CN113289694B - Method for regenerating palladium catalyst in anthraquinone process hydrogen peroxide production - Google Patents
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Abstract
The invention discloses a method for regenerating a palladium catalyst in the production of hydrogen peroxide by an anthraquinone method, which comprises the following steps of 1) adopting saturated steam to regenerate the used palladium catalyst, steaming and boiling the steam, and drying the steam by using dry nitrogen; 2) Soaking and recycling the palladium catalyst by adopting a specific solvent; 3) Then the mixture is soaked and circulated by a specific alkaline solution; 4) The catalyst was rinsed with purified water (deionized water) and dried with dry nitrogen before being put into production. By using the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone process, the service life of the palladium catalyst is greatly prolonged, the long-period stable operation of a production line is ensured, the method is a new high-efficiency regeneration technology, the service life of the palladium catalyst can be further prolonged, and the service activity of the palladium catalyst is recovered.
Description
[ field of technology ]
The invention relates to the technical field of catalysts, in particular to a method for regenerating a palladium catalyst in the production of hydrogen peroxide by an anthraquinone process.
[ background Art ]
Hydrogen peroxide is an important inorganic chemical product and is widely applied in the industrial fields of medical treatment, papermaking, chemical industry, food, electronics, organic synthesis, environmental protection and the like. In recent years, along with the continuous improvement of ecological protection consciousness of people, the application of hydrogen peroxide as a green oxidant in some emerging chemical clean production processes is also continuously expanded, and the hydrogen peroxide is applied to new technologies such as cyclohexanone, caprolactam, epoxypropane and the like. With some new applications of hydrogen peroxide and from the environmental protection perspective, the demand of hydrogen peroxide will be increased increasingly, so as to promote the hydrogen peroxide yield to keep continuously growing.
Among the hydrogen peroxide production methods, the anthraquinone method is the most important production method, and accounts for more than 98% of the whole hydrogen peroxide productivity. The anthraquinone method for producing hydrogen peroxide uses 2-ethyl anthraquinone (EAQ, hereinafter referred to as anthraquinone) as a reaction carrier, and uses heavy aromatic hydrocarbon (AR), trioctyl phosphate (TOP) and acetate as mixed solvents to prepare a solution with a certain composition (hereinafter referred to as working solution). The working solution and hydrogen are introduced into a hydrogenation tower filled with palladium catalyst to carry out hydrogenation reaction under certain temperature and pressure, thus obtaining corresponding 2-ethyl hydro anthraquinone (HEAQ, hydro anthraquinone) solution (hydrogenated solution). After entering the oxidation tower, the hydrogenated liquid is oxidized by air under certain pressure and temperature, and the hydro-anthraquinone in the working liquid is recovered to the original anthraquinone, and hydrogen peroxide is generated. The working solution containing hydrogen peroxide (abbreviated as oxidizing solution) enters an extraction tower, and the working solution containing hydrogen peroxide is extracted by pure water by utilizing the difference of the solubility of the hydrogen peroxide in water and the working solution and the density difference of the working solution and the water to obtain an aqueous solution containing hydrogen peroxide (commonly called hydrogen peroxide). The hydrogen peroxide aqueous solution is purified by heavy aromatic hydrocarbon (soluble organic impurities in the hydrogen peroxide are removed) and air is purged, so that the hydrogen peroxide product with the concentration of 27.5 percent or 35 percent can be obtained. The working solution (raffinate for short) after pure water extraction is firstly separated by a high-efficiency coalescer, the raffinate after water diversion by the coalescer directly enters a circulating working solution storage tank in one part (about 30 percent), the water is removed in the other part (about 70 percent) by a vacuum dehydrator, and the dried working solution is regenerated by a post-treatment clay bed to become fresh working solution for continuous recycling. During the cyclic operation (hydrogenation process), part of the 2-ethylanthraquinone gradually becomes tetrahydro-2-ethylanthraquinone (H4 EAQ) and accumulates in the working fluid, which is also one of the important carriers of the process, which can also be repeatedly hydrogenated, oxidized, to generate hydrogen peroxide. The presence of certain amounts of tetrahydro-2-ethylanthraquinone will be advantageous for increasing the hydrogenation reaction rate and inhibiting the formation of other by-products.
At present, the industrial anthraquinone method for producing hydrogen peroxide mainly comprises a fixed bed process and a fluidized bed process, wherein palladium is used as a main active component of a catalyst, more than 90% of hydrogen peroxide production devices in China adopt the fixed bed process, and the fixed bed process mainly comprises hydrogenation, oxidation, extraction and post-treatment, wherein the hydrogenation is a core of the whole process, and the palladium catalyst is more a soul of the whole hydrogenation. The commercial palladium catalyst for producing hydrogen peroxide by the domestic anthraquinone method mainly comprises the following components: bar, tri (tetra) leaf grass, toothed sphere, rolling sphere and drop sphere palladium catalysts. The strip-shaped and tri (tetra) leaf grass type palladium catalysts have fragile defects in production, packaging, transportation, loading and unloading, bed filling and use due to appearance reasons; the tooth-ball type palladium catalyst has the advantages that the shape of the catalyst has a groove structure, the activity is higher in the initial use, but along with the extension of the use time, the degradation products and the alumina powder of the system are easy to accumulate in the groove on the outer surface, the degradation products are difficult to remove in the regeneration process after the first use period is finished, the activity is fast to drop, and the subsequent use effect is poor; the spherical palladium catalyst (rolling sphere and dropping sphere) prepared by the rolling granulation method is extremely easy to remove palladium and powder in the use process due to the forming mode, and has the defects of quicker noble metal falling, quick activity attenuation, low residual value and the like.
In the anthraquinone method hydrogen peroxide production process, a palladium catalyst is used as a main catalyst for hydrogenation reaction in a hydrogenation process, and the quality of performance directly influences the stable operation and the productivity of production equipment; however, in the use process of the palladium catalyst, degradation products generated by the reaction and active alumina dust in the previous process are brought in, so that the active center of the surface of the palladium catalyst is covered by the substances, the activity (hydrogen absorption capacity) of the palladium catalyst is affected, and when the activity of the palladium catalyst is seriously reduced, the stable operation and the productivity of production equipment are seriously affected. Therefore, when the activity of the palladium catalyst can not meet the production requirement, the palladium catalyst with severely reduced activity is required to be regenerated, so that the activity of the palladium catalyst is recovered, and the production requirement is further met.
At present, in the production process of hydrogen peroxide by an anthraquinone method, most of alkylanthraquinone hydrogenation catalysts are supported palladium catalysts, and most of supports are alumina or aluminosilicate; the palladium content was 0.3%. The preparation of the carrier palladium catalyst comprises the steps of immersing an alumina carrier in a quantitative palladium chloride solution, and loading palladium chloride on the surface of the alumina to form a thin eggshell-shaped palladium salt layer; the palladium oxide carrier catalyst is changed into yellow brown after being dried and converted, and before being used, the palladium oxide carrier catalyst is changed into palladium black and water after being activated by hydrogen. In the existing production, the palladium catalyst regeneration technology of most hydrogen peroxide manufacturers in China adopts the traditional saturated steam regeneration technology, the traditional saturated steam regeneration technology cannot thoroughly remove the active center of the deactivated palladium catalyst surface, when the palladium catalyst is put into production after regeneration, the active center cannot fully play a role due to a covering which is not thoroughly removed on the palladium catalyst surface, and only a small part of the active center can work, wherein the performance is that the palladium catalyst is affected by diffusion, the reaction temperature must be higher than that of the normal state, so that the catalyst is greatly damaged, the uncovered active center is overloaded to work and lose efficacy or the activity is seriously attenuated, and the activity of the covered active center is reduced due to the growth of palladium particles due to the rise of the temperature, so that the effect is very bad. The defect of regeneration technology will lead to serious consequences such as low efficiency of palladium catalyst, reduced service cycle, etc., and cause the situation of high production cost and low production stability.
Therefore, there is an urgent need to find a new method for regenerating palladium catalyst.
[ invention ]
At present, most of domestic hydrogen peroxide manufacturers adopt the conventional saturated steam regeneration technology, the conventional saturated steam regeneration technology cannot thoroughly remove the active center of the deactivated palladium catalyst surface, and when the palladium catalyst is put into production after regeneration, the active center cannot fully play a role due to a covering which is not thoroughly removed from the palladium catalyst surface, and only a small part of the active center can be used for working.
The aim of the invention is achieved by the following technical scheme:
the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method comprises the following steps:
1) The method comprises the following steps of (1) carrying out regeneration treatment on a palladium catalyst (catalyst) to be regenerated by adopting saturated steam: introducing saturated steam into the palladium catalyst to be regenerated, controlling the pressure of the palladium catalyst bed to be 0.2MPa and the pure water flow to be 4-5m 3 And (3) stopping boiling and regenerating when the regenerated condensate is not turbid and has lighter color according to the volume ratio of 2:1, and introducing clean dry nitrogen to control the moisture content of the palladium catalyst to be below 100 ppm;
2) Soaking and recycling the palladium catalyst: mixing aromatic hydrocarbon and trioctyl phosphate according to a volume ratio of 3:1 to obtain a mixed solution; mixing the solution and the palladium catalyst obtained in the previous step, soaking according to the volume ratio of (1.5-2.0): 1, wherein the soaking temperature is 40-50 ℃ and the soaking time is 30min, and mixing the solution by 15M 3 Circulation/h, wherein the circulation time is 1.5h;
3) Soaking and recycling the palladium catalyst obtained in the previous step by using an alkaline solution: washing palladium catalyst with alkaline solution with pH=11-12 for 2-3 times, soaking in alkaline solution at 40-45deg.C for 30min at 15M according to volume ratio of (1.5-2.0): 1 to obtain palladium catalyst 3 Circulation/h, wherein the circulation time is 1.5h;
4) Soaking and recycling the palladium catalyst obtained in the previous step by deionized water: washing palladium catalyst with deionized water for 2-3 times, soaking with deionized water and the above steps to obtain palladium catalyst according to volume ratio of (1.5-2.0): 1 at 40-45deg.C for 30min, wherein deionized water is 15M 3 Circulation/h, wherein the circulation time is 1.5h; and drying the obtained palladium catalyst or drying the palladium catalyst by using dry steam, and purging the palladium catalyst with nitrogen when the palladium catalyst is hot until no water remains, so as to be ready for use.
In the invention, the following components are added:
and step 1), introducing saturated steam into the palladium catalyst to be regenerated, namely cutting out the palladium catalyst bed to be regenerated, closing a working solution and hydrogen inlet and outlet valves connected with the palladium catalyst bed to be regenerated, opening a saturated steam inlet valve and a regenerated condensate outlet valve, and introducing saturated steam.
The aromatic hydrocarbon in the step 2) is selected from benzene, toluene or o-xylene, and the aromatic hydrocarbon is mixed in any proportion.
The mixed solution in the step 2) adopts 15M 3 And (3) circulating for 1.5 hours, wherein the fresh mixed solution is replaced in the circulating process until the mixed solution is not turbid and has lighter color.
The alkaline solution in the step 3) is selected from NaOH solution or KOH solution.
The alkaline solution in step 3) is 15M 3 And (3) circulating for 1.5 hours, and replacing the alkali liquor after the circulation is completed once, wherein the circulation is completed twice, and the alkali liquor is discharged after the circulation is completed.
The deionized water in the step 4) adopts 15M 3 And (3) circulating for 1.5 hours, replacing new deionized water after the circulation is completed once, and repeating the circulating steps until the pH of the discharged washing water is neutral and clear.
And (3) drying in the step (4) at 100-130 ℃.
Compared with the prior art, the invention has the following advantages:
1. in the prior art, in the production process of the anthraquinone hydrogen peroxide, hydrogenation reaction is completed in a hydrogenation tower filled with a palladium catalyst as a main reaction, asymmetric hydrogenation and even aromatic ring hydrogenation can occur in addition to carbonyl symmetric hydrogenation in the hydrogenation process of the anthraquinone, and hydrogen peroxide (collectively referred to as degradation products) can not be generated by circulation of hydrogenation products except for tetrahydroanthraquinone; the existence of degradation products gradually occupies the active center of the palladium catalyst after daily accumulation and monthly accumulation, so that the activity of the palladium catalyst is reduced, the product quality and the productivity are affected, and the active center of the palladium catalyst covered by the degradation products cannot be effectively removed by using the traditional saturated steam. The method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method adopts the mixed solution of aromatic hydrocarbon and trioctyl phosphate as a specific solvent (organic solvent) for soaking and circulating treatment, and mainly aims to remove the degradation products partially covered on the surface of the palladium catalyst by using the aromatic hydrocarbon, and remove the degradation products partially covered on the surface of the palladium catalyst by using the trioctyl phosphate, so that the removal rate of the degradation products covering the active center of the palladium catalyst can reach 95%, and the activity recovery of the palladium catalyst is improved.
2. In the daily use process of the palladium catalyst, as the active alumina balls exist in the previous working procedure, part of alumina dust can be brought into a hydrogenation tower filled with the palladium catalyst, and the palladium catalyst gradually forms gel aluminum salt and gradually covers the active center of the palladium catalyst, so that the activity of the palladium catalyst is reduced. According to the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method, the specific alkaline solution is adopted for soaking and circulating treatment, so that the removal rate of the aluminum salt gel covering the active center of the palladium catalyst can reach 94%, and the activity recovery of the palladium catalyst is improved.
[ description of the drawings ]
FIG. 1 is a diagram of a regenerated palladium catalyst according to example 1 of the present invention.
FIG. 2 is a diagram of a palladium catalyst before regeneration in example 1 of the present invention.
[ detailed description ] of the invention
The following describes the invention in more detail with reference to examples.
Example 1:
the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method comprises the following steps:
1) The palladium catalyst to be regenerated is regenerated by saturated steam: cutting off the palladium catalyst bed to be regenerated, closing the inlet and outlet valves of working solution and hydrogen connected with the palladium catalyst bed to be regenerated, opening the inlet valve of saturated steam and the outlet valve of regenerated condensate, introducing saturated steam, controlling the pressure of the palladium catalyst bed to be 0.2MPa and the pure water flow to be 4m 3 And/h, the regeneration time is 10h, the saturated steam and the palladium catalyst to be regenerated are mixed according to the volume ratio of 2:1,stopping steaming and regenerating when the regenerated condensate is not turbid and has lighter color, and introducing clean dry nitrogen, and stopping introducing dry nitrogen after the moisture content of the palladium catalyst is controlled below 100 ppm;
2) Soaking and recycling the palladium catalyst: mixing aromatic hydrocarbon (benzene) and trioctyl phosphate according to a volume ratio of 3:1 to obtain a mixed solution; mixing the solution and the palladium catalyst obtained in the previous step, soaking according to the volume ratio of 1.5:1, wherein the soaking temperature is 40 ℃, the soaking time is 30min, and the mixed solution adopts 15M 3 And (3) circulating for 1.5 hours, and replacing the fresh mixed solution in the circulating process until the mixed solution is not turbid and has lighter color;
3) Soaking and recycling the palladium catalyst obtained in the previous step by using an alkaline solution: washing the palladium catalyst with alkaline solution (NaOH solution) with pH=11 for 2 times, soaking the palladium catalyst with alkaline solution and the palladium catalyst obtained in the previous step according to the volume ratio of 1.5:1, wherein the soaking temperature is 42 ℃, the soaking time is 30min, and the alkaline solution adopts 15M 3 And (3) circulating for 1.5 hours, replacing new alkali liquor after the circulation is completed once, and discharging after the circulation is completed twice;
4) Soaking and recycling the palladium catalyst obtained in the previous step by deionized water: firstly, cleaning a palladium catalyst for 2 times by deionized water, then, soaking the palladium catalyst by deionized water and the previous step according to the volume ratio of 2.0:1, wherein the soaking temperature is 40 ℃, the soaking time is 30min, and the deionized water adopts 15M 3 And (3) circulating for 1.5 hours, replacing new deionized water after the circulation is completed once, and repeating the circulating steps until the pH value of the discharged washing water is neutral and clear;
and drying the obtained palladium catalyst at 130 ℃, and purging with nitrogen when the palladium catalyst is hot until no water remains.
Example 2:
the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method comprises the following steps:
1) The palladium catalyst to be regenerated is regenerated by saturated steam: cutting off the palladium catalyst bed to be regenerated, and closing the connection with the palladium catalyst bed to be regeneratedThe working solution and hydrogen inlet and outlet valves of the (2) are opened, the saturated steam inlet valve and the regenerated condensate outlet valve are opened, saturated steam is introduced, the pressure of the palladium catalyst bed is controlled to be 0.2MPa, and the pure water flow is controlled to be 5m 3 And (3) stopping boiling and regenerating when the regenerated condensate is not turbid and has lighter color according to the volume ratio of 2:1, and introducing clean dry nitrogen to control the moisture content of the palladium catalyst to be below 100 ppm;
2) Soaking and recycling the palladium catalyst: mixing aromatic hydrocarbon (toluene) and trioctyl phosphate according to a volume ratio of 3:1 to obtain a mixed solution; mixing the solution and the palladium catalyst obtained in the previous step, soaking according to the volume ratio of 2.0:1, wherein the soaking temperature is 50 ℃, the soaking time is 30min, and the mixed solution adopts 15M 3 And (3) circulating for 1.5 hours, and replacing the fresh mixed solution in the circulating process until the mixed solution is not turbid and has lighter color;
3) Soaking and recycling the palladium catalyst obtained in the previous step by using an alkaline solution: washing the palladium catalyst with alkaline solution (NaOH solution) with pH=12 for 3 times, soaking the palladium catalyst with alkaline solution and the palladium catalyst obtained in the previous step according to the volume ratio of 1.8:1, wherein the soaking temperature is 45 ℃, the soaking time is 30min, and the alkaline solution adopts 15M 3 And (3) circulating for 1.5 hours, replacing new alkali liquor after the circulation is completed once, and discharging after the circulation is completed twice;
4) Soaking and recycling the palladium catalyst obtained in the previous step by deionized water: washing the palladium catalyst with deionized water for 2 times, soaking the palladium catalyst with deionized water and the palladium catalyst obtained in the previous step according to the volume ratio of 1.5:1, wherein the soaking temperature is 40 ℃, the soaking time is 30min, and the deionized water adopts 15M 3 And (3) circulating for 1.5 hours, replacing new deionized water after the circulation is completed once, and repeating the circulating steps until the pH value of the discharged washing water is neutral and clear;
and drying the obtained palladium catalyst at the temperature of 100 ℃, and purging with nitrogen when the palladium catalyst is hot until no water remains.
Example 3:
the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method comprises the following steps:
1) The palladium catalyst to be regenerated is regenerated by saturated steam: cutting off the palladium catalyst bed to be regenerated, closing the inlet and outlet valves of working solution and hydrogen connected with the palladium catalyst bed to be regenerated, opening the inlet valve of saturated steam and the outlet valve of regenerated condensate, introducing saturated steam, controlling the pressure of the palladium catalyst bed to be 0.2MPa and the flow rate of pure water to be 4.5m 3 And (3) stopping boiling and regenerating when the regenerated condensate is not turbid and has lighter color according to the volume ratio of 2:1, and introducing clean dry nitrogen to control the moisture content of the palladium catalyst to be below 100 ppm;
2) Soaking and recycling the palladium catalyst: mixing aromatic hydrocarbon (benzene and o-xylene are mixed according to an equal volume ratio) and trioctyl phosphate according to a volume ratio of 3:1 to obtain a mixed solution; mixing the solution and the palladium catalyst obtained in the previous step, soaking according to the volume ratio of 1.8:1, wherein the soaking temperature is 45 ℃, the soaking time is 30min, and the mixed solution adopts 15M 3 And (3) circulating for 1.5 hours, and replacing the fresh mixed solution in the circulating process until the mixed solution is not turbid and has lighter color;
3) Soaking and recycling the palladium catalyst obtained in the previous step by using an alkaline solution: washing the palladium catalyst with alkaline solution (KOH solution) with pH=11 for 2 times, soaking the palladium catalyst with alkaline solution and the palladium catalyst obtained in the previous step according to the volume ratio of 2.0:1, wherein the soaking temperature is 40 ℃, the soaking time is 30min, and the alkaline solution adopts 15M 3 And (3) circulating for 1.5 hours, replacing new alkali liquor after the circulation is completed once, and discharging after the circulation is completed twice;
4) Soaking and recycling the palladium catalyst obtained in the previous step by deionized water: washing the palladium catalyst with deionized water for 3 times, soaking the palladium catalyst with deionized water and the palladium catalyst obtained in the previous step according to the volume ratio of 1.8:1 at 45 ℃ for 30min, wherein the deionized water is 15M 3 Cycle/h, cycle time 1.5hAfter the circulation is completed once, new deionized water is replaced, and the circulation steps are repeated until the pH value of the discharged washing water is neutral and clear;
and drying the obtained palladium catalyst by using dry steam, and purging the palladium catalyst with nitrogen when the palladium catalyst is hot until no water remains.
Comparative example 1:
a conventional saturated steam regenerated palladium catalyst is used.
Comparative example 2:
compared with the example 1, the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method lacks the step 2), namely, no specific solvent (organic solvent) is adopted for soaking and recycling treatment.
Comparative example 3:
compared with the method in example 1, the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method lacks the step 3), namely, no specific alkaline solution is adopted for soaking and recycling treatment.
Comparative example 4:
compared with the embodiment 1, the method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method has the advantages that trioctyl phosphate is absent in the step 2), namely, aromatic hydrocarbon soaking and circulating treatment are directly adopted.
Experimental example:
period of use after regeneration of the palladium catalysts of comparative examples and comparative examples.
Table 1:
as can be seen from Table 1, by using the method for regenerating the palladium catalyst in the production of hydrogen peroxide by the anthraquinone process, the service life of the palladium catalyst is greatly prolonged (the palladium catalyst before regeneration is black, and the regenerated palladium catalyst is yellow brown), so that the long-period stable operation of the production line is ensured.
The method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone method is a new high-efficiency regeneration technology, can further improve the service life of the palladium catalyst and recover the service activity of the palladium catalyst.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (3)
1. The method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone process is characterized by comprising the following steps of: the method comprises the following steps:
1) The palladium catalyst to be regenerated is regenerated by saturated steam: introducing saturated steam into the palladium catalyst to be regenerated, controlling the pressure of the palladium catalyst bed to be 0.2MPa and the pure water flow to be 4-5m 3 And (3) stopping boiling and regenerating when the regenerated condensate is not turbid and has lighter color according to the volume ratio of 2:1, and introducing clean dry nitrogen to control the moisture content of the palladium catalyst to be below 100 ppm;
2) Soaking and recycling the palladium catalyst: mixing aromatic hydrocarbon and trioctyl phosphate according to a volume ratio of 3:1 to obtain a mixed solution; mixing the solution and the palladium catalyst obtained in the previous step, soaking according to the volume ratio of (1.5-2.0): 1, wherein the soaking temperature is 40-50 ℃ and the soaking time is 30min, and mixing the solution by 15M 3 Circulation/h, wherein the circulation time is 1.5h; the aromatic hydrocarbon is selected from benzene, toluene or o-xylene, and is in any proportion when mixed;
3) Soaking and recycling the palladium catalyst obtained in the previous step by using an alkaline solution: washing palladium catalyst with alkaline solution with pH=11-12 for 2-3 times, soaking in alkaline solution at 40-45deg.C for 30min at 15M according to volume ratio of (1.5-2.0): 1 to obtain palladium catalyst 3 Circulation/h, wherein the circulation time is 1.5h; the alkaline solution is selected from NaOH solution or KOH solution;
4) Soaking and recycling the palladium catalyst obtained in the previous step by deionized water: firstly, deionized water is used for cleaningThe palladium catalyst is obtained by 2-3 times, deionized water and the previous steps, the palladium catalyst is soaked according to the volume ratio of (1.5-2.0): 1, the soaking temperature is 40-45 ℃ and the soaking time is 30min, and the deionized water adopts 15M 3 Circulation/h, wherein the circulation time is 1.5h; and drying the obtained palladium catalyst or drying the palladium catalyst by using dry steam, and blowing nitrogen to be hot until no water remains, so that the degradation product removal rate of the active center of the palladium catalyst reaches 95% or the removal rate of the aluminum salt of the active center of the palladium catalyst reaches 94%.
2. The method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone process according to claim 1, which is characterized in that: and step 1), introducing saturated steam into the palladium catalyst to be regenerated, namely cutting out the palladium catalyst bed to be regenerated, closing a working solution and hydrogen inlet and outlet valves connected with the palladium catalyst bed to be regenerated, opening a saturated steam inlet valve and a regenerated condensate outlet valve, and introducing saturated steam.
3. The method for regenerating the palladium catalyst in the production of the hydrogen peroxide by the anthraquinone process according to claim 1, which is characterized in that: and (3) drying in the step (4) at 100-130 ℃.
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| CN105152137A (en) * | 2015-09-28 | 2015-12-16 | 湘潭大学 | Hydrogen peroxide working solution regenerant used in preparation of hydrogen peroxide process according to anthraquinone method and preparation method of hydrogen peroxide working solution regenerant |
| CN106268864A (en) * | 2016-09-22 | 2017-01-04 | 福建省福大百阳化工科技有限公司 | A kind of renovation process of palladium catalyst |
| CN111437889A (en) * | 2020-04-01 | 2020-07-24 | 安徽泉盛化工有限公司 | Regeneration method of catalyst of hydrogenation system for producing hydrogen peroxide by anthraquinone process |
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| CN104475175A (en) * | 2014-12-17 | 2015-04-01 | 烟台百川汇通科技有限公司 | Method for generating palladium catalyst for producing hydrogen peroxide by using anthraquinone process |
| CN105057006A (en) * | 2015-08-17 | 2015-11-18 | 浙江巴陵恒逸己内酰胺有限责任公司 | Method for regenerating palladium catalyst for production of hydrogen peroxide solution through anthraquinone process |
| CN110980654B (en) * | 2019-12-30 | 2023-04-14 | 广西田东达盛化工科技有限公司 | Method for cleaning active alumina balls in hydrogen peroxide production |
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| CN106268864A (en) * | 2016-09-22 | 2017-01-04 | 福建省福大百阳化工科技有限公司 | A kind of renovation process of palladium catalyst |
| CN111437889A (en) * | 2020-04-01 | 2020-07-24 | 安徽泉盛化工有限公司 | Regeneration method of catalyst of hydrogenation system for producing hydrogen peroxide by anthraquinone process |
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