] Weigh 50.0g of phenolic resin, add a small amount of water and knead into a mass. After extrusion and pelletization, send it into a tubular heating furnace and solidify it at 150℃ for 12h under nitrogen atmosphere. After cooling, carbonize the particles at 800℃ for 4h under nitrogen atmosphere. Finally, heat the granular carbon carrier to 700℃ under protective atmosphere, introduce water vapor at 0.1g / min for 1h for activation, and obtain granular carbon carrier A after natural cooling.

[0076] Weigh 8.0g of the above-mentioned granular carbon support A and evacuate for 10 minutes, add a palladium nitrate solution with a concentration of 0.25mg / mL, and dilute it with water to 40mL, add the solution to the carbon support, and immerse and stir at 60°C for 1h, add 32mL of ethanol after cooling to room temperature, remove the solvent on a rotary evaporator, and dry the obtained catalyst in an oven at 60°C for 12h. Finally, a selective hydrogenation purification catalyst with an active component content of 0.3‰wt was prepared, which was recorded as catalyst A.

[0077] Embodiment 2-4

[0078] The method of Example 1 is followed, except that the activation temperature of the carbon carrier is different, and the carbon carrier B, carbon carrier C, and carbon carrier D are obtained respectively, and the catalysts prepared are respectively labeled as catalyst B, catalyst C, and catalyst D. The specific conditions are shown in Table 1.

[0079] Table 1

[0080]

[0081] Embodiment 5-7

[0082] The method of Example 1 is followed, except that the carbon carriers are prepared using different activation times, and the catalysts prepared using the carriers are respectively labeled as Catalyst E, Catalyst F, and Catalyst G. The specific conditions are shown in Table 2.

[0083] Embodiment 8-10

[0084] The method of Example 1 is followed, except that the carbon carrier is prepared at different water vapor flow rates, and the catalysts prepared using the carrier are respectively labeled as catalyst H, catalyst I, and catalyst J. The specific conditions are shown in Table 3.

[0085] Comparative Example 1

[0086] The method of Example 1 was followed, except that the carbon carrier was not subjected to activation treatment. The prepared catalyst was labeled as Catalyst K.

[0087] Table 2

[0088]

[0089] Table 3

[0090]

[0091] After testing, the number of oxygen-containing groups on the carbon support in the present invention is significantly increased compared with that in Comparative Example 1, especially the content of carboxyl and phenolic hydroxyl groups.

[0092] Application Examples

[0093] The prepared catalyst was subjected to a micro-reaction experiment simulating the pre-hydrogenation reaction of acetylene, and the reaction conditions were as follows:

[0094] 5 mL of catalyst was loaded into a stainless steel tube reactor, and after reduction with hydrogen, the feed gas for simulating pre-deethanization and pre-hydrogenation was introduced into the reactor. The composition (molar fraction) of the feed gas was: C2H2: 0.102%, C2H6: 12.07%, C2H4 balance, H2: 23.60%, CO: 0.0806%, and the volume space velocity was 8000 h -1 .

[0095] The catalytic performance of the above catalysts for selective hydrogenation of acetylene was evaluated, wherein the catalysts of the examples and comparative examples were directly evaluated. The conversion and selectivity of acetylene pre-hydrogenation to ethylene for each catalytic reaction at 60°C are listed in Table 4.

[0096] The calculation method of conversion and selectivity of acetylene pre-hydrogenation to ethylene is:

[0097]

[0098]

[0099] Table 4 Pre-hydrogenation process simulation test results (average value at 60°C)

[0100]

[0101] From the results of the above embodiments in Tables 1 to 3, it can be seen that the catalyst prepared from the carbon carrier obtained in the embodiments of the present invention not only has a higher specific surface area and a higher pore volume, but also, on this basis, has a higher strength, and is more suitable for industrial applications than the carbon carrier in the prior art. Moreover, the carbon material obtained by the preparation method of the present invention is different from the activated carbon for adsorption. Although the activated carbon for adsorption has a large specific surface area, the activated carbon for adsorption is mainly microporous, which affects mass transfer as a catalyst carrier and easily leads to carbon deposition and deactivation of the catalyst.

[0102] It can be seen from Table 4, Examples 1 to 10 and Comparative Example 1 that the activation of the present invention has a significant effect on the physical and chemical properties of the catalyst, and can not only improve the physical properties of the catalyst, but also improve the catalytic performance. The catalyst of the present invention has a higher ethylene selectivity on the basis of a higher acetylene conversion rate, and has achieved unexpected technical effects.

[0103] By comparing Example 1 and Example 3 with Example 2 and Example 4, it can be seen that the pore volume of the catalyst can be further improved and the catalytic performance can be improved within a more preferred activation temperature range, and the technical scheme within the preferred activation temperature range of the present invention has further achieved unexpected technical effects.

[0104] By comparing Example 1 and Example 6 with Example 5 and Example 7, it can be seen that within a more preferred activation time range, the obtained catalyst has higher mechanical strength and catalytic performance, and the technical scheme within the preferred activation time range of the present invention has further achieved unexpected technical effects.

[0105] By comparing Example 1 and Example 9 with Example 8 and Example 10, it can be seen that under more preferred water vapor flow conditions, the physical texture properties and catalyst performance of the carrier and the catalyst can be further improved; the technical scheme within the preferred activation water vapor flow range of the present invention has further achieved unexpected technical effects.

[0106] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

[0107] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

[0108] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0109] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0110] The endpoints and any values ​​of the scope disclosed in the present application document are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in this article.

[0111] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

[0112] Moreover, any embodiment described in this document may be freely combined with one or more other embodiments described in this document, and the technical solutions or technical ideas formed thereby are deemed to be part of the original disclosure or original record of the present invention, and should not be regarded as new content that has not been disclosed or anticipated in this document, unless a person skilled in the art considers that the combination is obviously unreasonable.

Claims

1. A method for preparing a carbon carrier, comprising mixing a synthetic resin and a solvent into agglomerates, forming and granulating the particles, and then sequentially curing, carbonizing and activating the particles to obtain the carbon carrier; The activation conditions include: Under a protective atmosphere, the carbonized particles are activated at 600-1000° C. for 1-10 hours at a water vapor flow rate of 0.01-0.2 g / min.

2. The preparation method according to claim 1, characterized in that: The activation conditions include: a water vapor flow rate of 0.06-0.1 g / min; and / or, Activation temperature: 700-800°C; and / or, Activation time: 1-4h.

3. The preparation method according to claim 1 or 2, characterized in that: The artificial synthetic resin is selected from at least one of phenolic resin, melamine formaldehyde resin, furan resin and benzoxazine resin; and / or, The solvent is selected from at least one of water, ethanol, acetonitrile and hexane; and / or, The molding method is selected from at least one of compression molding, extrusion molding, spray drying molding, oil molding, spray granulation molding, cooling granulation molding, and fibrous carrier molding.

4. The preparation method according to claim 1 or 2, characterized in that: The curing method comprises: The formed particles are cured at 50-250° C. for 1-24 hours under a protective atmosphere; and / or, The carbonization conditions include: The solidified particles are carbonized at 700-1000°C for 1-8h under a protective atmosphere.

5. A carbon carrier, the carbon carrier is prepared by the preparation method according to any one of claims 1 to 4; preferably, The carbon carrier has at least one of the following characteristics: The lateral pressure strength is above 40N; The specific surface area is 150m 2 / g or more; The pore volume is 0.1 cm 3 / g or more; The oxygen-containing group of the carbon carrier is at least one of a carbonyl group, a carboxyl group, an ether group and a phenolic hydroxyl group.

6. A catalyst, comprising a carbon carrier and an active component supported on the carbon carrier; the active component is at least one of the noble metal elements of Group VIIIB; the carbon carrier is selected from the carbon carrier prepared by the preparation method of any one of claims 1 to 4 or the carbon carrier according to claim 5.

7. The catalyst according to claim 6, characterized in that: Based on the total weight of the catalyst being 100 wt%, the content of the active component is 0.001-10 wt%; the content of the carbon carrier is 90-99.999 wt%; and / or, The active component is palladium element.

8. A method for preparing the catalyst according to claim 6 or 7, comprising loading a precursor compound containing the active component onto the carbon carrier, and obtaining the catalyst through post-treatment; preferably, the loading method is an impregnation method.

9. The preparation method according to claim 8, characterized in that: The preparation method comprises: The vacuum-treated carbon support is mixed with a solution of a precursor compound containing the active component, impregnated, optionally washed, and dried to obtain the catalyst; preferably, The content of the metal element in the precursor compound of the active component is 0.001-10 wt %, based on the sum of the mass of the metal element in the precursor compound of the active component and the mass of the carbon carrier being 100 wt %; and / or, The precursor compound of the main active component is selected from palladium salts. Preferably, the palladium salt is selected from at least one of inorganic palladium salts and organic palladium salts; more preferably, the inorganic palladium salt is selected from at least one of palladium chloride, palladium nitrate, and palladium sulfate, and / or the organic palladium salt is selected from at least one of palladium acetate and palladium acetylacetonate.

10. The preparation method according to claim 9, characterized in that: The impregnation conditions include: the impregnation temperature is 35-55°C; and / or, the impregnation time is 0.5-2h; and / or, The solvent used for the solution of the precursor compound containing the active component includes an inorganic solvent and / or an organic solvent. Preferably, the inorganic solvent is selected from at least one of water, hydrochloric acid, and nitric acid, and / or the organic solvent is selected from at least one of acetic acid and ethanol; and / or, The drying treatment conditions include: the drying treatment temperature is 80-120° C., and / or the drying treatment time is 5-24 hours.

11. A selective hydrogenation purification method, comprising subjecting a raw gas containing acetylene and hydrogen to a selective hydrogenation reaction under the action of a catalyst; in, The catalyst is the catalyst according to claim 6 or 7 or a catalyst prepared by the preparation method according to any one of claims 8 to 10.

12. The method according to claim 11, characterized in that: In the raw gas, the molar fraction of acetylene is 0.1-10%, and / or the molar fraction of hydrogen is 1-30%. Preferably, the raw gas comes from the raw gas containing acetylene in the pre-deethanization pre-hydrogenation process; and / or, The conditions of the selective hydrogenation reaction include: a temperature of 10-180°C, and / or a volume space velocity of 1000-20000h -1 .

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