CN103769093A - Anthraquinone hydrogenation catalyst and preparation method thereof - Google Patents
Anthraquinone hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103769093A CN103769093A CN201210409617.XA CN201210409617A CN103769093A CN 103769093 A CN103769093 A CN 103769093A CN 201210409617 A CN201210409617 A CN 201210409617A CN 103769093 A CN103769093 A CN 103769093A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- anthraquinone
- rare earth
- accordance
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses an anthraquinone hydrogenation catalyst and a preparation method thereof. The catalyst is composed of nano magnesium oxide, silicon oxide, rare earth elements, boron, and an active metal component; based on the weight of the catalyst, rare earth elements (in an oxide form) account for 0.5% to 8.0% of the weight of the catalyst, the metal elements in the active metal component account for 0.1% to 8.0% of the weight of the catalyst, silicon oxide accounts for 0.1% to 8.0% of the weight of the catalyst, boron accounts for 0.1% to 5.0% of the weight of the catalyst, and the balance being nano magnesium oxide. The catalyst is used during the process of hydrogen peroxide production through an anthraquinone method, and has the characteristics of high hydrogenation efficiency and little degradation of anthraquinone.
Description
Technical field
The present invention relates to a kind of anthraquinone hydrogenation catalyst.In particular, the technology that the present invention relates to the preparation method of anthraquinone hydrogenation catalyst used in a kind of hydrogen dioxide solution production by anthraquinone process process, this catalyst and produce for hydrogen peroxide.
Background technology
Hydrogen peroxide, has another name called hydrogen peroxide, is a kind of important industrial chemicals, industrial as far back as just existing production of 19 middle of century, is one of main Essential Chemistry product in the world.Along with the growth of social demand, especially 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 numerous areas such as papermaking, weaving, chemicals are synthetic, military project, electronics, food processing, medicine, cosmetics, environmental protection, metallurgy.Because hydrogen peroxide decomposes rear water and the oxygen of producing, 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, under catalyst exists, anthraquinone hydrogenation is reduced with hydrogen, generate hydrogen anthraquinone, the latter is oxidized through air or oxygen, obtains H
2o
2, hydrogen anthraquinone is oxidized to anthraquinone simultaneously.Then, the H in water extraction working solution
2o
2, obtain H through separating
2o
2the aqueous solution; Also can further distill refiningly, obtain high concentration H
2o
2, raffinate is got back to after treatment hydrogenation stage 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 the circulation H of unit
2o
2productive rate and reduce the degraded of anthraquinone, thereby simplification of flowsheet, improve working solution cyclic utilization rate, reduce production costs, 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 makes working solution degraded serious, and raney nickel catalyst is difficult to the shortcomings such as regeneration after there is the spontaneous combustion of chance air, inactivation.Therefore exploitation had both had high activity, had again the catalyst tool that working solution degrades low and was of great significance.
USP4240933 discloses a kind of hydrogenation catalyst of hydrogen dioxide solution production by anthraquinone process.This catalyst is take the amorphous silica of 10 ~ 100 microns of particle diameters as 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 that specific area is 5 ~ 108m
2α-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 ℃ 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 of 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 by the core composition 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, and auxiliary agent is to be selected from one or more in titanium, zirconium, manganese, lanthanum, cerium etc.CN101804346A discloses a kind of catalyst for anthraquinone hydrogenation, and the preparation method of this catalyst is that Technique of Nano Pd is impregnated on natural plants cape jasmine and is 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 that adds surfactant, and specific surface is 200 ~ 1200m
2/ g.
Summary of the invention
For weak point of the prior art, the invention provides anthraquinone hydrogenation catalyst that a kind of activity is high, anthraquinone degradation rate is low and preparation method thereof.
Inventor finds through a large amount of research, the degraded of anthraquinone and the character of catalyst and operating condition are closely related, when the pore size of catalyst hour, because larger molecule resistances in duct such as hydrogen anthraquinone are larger, desorption timely, causes deep reaction and degrades; The acid centre of catalyst, especially B acid site, can strong adsorption working solution molecule and react, and causes its degraded; Too high when catalyst activity, degree of hydrogenation is excessive, can generate even other grease of tetrahydro-anthraquinone, octahydro anthraquinone, causes working solution degraded to increase; And if catalyst activity is when lower, along with the rising of reaction temperature, the degradation rate of anthraquinone also raises gradually.So improve the production efficiency of hydrogen peroxide, just must guarantee that catalyst has suitable pore size and moderate hydrogenation activity, higher active component decentralization not only can 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 weak adsorption potential to absorption, but when introducing in catalyst after rare earth element, active metal all shows as strong adsorption property to the adsorption potential of hydrogen, and these strong hydrogen adsorption potentials required active hydrogen atom supplier of anthraquinone hydrogenation just.The introducing of boron, can form active of class amorphous alloy structure with active metal atom, improves the decentralization of metal and the stability of active phase, reduces the content of active metal and the production cost of catalyst.
Consisting of of anthraquinone hydrogenation catalyst of the present invention: nano magnesia, silica, rare earth element, boron and active metal component, take the weight of catalyst as benchmark, rare earth element is take the content of oxide as 0.5% ~ 8.0%, active metal component is take the content of element as 0.1% ~ 8.0%, silica content 0.1% ~ 8.0%, boron content is 0.1% ~ 5.0%, and surplus is nano magnesia.
The composition of anthraquinone hydrogenation catalyst of the present invention is preferably as follows: take the weight of catalyst as benchmark, rare earth element is take the content of oxide as 1.0% ~ 5.0%, active metal component is take the content of element as 0.2% ~ 5.0%, silica content is 0.5 % ~ 5.0%, boron content is 0.5% ~ 3.0%, 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 using, wherein the volume of C9 and/or C10 aromatic hydrocarbons accounts for the more than 95% of heavy aromatics) and trioctyl phosphate in the solution that forms, wherein the volume ratio of heavy aromatics and trioctyl phosphate is 5:1 ~ 1:1.In the working solution using, the concentration of anthraquinone is 80g/L ~ 150 g/L.The process conditions of anthraquinone hydrogenation can adjusted in a big way, for example, and hydrogen partial pressure 0.1MPa ~ 2.0MPa, 10 ℃ ~ 100 ℃ of reaction temperatures, 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, 30 ℃ ~ 80 ℃ of reaction temperatures, volume space velocity 2 h
-1~ 20h
-1, gas agent volume ratio 20 ~ 500.
Catalyst of the present invention is for the technical process of hydrogen dioxide solution production by anthraquinone process, has the high and anthraquinone of the hydrogenation efficiency feature such as low of degrading.
The specific embodiment
A kind of concrete preparation method of catalyst of the present invention is provided below, but is not limited to the method, concrete steps are:
(1), prepare nano magnesia;
(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), add pore creating material, Ludox and water kneading and compacting in the rare earth modified nano magnesia that obtains toward step (2),, through super-dry and roasting, obtain catalyst carrier;
(4), supported active metal component in the catalyst carrier that obtains toward step (3), through super-dry and roasting, obtain catalyst precarsor;
(5) process with the catalyst precarsor that boron-containing compound makes step (4), obtain catalyst.
Nano magnesia described in step (1) can adopt conventional method preparation, such as: magnesium-containing compound is dissolved in solvent, add dispersant, after fully 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 solubility magnesium-containing compound, more preferably one or more in magnesium nitrate, magnesium chloride etc.Described dispersant is the material that can make particle disperse, and such as surfactant, organic alcohols etc., be preferably alcohols, more preferably ethylene glycol.Described precipitating reagent can make the material of magnesium precipitate, for example alkali compounds, preferably one or more in NaOH, potassium hydroxide, sodium carbonate, potash etc.Described reaction temperature is 5 ℃ ~ 60 ℃, is preferably 10 ℃ ~ 30 ℃, more preferably 15 ℃ ~ 25 ℃.Described being dried can be now any type of dry, is preferably low-temperature microwave dry.Described baking temperature is normal temperature ~ 300 ℃, and be 10 minutes ~ 24 hours drying time.Described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8 hours.
Nano magnesia supported rare earth element described in step (2), can adopt at present all carrying methods, and for example infusion process or spray method is preferably saturated infusion process.Employing can, for organic matter or the inorganic matter containing rare earth element, be preferably the inorganic matter containing rare earth element, such as, in nitrate, the sulfate etc. of rare earth element one or more containing the compound of rare earth element.Described baking temperature is normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time.Described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8.0 hours.
Pore creating material described in step (3) is that the material that makes 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.Be preferably polyvinyl alcohol.The addition of described pore creating material, with catalyst carrier weighing scale, is 0.5% ~ 5%.Described Ludox is the silica containing material of colloidal, and for example cataloid, low sodium Ludox and sodium-free silica sol, be preferably sodium-free silica sol.Described shape can be the particle of any state, such as spherical, strip etc., and the cross section of strip can be the irregular strip of various shape, for example circle, leafy careless shape, butterfly or gear shape etc.Described moulding can adopt extruded moulding, also can adopt other conventional forming method.Described is dried as normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time.Described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8 hours.
Carrying method described in step (4) can adopt at present conventional Metal Supported method, and such as dipping, ion-exchange or coating etc. are preferably the method for dipping, the more preferably method of saturated dipping.The method of saturated dipping is exactly the solution that is mixed with carrier saturated extent of adsorption with a certain amount of active metal component compound, then solution is mixed with carrier.Active metal component is one or more in group VIII element, be preferably one or more in platinum, palladium and ruthenium, more preferably platinum is or/and palladium, activity component metal compound can adopt the conventional salt that is dissolved in water in this area, for example platinum acid chloride solution, platinum amine complex solution, palladium amine complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof.Described is dried as normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time.Described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8 hours.
Boron-containing compound described in step (5) is the compound with reproducibility, for example, in sodium borohydride and lithium borohydride one or more.The method that the described catalyst precarsor with boron-containing compound makes step (4) is processed, for example infusion process or spray method, is preferably saturated infusion process.After dipping, be dried and calcination process, obtain catalyst.Wherein said is dried as normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time.Described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8 hours.
It is catalyst carrier component that catalyst of the present invention adopts compared with the nano magnesia of macropore size, low B acid amount, and it is carried out to modification with rare earth element, in the process of moulding, add appropriate silicon to improve the specific surface of carrier, be prepared into the nano oxidized magnesium carrier of rare earth element and silicon modification, then boron and active metal component in load, reach and improve hydrogen peroxide productive rate, reduce the object of working solution degraded.
Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in following embodiment.
Catalyst of the present invention is to adopt 20ml small fixed reactor to evaluate, and loaded catalyst is 20ml, and appreciation condition is: hydrogen partial pressure 0.3MPa, 55 ℃ of reaction temperatures, volume space velocity 10.0h
-1, gas agent volume ratio 200.Working solution used consists of: EAQ content 120 grams per liters, heavy aromatics (50%(weight) trimethylbenzene and 50%(weight) durol BTX aromatics) and trioctyl phosphate be 7:3 according to volume ratio, get the product of continuous operation after 4 hours and carry out air oxidation 30 minutes and pure water extraction at 50 ℃, hydrogen peroxide content in assay products, the hydrogenation efficiency that calculates catalyst, unit is gH
2o
2/ L, analyzes EAQ content in raffinate, calculates EAQ degradation rate (loss late).
embodiment 1 (if there is no below special indicating, degree is all weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1), 5000 grams of magnesium nitrates are dissolved in 50 premium on currency, add 4000 grams of ethylene glycol, rapid stirring (1000 revs/min), under 25 ℃ of conditions, slowly add 5% sodium hydroxide solution, until make solution pH value reach 9, stop adding sodium hydroxide solution, continue to stir 10 minutes, centrifugation after still aging 10 hours, solid is through too low fiery microwave drying 1 hour, 400 ℃ of calcination process 2 hours, obtain nano magnesia, average grain diameter is 40nm;
(2) get 53 grams of La (NO
3)
36H
2o is dissolved in 1000 ml waters and forms solution, under the 935 grams of normal temperature of nano magnesia that obtain with (1) step, fully mix, 110 ℃ dry 4 hours, 380 ℃ of roastings 4 hours, obtain the nano magnesia of lanthanum modification;
(3) get 191 grams, the modified oxidized magnesium that (2) step obtains, 4 grams of polyvinyl alcohol, 5 grams, sesbania powder, 20 grams of (SiO of sodium-free silica sol
2content 30%) and water appropriate, fully kneading becomes plastic paste, it is 2.5 millimeters cylindric that extrusion becomes diameter, 130 ℃ dry 2 hours, 420 ℃ of roastings 2 hours, obtain catalyst carrier of the present invention;
(4) 0.85 grams of PdCl
2be dissolved in 100 grams of water, under the carrier normal temperature that the solution obtaining obtains with 98.5 grams of (3) steps, fully mix, left standstill 8 as a child, 80 ℃ dry 12 hours, 480 ℃ of roastings 4 hours, obtain a kind of catalyst precarsor of the present invention;
(5) getting 3.5 grams of sodium borohydrides is dissolved in 100 grams of ethanol, the catalyst precarsor that adds 99 grams of steps (4) to make, stirring at normal temperature 4 hours, heating solvent evaporated, 60 ℃ dry 8 hours, 480 ℃ of roastings 2 hours, obtain a kind of catalyst of the present invention, be 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 (1) step is used is magnesium chloride, and obtaining nano magnesia average grain diameter is 20nm; (2) in step, rare earth compound used is cerous nitrate; (5) sodium borohydride amount difference used in step; 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 (1) step is used is potassium hydroxide, and obtaining nano magnesia average grain diameter is 70nm; (2) rare earth compound content difference used in step, dioxide-containing silica difference used in (3) step; The amount difference of tin used in step (4), active metal component is ruthenium and content difference; (5) sodium borohydride amount difference used in step.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 boron amount difference used in (4) step; (4) in step, active metal component used is platinum, and content difference, obtains a kind of catalyst of the present invention, is numbered E-4, and 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 (1) step is used is magnesium sulfate, and obtaining nano magnesia average grain diameter is 80nm; (2) in step, rare earth compound used is lanthanum chloride,, and content difference; (3) dioxide-containing silica difference used in step, potassium borohydride amount difference used in (5) step; 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 active metal component used in (4) step is platinum and palladium, the weight ratio of platinum and palladium is 1:3, total content is in table 1, obtain a kind of catalyst of the present invention, be 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
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, difference is to cancel (1) step, use magnesia be commercially available common magnesia (particle diameter be 2 μ m ~ 30 μ m), catalyst is without boron-containing compound processing, 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
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, difference is to cancel (2) step, in catalyst, do not contain lanthanum, obtain comparative catalyst of the present invention, catalyst is without boron-containing compound processing, 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
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, difference be used carrier be common aluminium oxide (particle diameter be 2 μ m ~ 30 μ m), obtain comparative catalyst of the present invention, catalyst is without boron-containing compound processing, be 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 the each embodiment of table 1 (comparative example) catalyst(unreceipted content is weight percent content)
| Catalyst | Lanthana, % | Boron, % | Active metal component, % | Silica, % | Magnesia, % |
| E-1 | 2.0 | 1.0 | 0.5(Pd) | 3.0 | Surplus |
| E-2 | 2.0(cerium oxide) | 0.2 | 0.3(Pd) | 3.0 | Surplus |
| E-3 | 5.0 | 3.0 | 5.0(Ru) | 0.5 | Surplus |
| E-4 | 0.5 | 1.0 | 0.1(Pt) | 3.0 | Surplus |
| E-5 | 3.0 | 2.0 | 2.0(Pd) | 5.0 | Surplus |
| E-6 | 1.0 | 1.0 | 0.3(Pd)+ 0.1(Pt) | 3.0 | Surplus |
| C-1 | 2.0 | 0 | 0.5(Pd) | 3.0 | Surplus |
| C-2 | 0 | 0 | 0.5(Pd) | 3.0 | Surplus |
| C-3 | 2.0 | 0 | 0.5(Pd) | 3.0 | Surplus (aluminium oxide) |
the reactivity worth of the each catalyst of table 2
| Catalyst | Hydrogenation efficiency, gH 2O 2/L | Anthraquinone degradation rate, % |
| E-1 | 9.1 | 1.4 |
| E-2 | 8.3 | 1.1 |
| E-3 | 7.8 | 0.8 |
| E-4 | 9.3 | 1.4 |
| E-5 | 9.9 | 1.2 |
| E-6 | 9.0 | 1.3 |
| C-1 | 5.1 | 1.8 |
| C-2 | 5.9 | 2.6 |
| C-3 | 6.3 | 2.8 |
From the results shown in Table 2, catalyst of the present invention is producing in the reaction of hydrogen peroxide, hydrogenation efficiency apparently higher than comparative catalyst and the degradation rate of working solution lower than comparative catalyst's reaction result, this catalyst can also be used for other hydrogenation process.
Claims (18)
1. an anthraquinone hydrogenation catalyst, consist of: nano magnesia, silica, rare earth element, boron and active metal component, take the weight of catalyst as benchmark, rare earth element is take the content of oxide as 0.5% ~ 8.0%, active metal component is take the content of element as 0.1% ~ 8.0%, silica content 0.1% ~ 8.0%, boron content is 0.1% ~ 5.0%, surplus is nano magnesia.
2. according to catalyst claimed in claim 1, it is characterized in that the described hydrogenation catalyst for the preparation of hydrogen peroxide, take the weight of catalyst as benchmark, rare earth element is take the content of oxide as 1.0% ~ 5.0%, active metal component is take the content of element as 0.2% ~ 5.0%, silica content is 0.5 % ~ 5.0%, and boron content is 0.1% ~ 3.0%, and surplus is nano magnesia.
3. according to the catalyst described in claim 1 or 2, it is characterized in that the size of microcrystal of described nano magnesia is 10 nm ~ 80nm.
4. according to the catalyst 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 catalyst described in claim 1 or 2, it is characterized in that described rare earth element is one or both in lanthanum, cerium.
6. the preparation method of the arbitrary described catalyst of claim 1 ~ 5, comprising:
(1), prepare nano magnesia;
(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), add pore creating material, Ludox and water kneading and compacting in the rare earth modified nano magnesia that obtains toward step (2),, through super-dry and roasting, obtain catalyst carrier;
(4), supported active metal component in the catalyst carrier that obtains toward step (3), through super-dry and roasting, obtain catalyst precarsor;
(5) process with the catalyst precarsor that boron-containing compound makes step (4), obtain catalyst.
7. in accordance with the method for claim 6, it is characterized in that the preparation method for nanometer magnesium oxide described in step (1) is as follows: magnesium-containing compound is dissolved in solvent, add dispersant, after fully 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 ℃ ~ 60 ℃; Described baking temperature is normal temperature ~ 300 ℃, and be 10 minutes ~ 24 hours drying time, and described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8.0 hours.
8. in accordance with the method for claim 7, it is characterized in that described dispersant is ethylene glycol.
9. the method that in accordance with the method for claim 6, it is characterized in that the nano magnesia supported rare earth element described in step (2) is saturated infusion process.
10. in accordance with the method for claim 6, 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 catalyst carrier weighing scale, is 0.5% ~ 5%.
11. in accordance with the method for claim 6, it is characterized in that described Ludox is sodium-free silica sol.
12. in accordance with the method for claim 6, it is characterized in that the carrying method described in step (4) adopts saturated infusion process.
13. in accordance with the method for claim 6, it is characterized in that the boron-containing compound described in step (5) is one or more in sodium borohydride and lithium borohydride.
14. in accordance with the method for claim 6, it is characterized in that the method that the catalyst precarsor with boron-containing compound makes step (4) described in step (5) is processed is infusion process or sprays method, after dipping, be dried and calcination process, obtain catalyst; Wherein said is dried as normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time; Described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8 hours.
15. in accordance with the method for claim 6, it is characterized in that the described baking temperature of step (2) is normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time, and described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8.0 hours; The described baking temperature of step (3) is normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time, and described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8.0 hours; The described baking temperature of step (4) is normal temperature ~ 300 ℃, and be 0.5 hour ~ 24 hours drying time, and described sintering temperature is 400 ℃ ~ 800 ℃, and roasting time is 0.5 hour ~ 8.0 hours.
16. 1 kinds of anthraquinone methods of preparing hydrogen peroxide, is characterized in that adopting the arbitrary described catalyst of claim 1 ~ 5.
17. in accordance with the method for claim 16, it is characterized in that: anthraquinone is dissolved in to the working solution forming in heavy aromatics and trioctyl phosphate, wherein the volume ratio of heavy aromatics and trioctyl phosphate is 5:1 ~ 1:1; In the working solution using, 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, 10 ℃ ~ 100 ℃ of reaction temperatures, volume space velocity 1.0 h
-1~ 50.0h
-1, gas agent volume ratio 10 ~ 1000.
18. in accordance with the method for claim 17, it is characterized in that: the process conditions of anthraquinone hydrogenation are as follows: hydrogen partial pressure 0.2MPa ~ 1.0MPa, 30 ℃ ~ 80 ℃ of reaction temperatures, volume space velocity 2 h
-1~ 20h
-1, gas agent volume ratio 20 ~ 500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409617.XA CN103769093B (en) | 2012-10-24 | 2012-10-24 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409617.XA CN103769093B (en) | 2012-10-24 | 2012-10-24 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769093A true CN103769093A (en) | 2014-05-07 |
| CN103769093B CN103769093B (en) | 2015-08-12 |
Family
ID=50562127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210409617.XA Active CN103769093B (en) | 2012-10-24 | 2012-10-24 | A kind of anthraquinone hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769093B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669854A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation nonuniform porous channel zonal monolithic catalyst and preparation method thereof |
| CN107715917A (en) * | 2016-08-10 | 2018-02-23 | 中国科学院大连化学物理研究所 | Phosphoric acid sexual intercourse linked polymer supported palladium nanocatalyst and preparation and application |
| CN112717923A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424145A (en) * | 2002-12-25 | 2003-06-18 | 天津大学 | Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone |
| 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 |
-
2012
- 2012-10-24 CN CN201210409617.XA patent/CN103769093B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424145A (en) * | 2002-12-25 | 2003-06-18 | 天津大学 | Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669854A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation nonuniform porous channel zonal monolithic catalyst and preparation method thereof |
| CN106669854B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation and preparation method thereof |
| CN107715917A (en) * | 2016-08-10 | 2018-02-23 | 中国科学院大连化学物理研究所 | Phosphoric acid sexual intercourse linked polymer supported palladium nanocatalyst and preparation and application |
| CN112717923A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769093B (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109647399B (en) | Preparation method of monatomic catalyst for catalytic oxidation of aromatic VOCs at normal temperature | |
| CN102527377B (en) | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method | |
| CN101856615B (en) | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof | |
| CN101646491A (en) | The method of synthesis of cubic metal nanoparticles in the presence of two kinds of reducing agents | |
| Tan et al. | Self-supporting hierarchical PdCu aerogels for enhanced catalytic reduction of 4-nitrophenol | |
| Liu et al. | Promotional effect of Mn-doping on the catalytic performance of NiO sheets for the selective oxidation of styrene | |
| CN102728374B (en) | Preparation method of hydrotreatment catalyst | |
| CN104368374A (en) | High-dispersion monolithic catalyst for hydrogen peroxide synthesis, and preparation method and application thereof | |
| CN105498756B (en) | The catalyst of hydrogenation of carbon dioxide methanol | |
| CN103157468A (en) | Low-content supported ruthenium-palladium bimetal hydrogenation catalyst and preparation method thereof | |
| CN103769092B (en) | Hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof | |
| CN102728373A (en) | Preparation method of hydrotreating catalyst | |
| CN108067220A (en) | A kind of hydrogen peroxide synthesis loaded catalyst and its preparation method and application | |
| CN104069886A (en) | Preparation method and use of catalyst for preparation of cyclopentanone through hydrogenation of water phase furfural | |
| CN103769186B (en) | Anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN103769093B (en) | A kind of anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN103769091B (en) | A kind of anthraquinone hydrogenation catalyst preparing hydrogen peroxide and preparation method thereof | |
| CN108114729A (en) | A kind of anthraquinone hydrogenation catalyst and its preparation method and application | |
| CN104959136B (en) | A kind of preparation method for adding hydrogen into resin egg-shell catalyst | |
| CN103204830B (en) | A kind of cinnamic method of catalyzed oxidation | |
| CN101912783A (en) | Catalyst for combustion of ventilation air methane and preparation method thereof | |
| Aslam et al. | Cu nanoparticles confined within ZSM-5 derived mesoporous silica (MZ) with enhanced stability for catalytic hydrogenation of 4-nitrophenol and degradation of azo dye | |
| CN105642289B (en) | A kind of preparation method of synthesis gas full methanation catalyst | |
| CN104028267A (en) | Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation | |
| CN101618323A (en) | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |