CN103769092B - Hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof - Google Patents
Hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof Download PDFInfo
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Abstract
The invention discloses hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof.This catalyst consists of: nano magnesia, rare earth element, tin and active metal, with the weight of catalyst for benchmark, rare earth element with the content of oxide basis for 0.5% ~ 8.0%, Theil indices is 0.1% ~ 5.0%, active metal component is in the content of element for 0.1% ~ 8.0%, and surplus is nano magnesia.This catalyst is used for anthraquinone hydrogenation and produces in hydrogen peroxide process, has the features such as hydrogenation efficiency is high, anthraquinone less degradation.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst of hydrogen dioxide solution production by anthraquinone process.In particular, the present invention relates to a kind of for the preparation method of anthraquinone hydrogenation catalyst, this catalyst in hydrogen peroxide production process and the technology for Hydrogen Peroxide Production.
Background technology
Hydrogen peroxide, has another name called hydrogen peroxide, is a kind of important industrial chemicals, industrially produces as far back as 19 middle of century are just existing, is one of main Essential Chemistry product in the world.Along with the growth of social demand, especially the becoming more and more important of ecological environmental protection, hydrogen peroxide more and more becomes an important chemicals.As a kind of oxidant, bleaching agent, disinfectant, polymerization initiator and crosslinking agent, it is widely used in the numerous areas such as papermaking, weaving, chemicals synthesis, military project, electronics, food processing, medicine, cosmetics, environmental protection, metallurgy.Owing to producing water and oxygen after peroxide decomposition, to environment non-secondary pollution, belong to green chemical.In the production of hydrogen peroxide, what countries in the world were the most frequently used is anthraquinone.
Anthraquinone technique is anthraquinone derivative autoxidation method, and it is made into working solution with suitable organic solvent dissolution operation material-anthraquinone alkyl derivative, in the presence of a catalyst, with hydrogen, anthraquinone hydrogenation is reduced, generate hydrogen anthraquinone, the latter is oxidized through air or oxygen, obtains H
2o
2, hydrogen anthraquinone is oxidized to anthraquinone simultaneously.Then, with the H in water extraction working solution
2o
2, namely obtain H through being separated
2o
2the aqueous solution; Also can distill refining further, obtain high concentration H
2o
2, raffinate is got back to hydrogenation stage after treatment and is recycled.
Anthraquinone hydrogenation catalyst is one of key technology of this method production.The catalyst of high activity and high selectivity can improve unit circle H
2o
2productive rate and reduce the degraded of anthraquinone, thus the cyclic utilization rate of simplification of flowsheet, raising working solution, reduce production cost, improve product quality.Therefore, this field is one of focus of countries in the world hydrogen peroxide research always.
Current the most frequently used anthraquinone hydrogenation catalyst is supported palladium or raney nickel catalyst.Wherein loaded palladium catalyst activity is higher, but it is serious that working solution is degraded, and raney nickel catalyst is difficult to the shortcomings such as regeneration after there is the spontaneous combustion of chance air, inactivation.Therefore develop and both there is high activity, there is again the catalyst tool that working solution degrades low and be of great significance.
USP4240933 discloses a kind of hydrogenation catalyst of hydrogen dioxide solution production by anthraquinone process.This catalyst is with the amorphous silica of particle diameter 10 ~ 100 microns for carrier, and palladium is active component, auxiliary agent selected among zirconium, cerium, titanium, aluminium.USP4800075 discloses one anthraquinone hydrogenation catalyst in fixed bed reactors.The active component of this catalyst is palladium or platinum, and carrier is specific area is 5 ~ 108m
2α-the Al of/g
2o
3.CN99126993.4 discloses a kind of load type bimetal catalyst for process for prepairng hydrogen peroxide by anthraquinone, and its carrier is through 950 DEG C of baked aluminium oxide or titanium dioxide-aluminum oxide composite oxides, and active component is platinum and cobalt or nickel or ruthenium.This catalyst adopts the step impregnation method of additive competitive Adsorption to make.CN1616345A discloses a kind of anthraquinone hydrogenation catalyst preparing hydrogen peroxide, catalyst used is magnetic noble metal catalyst, by ball type carrier and be selected from platinum or/and palladium noble metal active component forms, ball type carrier is wherein aluminium oxide and magnetic-particle composition, and magnetic-particle is made up of the kernel of silica clad and iron compound.CN1990100A discloses a kind of anthraquinone hydrogenation catalyst, and the matrix of this catalyst is cordierite or foamed alumina, and active component is platinum or palladium, auxiliary agent be selected from titanium, zirconium, manganese, lanthanum, cerium etc. one or more.CN101804346A discloses a kind of catalyst for anthraquinone hydrogenation, and the preparation method of this catalyst is impregnated into by Technique of Nano Pd on natural plants cape jasmine to be prepared into hydrogenation catalyst.CN1544312A discloses a kind of anthraquinone hydrogenation catalyst, and this catalyst is made up of nickel, boron, metallic addition and carrier, and carrier is the molecular sieve composition adding surfactant, and specific surface is 200 ~ 1200m
2/ g.
Summary of the invention
For weak point of the prior art, the invention provides hydrogenation catalyst of the hydrogen dioxide solution production by anthraquinone process that a kind of activity is high, anthraquinone degradation rate is low and preparation method thereof.
Inventor finds through large quantifier elimination, the degraded of anthraquinone and the character of catalyst and operating condition closely related, when the pore size of catalyst is less, because larger molecule resistances in duct such as hydrogen anthraquinone are larger, can not desorption timely, cause deep reaction and degrade; The acid centre of catalyst, especially B acid site, can strong adsorption working solution molecule reacting, and causes it to degrade; When catalyst activity is too high, degree of hydrogenation is excessive, can generate tetrahydro-anthraquinone, octahydro anthraquinone even other grease, and causing working solution to be degraded increases; And if when catalyst activity is lower, along with the rising of reaction temperature, the degradation rate of anthraquinone also raises gradually.So will improve the production efficiency of hydrogen peroxide, just must ensure that catalyst has suitable pore size and moderate hydrogenation activity, higher active component decentralization can not only reduce the production cost of catalyst, also can improve the stability of catalyst.In addition, result of study shows, on conventional catalyst, active metal has strong adsorption potential and weakly stable position to absorption, but after introducing rare earth element in catalyst, active metal all shows as strong adsorption property to the adsorption potential of hydrogen, and the active hydrogen atom supplier of these strong hydrogen adsorption potentials just needed for anthraquinone hydrogenation.The introducing of tin, can form the active phase of class alloy structure with active metal atom, improve the decentralization of metal and the stability of active phase, reduce the content of active metal and the production cost of catalyst.
The hydrogenation catalyst of hydrogen dioxide solution production by anthraquinone process of the present invention, consist of: nano magnesia, rare earth element, tin and active metal, with the weight of catalyst for benchmark, rare earth element with the content of oxide basis for 0.5% ~ 8.0%, Theil indices is 0.1% ~ 5.0%, active metal component is in the content of element for 0.1% ~ 8.0%, and surplus is nano magnesia.
The hydrogenation catalyst of described hydrogen dioxide solution production by anthraquinone process is preferably as follows: with the weight of catalyst for benchmark, rare earth element with the content of oxide basis for 1.0% ~ 5.0%, Theil indices is 0.2% ~ 2.0%, and active metal component is in the content of element for 0.2% ~ 5.0%, and surplus is nano magnesia.
The crystal grain average grain diameter of described nano magnesia is 20 nm ~ 80nm.
Described active metal component is one or more in group VIII metal, is preferably one or more in platinum, palladium and ruthenium.
Described rare earth element is one or both in lanthanum, cerium.
Catalyst of the present invention is applicable to the technical process of hydrogen dioxide solution production by anthraquinone process, for anthraquinone is dissolved in heavy aromatics, (it is one or more in the aromatic hydrocarbons of 8 ~ 11 that described heavy aromatics is selected from carbon number to the working solution used, wherein the volume of C9 and/or C10 aromatic hydrocarbons accounts for more than 95% of heavy aromatics) and trioctyl phosphate in the solution that formed, wherein the volume ratio of heavy aromatics and trioctyl phosphate is 5:1 ~ 1:1.In the working solution used, the concentration of anthraquinone is 80g/L ~ 150 g/L.The process conditions of anthraquinone hydrogenation can adjust in a big way, such as, and hydrogen partial pressure 0.1MPa ~ 2.0MPa, reaction temperature 10 DEG C ~ 100 DEG C, volume space velocity 1.0 h
-1~ 50.0h
-1, gas agent volume ratio 10 ~ 1000, optimum condition is: hydrogen partial pressure 0.2MPa ~ 1.0MPa, reaction temperature 30 DEG C ~ 80 DEG C, volume space velocity 2 h
-1~ 20h
-1, gas agent volume ratio 20 ~ 500.
Catalyst of the present invention is used for the technical process of hydrogen dioxide solution production by anthraquinone process, has the high and anthraquinone of hydrogenation efficiency and to degrade the feature such as low.
Detailed description of the invention
There is provided a kind of concrete preparation method of catalyst of the present invention below, but be not limited thereto method, concrete steps are:
(1), nano magnesia is prepared;
(2), supported rare earth element on the nano magnesia of step (1) gained, through super-dry and calcination process, obtain rare earth modified nano magnesia;
(3) pore creating material is added in the rare earth modified nano magnesia, toward step (2) obtained, shaping, through super-dry and calcination process, obtain catalyst carrier;
(4) tin supported and active metal component in the catalyst carrier, toward step (3) obtained, through super-dry and calcination process, obtain catalyst.
Nano magnesia described in step (1) can adopt conventional method to prepare, such as: magnesium-containing compound is dissolved in solvent, add dispersant, after abundant mixing, under the condition of rapid stirring, control reaction temperature, slowly add precipitating reagent, through super-dry and roasting, obtain nano magnesia.Described magnesium-containing compound is preferably inorganic soluble magnesium-containing compound, is more preferably one or more in magnesium nitrate, magnesium chloride etc.Described dispersant is the material that can make Granular composite, such as surfactant, organic alcohols etc., is preferably alcohols, is more preferably ethylene glycol.Described precipitating reagent can make the material of magnesium precipitate, such as alkali compounds, one or more in preferred NaOH, potassium hydroxide, sodium carbonate, potash etc.Described reaction temperature is 5 DEG C ~ 60 DEG C, is preferably 10 DEG C ~ 30 DEG C, is more preferably 15 DEG C ~ 25 DEG C.Described drying can be present any type of drying, and be preferably low-temperature microwave dry, the temperature of described drying is normal temperature ~ 300 DEG C, and drying time is 10 minutes ~ 24 hours.Described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours.
Nano magnesia supported rare earth element described in step (2), can adopt carrying methods all at present, such as infusion process or spray method, is preferably saturated infusion process.Adopt the compound containing rare earth element for containing the organic matter of rare earth element or inorganic matter, the inorganic matter containing rare earth element can be preferably, such as, in the nitrate, sulfate etc. of rare earth element one or more.Described baking temperature is normal temperature ~ 300 DEG C, and drying time is 0.5 hour ~ 24 hours.Described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours.
Pore creating material described in step (3) is the material making carrier produce more micropores and mesopore, can be organic matter or inorganic matter, such as, in polyvinyl alcohol, hexadecyltrimethylammonium chloride, graphite, starch, cellulose and sesbania powder etc. one or more, are preferably polyvinyl alcohol.The addition of described pore creating material, with catalyst carrier weighing scale, is 0.5% ~ 5%.Described shape can be the particle of any state, and such as spherical, strip etc., the cross section of strip can be the irregular strip of various shape, such as circle, leafy careless shape, butterfly or gear shape etc.Described shapingly can adopt extruded moulding, also can adopt the forming method of other routine.Described baking temperature is normal temperature ~ 300 DEG C, and drying time is 0.5 hour ~ 24 hours.Described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours.
Carrying method described in step (4) can adopt metal supporting method conventional at present, such as dipping, ion-exchange or coating etc., is preferably the method for dipping, is more preferably the method for saturated dipping.The method of saturated dipping is exactly the solution being mixed with carrier saturated extent of adsorption with the compound of a certain amount of active metal component and auxiliary agent tin, is then mixed with carrier by solution.Active metal component is one or more in group VIII element, be preferably in platinum, palladium and ruthenium one or more, be more preferably platinum or/and palladium, the salt being dissolved in water that activity component metal compound can adopt this area to commonly use, such as platinum acid chloride solution, platinum amine complex solution, palladium amine complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof.The compound of described tin can be stanniferous organic matter or inorganic matter, be preferably stanniferous inorganic matter, such as, in sodium stannate, stannous chloride, nitric acid tin etc. one or more, load can adopt carrying methods all at present, such as infusion process or spray method, is preferably saturated infusion process.Described tin and active metal component can together with load in catalyst carrier, also can load in catalyst carrier respectively.Described baking temperature is normal temperature ~ 300 DEG C, and drying time is 0.5 hour ~ 24 hours.Described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours.
It is catalyst support component that catalyst of the present invention adopts compared with the nano magnesia of macropore size, low B acid amount, and with rare earth element, modification is carried out to it, be prepared into rare-earth element modified nano oxidized magnesium carrier, then tin and active metal component in load, reach and improve hydrogen peroxide productive rate, reduce the object of working solution degraded.
Further illustrate catalyst of the present invention and preparation process thereof below by embodiment, but invention should not be deemed limited in following embodiment.
The catalyst of the embodiment of the present invention and comparative example gained adopts 20ml small fixed reactor to evaluate, and loaded catalyst is 20ml, and appreciation condition is: hydrogen partial pressure 0.3MPa, reaction temperature 55 DEG C, volume space velocity 10.0h
-1, gas agent volume ratio 200.Working solution used consists of: EAQ content 120 grams per liter, heavy aromatics (50%(weight) trimethylbenzene and 50%(weight) durol BTX aromatics) and trioctyl phosphate be 7:3 according to volume ratio, get continuously the product of running after 4 hours and carry out air oxidation 30 minutes and pure water extraction at 50 DEG C, hydrogen peroxide content in assay products, calculate the hydrogenation efficiency of catalyst, unit is gH
2o
2/ L, analyzes EAQ content in raffinate, calculates EAQ degradation rate (loss late).
embodiment 1 (if do not have special indicating below, degree is all weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1), by 5000 grams of magnesium nitrates be dissolved in 50 premium on currency, add 4000 grams of ethylene glycol, rapid stirring (1000 revs/min), under 25 DEG C of conditions, slowly add the sodium hydroxide solution of 5%, until make solution ph reach 9, stop adding sodium hydroxide solution, continue stirring 10 minutes, centrifugation after still aging 10 hours, solid through too low fiery microwave drying 1 hour, 400 DEG C of calcination process 2 hours, obtain nano magnesia, average grain diameter is 40nm;
(2) 53 grams of La (NO are got
3)
36H
2o is dissolved in 1000 ml waters and forms solution, fully mixes under the nano magnesia obtained 970 grams of normal temperature with step (1), 110 DEG C of dryings 4 hours, and 380 DEG C of roastings 4 hours, obtain the nano magnesia of lanthanum modification;
(3) get 200 grams, the modified oxidized magnesium that step (2) obtains, polyvinyl alcohol 4 grams, 5 grams, sesbania powder and water are appropriate, and abundant kneading becomes plastic paste, extrusion becomes diameter to be the cylindric bar of 2.5 millimeters, 130 DEG C of dryings 2 hours, 420 DEG C of roastings 2 hours, obtain catalyst carrier of the present invention;
(4) 0.96 gram of SnCl, is got
22H
2o and 0.85 gram PdCl
2be dissolved in 100 grams of water, fully mix under the carrier normal temperature that the solution obtained and 99 grams of steps (3) obtain, leave standstill after 8 hours, 80 DEG C of dryings 12 hours, 480 DEG C of roastings 4 hours, obtain a kind of catalyst of the present invention, are numbered E-1, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
embodiment 2
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the magnesium source that step (1) uses is magnesium chloride, and obtaining nano magnesia average grain diameter is 20nm; (2) rare earth compound used in step is cerous nitrate, and in step (4), tin used is different with the amount of palladium; Obtain a kind of catalyst of the present invention, be numbered E-2, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
embodiment 3
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the precipitating reagent that step (1) uses is potassium hydroxide, and obtaining nano magnesia average grain diameter is 70nm; Rare earth compound content used in step (2) is different, and in step (4), the amount of tin used is different, and active metal component is ruthenium and content is different; Obtain a kind of catalyst of the present invention, be numbered E-3, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
embodiment 4
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that rare earth compound content used in step (2) is different, and tin amount used in step (3) is different; Active metal component used in step (4) is platinum, and content is different, and obtain a kind of catalyst of the present invention, be numbered E-4, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
embodiment 5
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the magnesium source that step (1) uses is magnesium sulfate, and obtaining nano magnesia grain average grain diameter is 80nm; Rare earth compound used in step (2) is lanthanum chloride, and content is different; Tin used in step (4) is different with palladium amount; Obtain a kind of catalyst of the present invention, be numbered E-5, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
embodiment 6
The preparation method of a kind of catalyst of the present invention is with embodiment 1, difference is that rare earth compound content used in step (2) is different, active metal component used in step (4) is platinum and palladium, the weight ratio of platinum and palladium is 1:3, total content, in table 1, obtains a kind of catalyst of the present invention, is numbered E-6, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
comparative example 1
The preparation method of a kind of comparative catalyst of the present invention is with embodiment 1, difference is cancellation step (1), magnesia is used to be commercially available common magnesia (particle diameter is 2 μm ~ 30 μm), obtain comparative catalyst of the present invention, be numbered C-1, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
comparative example 2
The preparation method of a kind of comparative catalyst of the present invention is with embodiment 1, and difference is to cancel (2) step, not containing lanthanum in catalyst, obtain comparative catalyst of the present invention, be numbered C-2, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
comparative example 3
The preparation method of a kind of comparative catalyst of the present invention is with embodiment 1, difference is that used carrier is common aluminium oxide (particle diameter is 2 μm ~ 30 μm), obtains comparative catalyst of the present invention, is numbered C-3, its composition is shown in Table 1, catalyst hydrogenation efficiency and anthraquinone degradation rate the results are shown in Table 2.
the composition of each embodiment of table 1 (comparative example) catalyst(unreceipted content is weight percent content)
| Catalyst | Lanthana, % | Tin, % | Active metal component, % | Magnesia, % |
| E-1 | 2.0 | 0.5 | 0.5(Pd) | Surplus |
| E-2 | 2.0(cerium oxide) | 0.3 | 0.3(Pd) | Surplus |
| E-3 | 5.0 | 2.0 | 5.0(Ru) | Surplus |
| E-4 | 0.5 | 1.0 | 0.1(Pt) | Surplus |
| E-5 | 3.0 | 0.1 | 2.0(Pd) | Surplus |
| E-6 | 1.0 | 0.5 | 0.3(Pd)+ 0.1(Pt) | Surplus |
| C-1 | 2.0 | 0.5 | 0.5(Pd) | Surplus |
| C-2 | 0 | 0.5 | 0.5(Pd) | Surplus |
| C-3 | 2.0 | 0.5 | 0.5(Pd) | Surplus (aluminium oxide) |
the reactivity worth of each catalyst of table 2
| Catalyst | Hydrogenation efficiency, gH 2O 2/L | Anthraquinone degradation rate, % |
| E-1 | 7.6 | 1.3 |
| E-2 | 7.2 | 1.2 |
| E-3 | 7.5 | 1.1 |
| E-4 | 9.1 | 1.5 |
| E-5 | 8.3 | 1.3 |
| E-6 | 9.8 | 1.6 |
| C-1 | 5.1 | 1.8 |
| C-2 | 5.9 | 2.3 |
| C-3 | 6.3 | 2.5 |
From the results shown in Table 2, catalyst of the present invention is in the reaction of producing hydrogen peroxide, and the degradation rate of hydrogenation efficiency working solution apparently higher than comparative catalyst is lower than the reaction result of comparative catalyst, and this catalyst can also be used for other hydrogenation process.
Claims (15)
1. a preparation method for the hydrogenation catalyst of hydrogen dioxide solution production by anthraquinone process, comprising:
(1), nano magnesia is prepared;
(2), supported rare earth element on the nano magnesia of step (1) gained, through super-dry and roasting, obtain rare earth modified nano magnesia;
(3) pore creating material is added in the rare earth modified nano magnesia, toward step (2) obtained, shaping, through super-dry and roasting, obtain catalyst carrier;
(4) tin supported and active metal component in the catalyst carrier, toward step (3) obtained, through super-dry and roasting, obtain catalyst;
Wherein, with the weight of catalyst for benchmark, rare earth element is with the content of oxide basis for 0.5% ~ 8.0%, and Theil indices is 0.1% ~ 5.0%, and active metal component is in the content of element for 0.1% ~ 8.0%, and surplus is nano magnesia.
2. in accordance with the method for claim 1, it is characterized in that the hydrogenation catalyst of described hydrogen dioxide solution production by anthraquinone process, with the weight of catalyst for benchmark, rare earth element with the content of oxide basis for 1.0% ~ 5.0%, Theil indices is 0.2% ~ 2.0%, active metal component is in the content of element for 0.2% ~ 5.0%, and surplus is nano magnesia.
3., according to the method described in claim 1 or 2, it is characterized in that the crystal grain average grain diameter of described nano magnesia is 20 nm ~ 80nm.
4., according to the method described in claim 1 or 2, it is characterized in that described active metal component is one or more in platinum, palladium and ruthenium.
5., according to the method described in claim 1 or 2, it is characterized in that described rare earth element is one or both in lanthanum, cerium.
6. in accordance with the method for claim 1, it is characterized in that the preparation method for nanometer magnesium oxide described in step (1) is as follows: be dissolved into by magnesium-containing compound in solvent, add dispersant, after abundant mixing, under the condition of rapid stirring, control reaction temperature, slowly add precipitating reagent, then through super-dry and roasting, obtain nano magnesia, wherein said magnesium-containing compound is one or more in magnesium nitrate, magnesium chloride; Described dispersant be in surfactant and organic alcohols one or more; Described precipitating reagent is one or more in NaOH, potassium hydroxide, sodium carbonate, potash; Reaction temperature is 5 DEG C ~ 60 DEG C; Described baking temperature is normal temperature ~ 300 DEG C, and drying time is 10 minutes ~ 24 hours, and described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours.
7. in accordance with the method for claim 6, it is characterized in that described dispersant is ethylene glycol.
8. the method that in accordance with the method for claim 1, it is characterized in that the nano magnesia supported rare earth element described in step (2) is saturated infusion process.
9. in accordance with the method for claim 1, it is characterized in that the pore creating material described in step (3) is one or more in polyvinyl alcohol, hexadecyltrimethylammonium chloride, graphite, starch, cellulose and sesbania powder; The addition of described pore creating material, with the weighing scale of catalyst carrier, is 0.5% ~ 5.0%.
10. in accordance with the method for claim 1, it is characterized in that the carrying method described in step (4) adopts saturated infusion process.
11. in accordance with the method for claim 1, and it is characterized in that the baking temperature described in step (2) is normal temperature ~ 300 DEG C, drying time is 0.5 hour ~ 24 hours, and described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours; Baking temperature described in step (3) is normal temperature ~ 300 DEG C, and drying time is 0.5 hour ~ 24 hours, and described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours; Baking temperature described in step (4) is normal temperature ~ 300 DEG C, and drying time is 0.5 hour ~ 24 hours, and described sintering temperature is 400 DEG C ~ 800 DEG C, and roasting time is 0.5 hour ~ 8.0 hours.
12. 1 kinds of anthraquinone hydrogenation catalysts, is characterized in that adopting the arbitrary described method preparation of claim 1 ~ 11.
The method of 13. 1 kinds of hydrogen dioxide solution production by anthraquinone process, is characterized in that adopting hydrogenation catalyst according to claim 12.
14. in accordance with the method for claim 13, it is characterized in that: anthraquinone is dissolved in the working solution formed in heavy aromatics and trioctyl phosphate, and wherein the volume ratio of heavy aromatics and trioctyl phosphate is 5:1 ~ 1:1; In the working solution used, the concentration of anthraquinone is 80g/L ~ 150 g/L; The process conditions of anthraquinone hydrogenation are as follows: hydrogen partial pressure 0.1MPa ~ 2.0MPa, reaction temperature 10 DEG C ~ 100 DEG C, volume space velocity 1.0 h
-1~ 50.0h
-1, gas agent volume ratio 10 ~ 1000.
15. in accordance with the method for claim 14, it is characterized in that: the process conditions of anthraquinone hydrogenation are as follows: hydrogen partial pressure 0.2MPa ~ 1.0MPa, reaction temperature 30 DEG C ~ 80 DEG C, volume space velocity 2 h
-1~ 20h
-1, gas agent volume ratio 20 ~ 500.
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| CN106669665A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Integral catalyst for hydrogen peroxide production process through anthraquinone process and preparation method of integral catalyst |
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| CN105582911B (en) * | 2014-10-22 | 2017-11-24 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of preparation method of anthraquinone hydrogenation catalyst |
| CN114618477B (en) * | 2020-12-10 | 2023-06-20 | 中国科学院大连化学物理研究所 | Catalyst and preparation method and application thereof |
| CN114180533B (en) * | 2021-12-29 | 2024-07-02 | 滨化技术有限公司 | Green regeneration method and device for octahydroanthraquinone in working solution for hydrogen peroxide production |
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| CN102658207A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1435277A (en) * | 2003-02-21 | 2003-08-13 | 福州大学 | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof |
| CN1562466A (en) * | 2004-03-19 | 2005-01-12 | 上海苏鹏实业有限公司 | Special form type palladium catalyst in use for preparing hydrogen peroxide and preparation method |
| CN101497040A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
| CN102658207A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669665A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Integral catalyst for hydrogen peroxide production process through anthraquinone process and preparation method of integral catalyst |
| CN106669665B (en) * | 2015-11-11 | 2019-03-19 | 中国石油化工股份有限公司 | The integral catalyzer and preparation method thereof of hydrogen dioxide solution production by anthraquinone process process |
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