TWI355293B - - Google Patents

Description

1355293 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a metal palladium catalyst (hereinafter referred to as a load (tetra)/carbon catalyst) of 13 males on activated carbon, and a preparation method thereof, in particular, A supported palladium/carbon catalyst for purifying crude terephthalic acid (terephthalicadd) by selective hydrogenation reaction and a preparation method thereof. [Prior Art] The supported type/carbon catalyst is widely used for selective hydrogenation of unsaturated organic matters. In particular, the supported mono/carbon catalyst is suitable for the purification of crude terephthalic acid, in which some impurities such as p-carboxybenzaldehyde (4-CBA) in crude terephthalic acid are converted into other compounds by hydrogenation, Subsequent terephthalic acid production can be separated and purified by the method of B-day. Since the epoch/carbon catalyst usually uses a single active component, the improvement in the prior art mainly focuses on the structure of the support and the distribution of the metal Pd on the support, and these aspects do have a great effect on the performance of the catalyst. Impact. Since the hydrogenation refining reaction process is a first-order reaction, the reaction rate is fast, and it is difficult for the reactants to penetrate into the inside of the catalyst particles to carry out the reaction during the reaction, which makes the active components inside the particles ineffective. Therefore, in order to make full use of the noble metal, the palladium/carbon catalyst is usually made into an eggshell type, that is, the noble metal of the active component is mainly supported on the surface of the carrier. Since the hydrogenation reaction is carried out on the surface of the metal Pd, generally, for a catalyst having the same metal Pd loading, the higher the dispersion of the metal pd in the catalyst and/or the higher the crystallite content of the metal Pd supported in the catalyst and/or Or the better the thermal stability of the catalyst, the higher the activity of the catalyst, and the longer the life is 1355529. If a Pd-containing compound (such as sodium chloropalladate or palladium chloride) solution is directly loaded onto the activated carbon, a very thin, shiny metallic Pd layer will appear soon on the surface of the activated carbon. Mainly because the surface of the activated carbon contains a reducing group such as an aldehyde group and a free electron, they are extremely easy to reduce the Pd ion to a zero-valent metal Pd. Therefore, the catalyst thus obtained has a very low metal Pd dispersion. One way to overcome this problem is to convert the Pd ions in the impregnation liquid containing the Pd compound into an insoluble compound before the impregnation process. For example, the water-soluble compound of Pd is hydrolyzed to insoluble Pd(OH)2 or PdO'H20 at room temperature and then loaded on activated carbon, followed by furfural, sodium citrate, glucose, citric acid or hydrazine. Reducing agent such as gas reduces the migration of Pd and grain growth. U.S. Patent No. 3,138,560 teaches the addition of hydrogen peroxide to the impregnation solution to hydrolyze the water-soluble compound of Pd to form an insoluble compound which is then impregnated. U.S. Patent No. 4,476,242 teaches the use of an organic solvent such as decyl alcohol or pyridine to formulate an impregnation solution containing a Pd compound, which is said to be very effective in preventing Pd migration and grain growth. In addition, it has been reported that the conversion of the chloropalladic acid solution into a palladium-containing colloidal solution by adjusting the pH is said to prevent the reducing group on the surface of the active carbon from directly reducing the Pd ion to the zero-valent metal Pd. CN1698952A discloses the addition of nitrogen-containing polycarboxylic acids in a dipping solution for preparing a palladium/carbon catalyst. [Invention Summary] An object of the present invention is to provide A new supported palladium/carbon catalyst. The metal Pd in the catalyst has a higher dispersion, a higher amount of crystallites 3 and better thermal stability. When used in hydrorefining of crude terephthalic acid, the catalyst can provide high conversion to m-based benzoyl (4-CBA). Another object of the present invention is to provide a process for preparing the supported palladium on carbon catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In a first aspect, the present invention provides a supported palladium/carbon catalyst in which palladium supported on a carrier activated carbon is present in a crystal form of nanometer size, and wherein the particle size is less than 25 nm The crystallites account for 1% or more, preferably 85% by weight or more, more preferably 88% by weight or more, and most preferably 90% by weight or more, based on the total amount of the palladium crystallites. In the supported palladium/carbon catalyst of the present invention, the weight content of the metal pd is preferably in the range of 0.05 to 5%, more preferably in the range of 〇 2 to 3 5%, based on the total weight of the catalyst. In a preferred embodiment, the supported palladium is concentrated in the surface layer of the supported carbon such that the palladium/carbon catalyst has a palladium content of 0:50±0·10% by weight based on the total weight of the catalyst. The metal palladium in the layer having a depth of 5 nm under the surface of the supported carbon is more than 3% by weight, preferably 40% by weight or more, more preferably 50% by weight or more based on the total atomic weight in the layer; 300 under the surface of the carrier activated carbon The metal palladium in the layer having a nanometer depth accounts for 5% by weight or more, preferably 1% by weight or more, more preferably 15% by weight or more, and most preferably 20% by weight or more, based on the total atomic weight in the layer. In the supported type/carbon catalyst of the present invention, the supported portion is highly dispersed in the carrier active 1355293 carbon surface, and the dispersion thereof is not less than 5%, preferably not less than 10% 'more preferably not less than 15%, most preferably Not less than 20%. After calcining the catalyst at 500 C for 10 hours in a nitrogen stream bubbling through water at 25 ° C, the average grain size of the supported palladium is not more than 10 nrn 'preferably not more than 8.0 nm, more preferably not More than 7.0 nm, most preferably no more than 60 nm. In a second aspect, the invention provides a method of preparing a supported palladium/carbon catalyst, the method comprising the steps of:

a) firstly washing the activated carbon with an aqueous solution of a mineral acid, then washing with water to neutrality, and drying the washed activated carbon to obtain an activated carbon support; b) impregnating or spraying the active with an aqueous solution containing a Pd compound and an additive a carbon carrier, the Pd compound is supported on an activated carbon support to obtain a catalyst precursor, wherein the molar ratio of the additive to the pd compound in the aqueous solution is 0.01.1~2.0:1, and the additive is selected from the following formula: compound of:

Ri-(CH2)n-CHCOOH R2 ~ (CH2)m_ CCOOH R3- (CH2), -c

HCOOH wherein n, m and 1 are independently aristotles 6 L , the formula I is selected from the integers of o and 丨 〜5, and 'R2 and R3 are independently selected from η, ΓΗ χτττ CH3, NH2, OH and COOH; The pH of the palladium solution was adjusted to 7 ± 3; and C) the catalyst precursor was subjected to a reduction treatment with a reducing agent to obtain a supported _/carbon catalyst. According to a preferred embodiment, the above method further comprises: aging the catalyst precursor at a temperature of 0 to 80 ° C for 1 to 5 以前 before subjecting the 8 < S ) catalyst precursor to a reduction treatment. hour. There is no particular limitation on the activated carbon used in the present invention. An example of activated carbon is a surface area of more than 9 GGm 2 /g, a particle size of 4-8 mesh coconut shell activated carbon ° The concentration of the aqueous mineral acid solution used in the method of the present invention may be in the range of 0.01 to 5 m / liter Preferably, it is in the range of 〇.〇1~3〇莫/liter. Examples of the inorganic acid include, but are not limited to, hydrochloric acid, nitric acid, and phosphoric acid. The pickling time is not critical, but is preferably in the range of 〜 5 to 8 hours, more preferably in the range of 0.5 to 4 hours. The activated carbon is washed with the aqueous solution of the inorganic acid, washed with water until neutral, and then dried. Drying can usually be carried out by drying at a temperature of 8 Torr to 15 Torr < t for 0.5 to 1 hour, preferably 〇 5 to 6 hours. Examples of Pd compounds which can be used in the present invention include, but are not limited to, palladium halides, palladium acetate, palladium nitrate, palladium acid salt, and nitrogen acid. Basic salts of chloropalladic acid, palladium ammino-complexes, and combinations thereof. Preferably, the Pd compound is palladium acid or ethyl palladium acid. The pH of the solution containing the pd compound and the additive is preferably in the range of 4 to 9. The concentration of the Pd compound in the solution in terms of pd is preferably in the range of from 1 to 20% by weight, more preferably from 0.1 to 10% by weight, most preferably from 2 to 3.6 % by weight.

The amount of the additive in the Pd solution may vary depending on the P used (1 compound and the additive used in 1355529, but usually the molar ratio of the additive in the solution to the Pd compound in the Pd is in the range of 0.01:1 to 2:1. And the molar ratio of the additive to the Pd in the Pd compound is preferably in the range of 〇.〇5:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.0:1. Some examples of I compounds are as follows:

R wide (CH2)n-CHC〇〇H

I R2 - (CH2)m- CCOOH R3-(CH2)i -chcooh Additive A Ri = R2=R3 = H n=m=l=0 Additive B Ri= R3 = Η ; R2=NH2 n = 5 ; m = 1=1 additive C Ri= CH3 ; R2 = R3=H n=4 ; m=l=0 additive D Ri=R2= H ; R3= OH n=m=3 ; 1=1 additive E Ri=R3=H R2=co〇hn=m=l=〇Additive F Ri= R3 = H ; R2=OH n=m=l=0 An example of a reducing agent for reducing the catalyst precursor includes, but is not limited to, formic acid ( F〇rmic acid ), sodium sulphate (s〇diUm formate), formaldehyde, hydrazine hydrate, glucose, temper, and combinations thereof. Preferably, the reducing agent is sodium formate or hydrazine hydrate. The amount of the reducing agent depends on the amount of the active component pd, and is usually 丨1 to 1 times, preferably 2 to 5 times, the amount required for the reduction reaction theory. The reduction treatment of the catalyst carcass can be carried out according to procedures and conditions well known to those skilled in the art. For example, the reduction treatment can be carried out at a temperature of 〇~2〇〇t, preferably 20 to 12 ° C for 0.5 to 24 hours, preferably hours, more preferably

C S 10 1355293 1 to 4 hours. According to a preferred embodiment, the process for preparing a supported palladium/carbon catalyst of the present invention comprises the steps of: 1) washing the granulated or shaped activated carbon support with an aqueous acid solution for 5 to 8 hours, the acid of the aqueous acid solution The concentration is 0.01~3 〇mol/L, the acid is one selected from the group consisting of hydrochloric acid, oxalic acid and disc acid; 2) the acid washed activated carbon carrier is washed with water to neutral, then at 8〇~150 Drying for 0.5 to 1 hour under C conditions gives a treated activated carbon support; 3) impregnating or spraying the treated activated carbon support with an aqueous solution containing a water-soluble Pd compound and an additive of the following formula: The pd compound is supported on the treated activated carbon support to obtain a catalyst precursor. The content of the Pd compound in the aqueous solution is 〇丨~丨〇% by weight in terms of pd, and the molar ratio of the additive to Pd is 0.05. : within the range of 1 to 1.5: 1, the pH of the aqueous solution is adjusted to 7 ± 3,

Ri-(CH2)„-CHCOOH

R2-(CH2)m-cCOOH

I

R3-(CH2)i-CHCOOH wherein n, 1 are independently o or any integer from 1 to 5; and R1, R2 and R3 are independently selected from OH, hydrazine, CH3, hydrazine 2 and COOH; The catalyst precursor from step 3) is reduced to 8 by the reduction of the Pd ion of the Pd compound by the reduction of the catalyst precursor after the aging to 8 (TC temperature aging for 1 to 50 hours; and 11 1355293 5). Pd, got: processing, and the prior art (four), this day (four) has the advantage of being made. . . It has a high metal pd dispersion and a high crystallite content, and has a long activity and a long service life. [Embodiment] The present invention will be described by way of examples, but without limiting the scope of the invention. In the embodiment, the following test methods are employed:

(1) Dispersion of metallic palladium: The dispersion of the metallurgy was measured by a gas oxygenation method using a chemical adsorption instrument. The degree of dispersion is calculated according to the following formula: Dispersity = ((2xV«xMPd) / (3x22400xWttXCPd)) xi 〇 0% where: Va represents the hydrogen adsorption amount of the sample, and MPd represents the atomic weight of the sample,

The W sample indicates the weight of the sample, and Cpd indicates the content of the sample. (2) Crystallite content: The term "crystallite content" as used in the present invention means the content of crystals having a particle diameter of less than 2.5 nm. The content of palladium in the catalyst was determined by X-ray spectrometer. The particle size of the metal palladium crystallites was measured by χ-ray diffraction (XRD), and then the crystallite content was calculated by the following formula: Microcrystalline content = (particle diameter is less than 2.5 nm metal palladium grain weight / total metal palladium weight) X 100% 12 (S ) 1355293 (3) Thermal stability: Determination of palladium grains of palladium/carbon catalyst by X-ray diffraction (XRD) The average particle size. The catalyst was then calcined at 5 Torr»c for 1 hour after bubbling through a stream of 25 ° C water, and the average grain size of the grains was measured by a χ-ray diffraction (XRD). The average particle size of the palladium grains after calcination and the change in the average grain size of the grains before and after calcination indicate the thermal stability of the catalyst. The smaller the average grain size of the crystal grains after calcination, the better the thermal stability of the catalyst. At the same time, the smaller the change in the average particle diameter of the palladium grains before and after the calcination, the better the thermal stability of the catalyst. (4) Content of palladium in layers at different depths under the surface of the catalyst: Argon etching was performed on the surface of the catalyst. After etching to a certain depth, the palladium content in the surface layer exposed after etching was measured by photoelectron spectroscopy (XPS) and Auger spectroscopy (AES) to obtain the palladium content in the layer at different depths under the catalyst surface. Example 1 100 g of coconut shell activated carbon which passed through a 4-mesh sieve but remained on an 8-mesh sieve and had a surface area of uoo m 2 /g was washed with a 200 mi 0·4 mol/liter aqueous solution of nitric acid for 2 hours. After removing the acid solution, the activated carbon was washed with deionized water until neutral, and then dried at 12 °t for 6 hours. Take an aqueous solution containing 3 % of chlorine, add deionized water = 40 ml, add 2 16 g of 1 (% by weight) of the additive a aqueous solution, and add deionized water to the solution volume. It is 6 〇 ml. An aqueous NaOH solution was added to adjust the pH of the quaternary solution to about 7. After the cerium-containing solution was stabilized for 18 G minutes, the above treated activated carbon was impregnated with the pd <S) 13 1355293 solution for 3 hours to obtain a catalyst precursor. The catalyst precursor was aged at room temperature for 24 hours, and then impregnated at (10) for 3 hours in a reducing solution prepared from 2 g of a 5% by weight aqueous solution of hydrazine hydrate and 200 g of pure water. After removing the liquid by filtration, the solid was washed to neutral with pure water and dried to obtain a catalyst product. Examples 2 to 24 Different Pd compounds and different additives were used to prepare a pd-containing solution, and the rest were the same as in Example 1. Specific Pd compound, containing pd solution

The Pd compound content (in terms of Pd), the specific additives, and the molar ratio of the additive to pd are listed in Table 1. Examples 25 to 30 The procedure of Example 1 was followed, except that different additives were used to prepare a Pd-containing solution (see Table 1 for specific additives), and a pd-containing solution was sprayed on activated carbon to obtain a catalyst precursor, and additionally The inorganic acid, inorganic acid concentration, pickling time, drying time, temperature, pH of the solution containing the additive and the Pd compound, reducing agent, reduction treatment temperature, and reduction treatment time as shown in Table 2. _Comparative Example No additives were added in the preparation of the Pd-containing solution, and the rest were the same as in Example 1. The catalysts prepared in the respective examples and comparative examples were subjected to measurement of dispersity, crystallite content, thermal stability, and content in layers at different depths of the catalyst surface, and the catalysts were evaluated under the following evaluation conditions. 3 and Table 4. Evaluation conditions of the catalyst: Catalyst dosage: 2.0 g 14 1355293 Crude terephthalic acid 4-CBA Amount: Reaction pressure: Hydrogen partial pressure: Reaction time: Reaction temperature: Add 4 -丨 4-CBA conversion =-

:30.0 g 1.0 g 70 Kg 5.0 Kg 1.0 hour 270〇C Amount of remaining 4-CBA Add 4-CBA amount xl 00%

15 1355293 Table 1 Example Pd compound additive Pd charge amount / activated carbon (% by weight) Additive / Pd (mole ratio) Example 1 gas palladium acid additive A 0.51 0.20 Example 2 gas palladium acid additive A 0.51 0.30 Example 3 Chloro palladium acid additive A 0.22 0.60 Example 4 Palladium acetate additive A 0.08 1.50 Example 5 Gas palladium acid additive B 0.51 0.20 Example 6 Gas palladium acid additive B 0.62 0.40 Example 7 Gas palladium acid additive B 0.51 0.60 Example 8 Palladium acetate additive B 3.55 0.80 Example 9 Gas palladium acid additive C 0.51 0.20 Example 10 Gas palladium acid additive C 0.51 0.40 Example 11 Chloro palladium acid additive C 0.51 0.60 Example 12 Palladium acetate additive C 0.15 1.00 Example 13 Palladium Acid Additive D 0.51 0.20 Example 14 Chloro palladium acid additive D 0.41 0.40 Example 15 Chloro palladium acid additive D 0.51 0.60 Example 16 Acetic acid saturated additive D 0.51 0.80 Example 17 Gas palladium acid additive E 0.51 0.20 Example 18 Gas palladium acid Additive E 1.00 0.40 Example 19 Gas Palladium Acid Additive E 0.51 0.60 Example 20 Acetic Acid Additive E 0.51 0.80 Example 21 Chloro palladium acid additive F 4.50 0.05 Example 22 Gas palladium acid additive F 0.51 0.40 Example 23 Gas palladium acid additive F 0.51 0.60 Example 24 Palladium acetate additive F 0.51 0.80 Example 25 Gas palladium acid additive A 0.51 0.20 Example 26 Gas Palladium Acid Additive B 0.51 0.40 Example 27 Chloro palladium Acid Additive C 0.51 0.60 Example 28 Gas Palladium Acid Additive D 0.51 0.80 Example 29 Gas Palladium Acid Additive E 0.51 0.50 Example 30 Gas Palladium Acid Additive F 0.51 0.50 Comparative Example Palladium Acid / 0.51 / 16 1355293

Table 2 Example No. Condition 25 26 27 28 29 30 Inorganic Acid Type Salt Nitric Acid Nitrate Nitric Acid Acid Acid Inorganic Acid Concentration (Molar/L) 0.4 0.1 3 0.4 0.01 0.4 Pickling Time (hours) 4 8 0.5 4 4 4 Drying temperature (°c) 150 120 120 80 120 120 Drying time (hours) 1 6 6 10 6 6 pH of the solution containing additives and Pd compounds 9 7 6 7 4 10 Solution Reducing agent type 曱Vinylformate Grape hydrate aldehyde Sodium aldehyde sodium glycoside reduction treatment temperature (°C) 50 80 120 200 120 80 Reduction treatment time (hours) 3 3 2 1 24 3 :(s ) 17 1355293 Table 3 Pd content (% by weight) dispersion in the catalyst of the example (%) Crystallite content (%) Average grain size (nm) 500 °C Average grain size after calcination (nm) Particle size change before and after calcination % 4- CBA conversion (%) Example 1 0.50 20 90 3.5 5.9 69 99.5 Example 2 0.50 23 91 3.6 6.0 67 99.7 Example 3 0.20 29 90 3.4 5.3 56 89.2 Example 4 0.08 21 92 2.7 5.3 96 -- Example 5 0.50 20 90 3.5 5.9 69 99.4 Example 6 0.60 26 90 3.6 6.0 67 99.8 Example 7 0.50 28 93 3.8 5.8 53 99.5 Example 8 3.50 20 92 3.3 5.9 79 99.6 Example 9 0.50 20 91 2.9 5.7 97 99.6 Example 10 0.50 22 92 3.8 5.6 47 99.8 Example 11 0.49 25 90 3.6 5.8 61 99.7 Example 12 0.15 28 91 3.0 5.7 90 -- Example 13 0.50 20 90 3.6 5.9 64 99.5 Example 14 0.40 21 92 3.3 5.6 70 99.5 Example 15 0.50 26 91 3.4 5.8 71 99.8 Example 16 0.49 25 90 3.2 5.9 84 99.9 Example 17 0.50 30 94 3.6 6.0 67 99.7 Example 18 0.98 27 90 3.7 5.9 59 100 Example 19 0.50 27 91 3.4 5.8 71 99.7 Example 20 0.50 28 91 3.5 5.7 63 99.8 Example 21 4.48 27 90 3.7 6.0 62 100 Example 22 0.50 28 92 3.6 5.9 64 99.7 Example 23 0.50 30 90 3.8 5.9 55 99.9 Example 24 0.50 28 91 3.3 5.9 79 99.7 Example 25 0.50 20 91 3.3 6.0 82 99.6 Example 26 0.50 20 90 3.5 5.9 69 99.7 Example 27 0.50 22 90 3.4 6.0 76 99.8 Example 28 0.49 26 91 3.7 5.9 59 99.9 Example 29 0.50 27 90 3.8 6.0 58 99.8 Example 30 0.50 28 92 3.0 5.7 90 99.6 Comparative Example 0.50 4 52 4.6 11.1 141 66.2 (s 18 1355293 Table 4 Pd content in the catalyst (% by weight) Saturated content (% by weight) in a layer having a depth of 5 nm under the surface of the catalyst Ι ε content (% by weight) in a layer having a depth of 300 nm under the surface of the catalyst Example 1 0.50 50.2 22.3 Example 2 0.50 51.2 23.7 Example 3 0.20 43.1 11.8 Example 4 0.08 30.1 5.9 Example 5 0.50 52.6 20.4 Example 6 0.60 57.8 28.0 Example 7 0.50 60.1 23.5 Example 8 3.50 63.4 29.3 Example 9 0.50 54.3 24.2 Example 10 0.50 51.4 23.6 Implementation Example 11 0.49 50.3 23.2 Example 12 0.15 40.6 11.3 Example 13 0.50 52.3 23.7 Example 14 0.40 50.4 20.5 Example 15 0.50 52.9 24.9 Example 16 0.49 50.4 23.1 Example 17 0.50 56.3 23.0 Example 18 0.98 70.1 30.3 Example 19 0.50 57.8 23.6 Example 20 0.50 53.5 23.8 Example 21 4.48 83.2 40.2 Example 22 0.50 56.1 21.2 Example 23 0.50 50.6 24.7 Example 24 0.50 53.4 25.3 Example 25 0.50 54.5 23.0 Example 26 0.50 55.6 27.4 Example 27 0.50 56.4 23.7 Example 28 0.49 53.3 23.9 Example 29 0.50 50.1 20.1 Example 30 0.50 56.5 24.7 Comparative Example 0.50 30.6 12.5 19 1355293 The patents, patent applications, non-patent documents and test methods mentioned in the specification of the present application are hereby incorporated by reference. While the invention has been described with respect to the preferred embodiments of the embodiments of the invention Therefore, the invention is not limited to the specific embodiments disclosed as the best mode for carrying out the invention, including all embodiments falling within the scope of the appended claims. [Simple diagram description] None [Main component symbol description] None 20

Claims (1)

1355293 For the invention patent No. 096129011 of the t-plate version X. Application for the patent garden: Announcement of this type of negative-cutting type/carbon catalysis 4ρτ where the loading is in the form of I crystallites, and it is less than 90% by weight of the total amount . "Micro...microcrystalline 2·^ shot the load surface/carbon pure agent described in the first paragraph of the patent range, the pot-loaded derivatization in the surface layer of the carrier activated carbon so that it is in the carbon/catalyst The content of the catalyst is 0.5 (four) 10 weights of the total weight of the catalyst. 'In the layer of 5 nm depth under the surface of the supported activated carbon == 3% by weight of the total atomic weight of the metal in the layer of nanometer depth. 5% by weight or more of the total atomic weight. \According to the load (iv)/carbon catalyst described in the second paragraph of the patent application, in the case where the content of the carbon catalyst is 0.50 010% by weight based on the total weight of the catalyst, the carrier is active. π main work body active stone surface under the surface of the depth of 5 nanometers of the sound = more than 40% by weight of the total atomic weight in the layer; in the carrier of the carrier: the amount of the degree of the metal in the layer The load-type handle/carbon catalyst according to any one of the first to third aspects of the invention, wherein the supported particles are in a surface state of the activated carbon of the carrier, and the dispersion degree thereof is not less than 5%. 5.=Supported saturated/carbon catalyst according to item 4 of the patent application scope, and The dispersity of the palladium is not less than 1%. The patented Μ1 to 3 of the load type/carbon reminder described in the item "" After bubbling through the 2nd generation of 21 1355293, the first genus of the lion's lions, 11 months, ,,, eve, 1UU, U), the average grain size of the load is not more than 10 hours after calcination in a nitrogen stream of water. 7. The supported type of carbon/catalyst according to any one of the above claims, wherein the catalyst contains 5 to 5 wt% of metal pd, based on the total amount of the catalyst. 8. The weight of the supported mono/carbon catalyst according to item 7 of the patent scope, wherein the catalyst contains 金属2 to 3.5% by weight of the total weight of the metal pd, the base (tetra). - A method for preparing a supported hammer/carbon catalyst according to item i of the patent application, comprising the steps of: a) first washing the activated carbon with a mineral acid aqueous solution, then washing with water to neutrality, and drying the washing Activated carbon to obtain an activated carbon carrier. b) using an aqueous solution containing a Pd compound and an additive Immersing or spraying the activated carbon support to support the Pd compound on the activated carbon support to obtain a catalyst precursor, wherein the molar ratio of the additive to the Pd compound in the aqueous solution is 0 01:1~2 0:1 The additive is selected from the group consisting of the following compounds: Rl-(CH2)n-CHCO〇H R2 - (CH2)m-CCOOH R3-(CH2)i-CHC00H wherein n, m*i are independently selected from hydrazine And an integer from i to 5, and h, R2 and R3 are independently selected from H, CH3 'NH2, 0H and c〇〇H; the pH of the sharp solution is adjusted to 7 ± 3; and 22 1355293 is replaced by version I 096129011 Inventive Patent Application Patent Application Revised Umbrella) C) The catalyst precursor is reduced with a reducing agent to obtain a supported Ιε/carbon catalyst. 10. The method according to claim 9, wherein the inorganic acid is at least one selected from the group consisting of hydrochloric acid, nitric acid and acid filling; the pickling time is 〇5 to 8 hours; and the acid concentration of the inorganic acid solution is 〇〇1~5 〇mol/L; Drying is carried out at a temperature of 80 to 150 ° C for 0.5 to 1 〇 hours. 11. The method according to claim 9 or 10, wherein the pd compound is selected from the group consisting of a phosphonium compound of Pd, palladium acetate, palladium nitrate, chloropalladium acid, a basic salt of chloropalladium acid, a palladium ammonia complex, and The combination of the percentage of Pd in the pd-containing solution is 〇〇1~2〇%; the molar ratio of Pd in the solution to the Pd compound is 〇〇1:1~2. 12. The method according to the above-mentioned patent scope, wherein the other compound is a gas acid or acetic acid; the pH of the solution containing the Pd compound and the additive is 4 to 9; and the weight concentration of Pd in the solution is 〇 ~~ι〇%; and the molar ratio of the additive to the Pd compound in the solution is 〇〇51~ 13. The method according to claim 9 or claim 1, further comprising pre-treating the catalyst precursor at a temperature of 8 〇〇c before the reduction treatment. 14. According to the scope of patent application! Selected from the method of a cockroach m 蜎 & quot 其中 其中 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ (8) Carrying 〇5 V under C/dishness 15. According to the patent scope of the patent, the “Property Precursor 23” 16. Before the reduction treatment, the temperature is aged at 8〇〇C and the temperature is aged 1~24 or Hydrazine hydrate; and the reduction treatment is carried out at a temperature of 20 to 12 〇 λ ζυ L for 1 to 1 〇 hours. A method for preparing a supported palladium/carbon catalyst according to the scope of the invention is as follows: 1) washing the granular or shaped activated carbon support with an aqueous acid solution for 0-5 to 8 hours. The acid concentration is 〇〇1~3 〇mol/L' acid is one of hydrochloric acid, nitric acid and phosphoric acid; 2) the acid washed activated carbon carrier is washed with water to neutral, then at 80~150 Drying at °C for 0.5 to 10 hours gives the treated activated carbon support; 3) impregnating or spraying the treated activated carbon support with an aqueous solution containing a water-soluble Pd compound and an additive of the following formula I, The Pd compound is supported on the treated activated carbon support to obtain a catalyst precursor. The content of the pd compound in the aqueous solution is 0.1 to 10% by weight in terms of Pd, and the molar ratio of the additive to Pd is 〇.〇5 : 1~1.5 : 1 , the pH of the aqueous solution is adjusted to 7 ± 3, Ri-(CH2)n-CHCOOH R2-(CH2)m-CCOOH R3-(ch2), -c HCOOH wherein n, m and 丨 are independently 0 or 1 to 5; and I, R2 and R3 are independently selected OH, hydrazine, CH3, NH2 and COOH; 24 1355293 4) aging the catalyst precursor from step 3) at a temperature of from 0 to 80 ° C for 1 to 50 hours; and 5) using a reducing agent for the aged catalyst precursor The reduction treatment is carried out to reduce the Pd ions in the Pd compound to the metal Pd to obtain a catalyst product. 25