CN103623820A - Preparation method of precious metal anthraquinone hydrogenation catalyst promoted by carbide - Google Patents
Preparation method of precious metal anthraquinone hydrogenation catalyst promoted by carbide Download PDFInfo
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- CN103623820A CN103623820A CN201310546079.3A CN201310546079A CN103623820A CN 103623820 A CN103623820 A CN 103623820A CN 201310546079 A CN201310546079 A CN 201310546079A CN 103623820 A CN103623820 A CN 103623820A
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Abstract
The invention discloses a preparation method of a precious metal anthraquinone hydrogenation catalyst promoted by carbide, belonging to the fields of materials and catalysis. The method particularly comprises the steps of (1) firstly, evenly mixing materials such as aluminium oxide and silicon oxide, and extruding the mixture to form a carrier; (2) dipping the formed carrier into a solution of carbide precursor; (3) after the carrier is dipped into the carbide precursor, drying the carrier, and carrying out high-temperature treatment in the inert atmosphere to obtain a carrier material modified by the carbide; (4) dipping the carrier modified by the carbide into a precious metal salt solution; (5) after the carrier material is dipped into the precious metal salt solution, cleaning the carrier material by water, and drying to obtain the load-type precious metal hydrogenation catalyst promoted by the carbide. According to the invention, the carbide, which is a cheap assistant catalytic material, is introduced, so that the whole catalytic activity of the catalyst is still maintained or even improved under the condition that the used amount of precious metal is reduced to 3wt%-10wt%.
Description
Technical field
The present invention relates to a kind of loaded noble metal catalyst that can be used for process for prepairng hydrogen peroxide by anthraquinone and preparation method thereof, belong to material and catalytic field.
Background technology
Anthraquinone is to produce at present both at home and abroad the main method of hydrogen peroxide, compare with other preparation method there is less energy consumption, cost is low, technical maturity, be easy to the advantages such as large-scale production.The know-why of process for prepairng hydrogen peroxide by anthraquinone is: with the derivative of suitable dissolution with solvents anthraquinone, under catalyst exists, with hydrogen, the anthraquinone in solvent is reduced to anthrahydroquinone, the latter's autoxidation under the existence of oxygen or air is anthraquinone and produces hydrogen peroxide.Gained mixture obtains aqueous hydrogen peroxide solution through water extraction and fractionation, further refines the product that concentrates and obtain various concentration, and the raffinate after extraction is got back to after treatment hydrogenation stage and recycled.
Process for prepairng hydrogen peroxide by anthraquinone used catalyst mainly contains Raney nickel and precious metals palladium catalyst.Raney nickel exist side reaction many, meet the easy spontaneous combustion of air, easily by oxygen and hydrogen peroxide poison, hydrogenator complex structure and lost efficacy after be difficult to the shortcomings such as regeneration, application is extremely restricted.Palladium catalyst have consumption few, active high, hydrogenation equipment simple, regeneration easily and the advantage such as easy-to-operate, become the main catalyst of domestic and international process for prepairng hydrogen peroxide by anthraquinone hydrogenation technique.
Hydrogen peroxide has another name called hydrogen peroxide; as a kind of free of contamination oxidant, bleaching agent, disinfectant, polymerization initiator, crosslinking agent and oxygenate, be widely used in the numerous areas such as papermaking, weaving, chemicals are synthetic, electronics, food processing, medicine, cosmetics, environmental protection, metallurgy.Demand is huge both at home and abroad, rapid development.But the price of hydrogen peroxide is higher both at home and abroad at present, has limited its application.Causing the major reason that hydrogen peroxide price is high, is that the content of precious metal palladium in process for prepairng hydrogen peroxide by anthraquinone fixed bde catalyst used is up to 0.3%.So, reducing the consumption of noble metal in catalyst, improve anthraquinone hydrogenation efficiency simultaneously, is one of critical path reducing hydrogen peroxide price.
Summary of the invention
It is a kind of by carrier material that the object of the invention is to provide, compound, efficient anthraquinone hydrogenation catalyst that helps that catalysis material and noble metal form and preparation method thereof.Mainly being, by introducing cheapness, helping catalysis material---carbide, when greatly reducing noble metal dosage, keeps even improving the whole catalytic activity of hydrogenation catalyst.The present invention is achieved through the following technical solutions: first carrier material be impregnated in the precursor solution of carbide, drying and high-temperature process, obtain the composite carrier that carbide is modified; Then composite carrier be impregnated in precious metal solution, drying is processed, and obtains the carried noble metal hydrogenation catalyst that carbide promotes.
The noble metal anthraquinone hydrogenation catalyst preparation method that carbide promotes, carries out according to following step:
1) first support material is mixed, be squeezed into bar shaped or rolling balling shape carrier that cross section is polygon row;
2) by the carrier impregnation of moulding in the aqueous solution of carbide precursor, stir;
3) by step 2) dipping carrier drying afterwards, high-temperature process under controlled atmosphere, obtains the composite carrier that carbide is modified;
4) step 3) gained composite carrier be impregnated in the solution of precious metal salt, stir;
5) the composite carrier water after step 4) dipping is cleaned and is dried, obtain the carried noble metal hydrogenation catalyst that carbide promotes.
Above-mentioned steps 1) described carrier material is aluminium oxide, and doped with one or more the mixture in silica, titanium oxide, zirconia or molecular sieve; The cross-sectional diameter of bar shaped carrier is 0.3-8 mm; The diameter of ball type carrier is 0.3-8 mm.
Above-mentioned steps 2) described carbide precursor, is the mixture of carbonaceous material and slaine.Wherein carbonaceous material be water soluble organic substance as glucose, sucrose, polyethylene glycol, polyvinyl alcohol etc., slaine is one or more mixtures in tungsten salt, molybdenum salt, vanadic salts.Tungsten salt is ammonium or alkali-metal tungstates, preferably ammonium metatungstate and sodium tungstate; Molybdenum salt is the molybdate of ammonium, alkali metal or magnesium, preferably positive ammonium molybdate and sodium molybdate; Vanadic salts is ammonium or alkali-metal vanadate, preferably ammonium metavanadate.In tungsten, molybdenum or vanadic salts solution, the atomic concentration sum of tungsten, molybdenum or vanadium is 0.001-5 mol L
-1, preferred 0.01-1 mol L
-1; In carbonaceous material, the mol ratio of carbon atom and above-mentioned metallic atom is 1-100:1, preferably 2-50:1.
Above-mentioned steps 2) volume that the described solution of carbide precursor and the volume ratio of carrier are 0.8-5:1(carrier is apparent volume, lower same); The hybrid infusion time is 0.3-10 hour.
Above-mentioned steps 3) described baking temperature is 50-300
oc, be 0.5-24 hour drying time; Indifferent gas is nitrogen or argon gas; Sintering temperature is 700-2000
oc; Roasting time is 0.3-10 hour.Described carbide is tungsten carbide, molybdenum carbide, one or more mixtures in vanadium carbide.
Above-mentioned steps 4) described precious metal salt solution is chloroplatinic acid, the acid of chlorine palladium or the mixed solution of the two, and pH value is 1-5; Platinum, palladium or the content of the mixture of the two in catalyst are 0.01-0.5 wt %; The volume ratio of precious metal solution and complex carrier is 0.8-5:1, and complex carrier dip time in acid solution is 0.3-5 hour.
Above-mentioned steps 5) described baking temperature is 50-150
oc, be 1-24 hour drying time.
The present invention compared with prior art, introduced cheap carbide as the catalysis material that helps of noble metal, in the situation that noble metal dosage only has typical catalyst 3-10%, also can keep even improving the overall activity of catalyst, thereby effectively reduce catalyst cost.Catalyst of the present invention is automatic reduction in catalysis anthraquinone hydrogenation course of reaction, without extra reduction process.
The specific embodiment
The evaluation system of anthraquinone hydrogenation reaction is to carry out on fixed bed device, and tube inner diameter is 10 mm.Working solution used is that anthraquinone is dissolved in the mixed solvent of aromatic hydrocarbons and trioctyl phosphate composition, consists of 2-EAQ 38 g L
-1, tetrahydrochysene 2-EAQ 80 g L
-1, heavy aromatics 650 g L
-1, trioctyl phosphate 200 g L
-1.2 ml catalyst are packed in reaction tube, and quartz sand is all loaded in upper and lower part.55
oc and hydrogen partial pressure are under the condition of 0.3 MPa, and working solution is carried with 36 ml h through pump
-1speed through beds.Keeping tail gas discharge capacity is 0.48 L h
-1.Each sample, after dioxygen oxidation, by liquor potassic permanganate titration, represents the activity of catalyst with the content of hydrogen peroxide in hydride.
With embodiment, the present invention is described further below, but scope of the present invention is not limited to this.
Embodiment 1
By aluminium oxide and silica in mass ratio 9:1 mix and be squeezed into the cylindrical bar that diameter is 0.3 mm, heap is than being 0.55 g ml
-1.Measure above-mentioned carrier 40 ml and be immersed in 32 ml containing 0.71 mol L
-1ammonium metatungstate and 0.83 mol L
-1in the mixed solution of glucose, flood 0.3 h.Isolate carrier, 50
oc is dried 24 h.By dry carrier under nitrogen atmosphere in 700
oc roasting 10 h, obtain the carrier that tungsten carbide is modified.In the 32 ml chlorine palladium acid solutions that it is 1.0 that carrier 40 ml that tungsten carbide is modified are immersed in containing 6.2 mg palladiums, pH, flood 0.3 h.Isolate carrier, carrier is washed with water to neutrality, 50
oc is dried 24 h, obtains catalyst finished product.The content of palladium in catalyst is 0.01 wt %, and the hydrogenation efficiency of catalyst is 4.5 g (H
2o
2) L
-1.
Embodiment 2
The concentration of ammonium metatungstate is 0.00014 mol L
-1, the concentration that adds of glucose is 0.0167 mol L
-1, other step is with embodiment 1.The content of palladium in catalyst is 0.03 wt %, and the hydrogenation efficiency of catalyst is 5.7 g (H
2o
2) L
-1.
Embodiment 3
The concentration of ammonium metatungstate is 0.0014 mol L
-1, the concentration of glucose is 0.0825 mol L
-1, other step is with embodiment 1.The content of palladium in catalyst is 0.03 wt %, and the hydrogenation efficiency of catalyst is 6.4 g (H
2o
2) L
-1.
Embodiment 4
The concentration of ammonium metatungstate is 0.14 mol L
-1, it is 0.17 mol L that glucose changes concentration into
-1sucrose, other step is with embodiment 1.The content of palladium in catalyst is 0.02 wt %, and the hydrogenation efficiency of catalyst is 8.7 g (H
2o
2) L
-1.
Embodiment 5
Changing ammonium metatungstate into concentration is 1 mol L
-1sodium tungstate, it is 60 g L that glucose changes concentration into
-1polyethylene glycol, other step is with embodiment 1.The content of palladium in catalyst is 0.02 wt %, and the hydrogenation efficiency of catalyst is 8.8 g (H
2o
2) L
-1.
Embodiment 6
Ammonium metatungstate is changed into the mixture of ammonium metatungstate and sodium tungstate, its concentration is respectively 0.1 and 0.28 mol L
-1sodium tungstate, it is 60 g L that glucose changes concentration into
-1polyvinyl alcohol, other step is with embodiment 1.The content of palladium in catalyst is 0.02 wt %, and the hydrogenation efficiency of catalyst is 9.2 g (H
2o
2) L
-1.
Embodiment 7
By aluminium oxide, silica and titanium oxide in mass ratio 9:0.8:0.2 mix and to roll into the ball type carrier that diameter is 0.3 mm, heap is than being 0.53 g ml
-1.Measure above-mentioned carrier 40 ml and be immersed in 200 ml containing 0.1 mol L
-1positive ammonium molybdate and 0.033 mol L
-1in the mixed solution of glucose, flood 10 h.Isolate carrier, 300
oc is dried 0.5 h.By dry carrier under nitrogen atmosphere in 2000
oc roasting 0.3 h, obtains the carrier that molybdenum carbide is modified.In the 200 ml chlorine palladium acid solutions that it is 5.0 that carrier 40 ml that molybdenum carbide is modified are immersed in containing 62 mg palladiums, pH, flood 5 h.Isolate carrier, carrier is washed with water to neutrality, 150
oc is dried 1 h, obtains catalyst finished product.The content of palladium in catalyst is 0.25 wt %, and the hydrogenation efficiency of catalyst is 12.7 g (H
2o
2) L
-1.
Embodiment 8
By aluminium oxide, silica and titanium oxide in mass ratio 9:0.8:0.2 mix and to be squeezed into the butterfly bar that diameter is 8 mm, heap is than being 0.26 g ml
-1, other step is with embodiment 7.The content of palladium in catalyst is 0.5 wt %, and the hydrogenation efficiency of catalyst is 7.2 g (H
2o
2) L
-1.
Embodiment 9
The total amount of palladium changes 6.2 mg into, and other step is with embodiment 7.The content of palladium in catalyst is 0.025 wt %, and the hydrogenation efficiency of catalyst is 9.6 g (H
2o
2) L
-1.
Embodiment 10
Change positive ammonium molybdate into 0.1 mol L
-1sodium molybdate, the total amount of palladium changes 6.2 mg into, other step is with embodiment 7.The content of palladium in catalyst is 0.025 wt %, and the hydrogenation efficiency of catalyst is 9.4 g (H
2o
2) L
-1.
Embodiment 11
Change positive ammonium molybdate into 0.1 mol L
-1magnesium molybdate, the total amount of palladium changes 6.2 mg into, other step is with embodiment 7.The content of palladium in catalyst is 0.025 wt %, and the hydrogenation efficiency of catalyst is 9.0 g (H
2o
2) L
-1.
Embodiment 12
By positive ammonium molybdate change into positive ammonium molybdate, sodium molybdate and the mixture of magnesium molybdate, concentration is respectively 0.04,0.04 and 0.02 mol L
-1, the total amount of palladium changes 6.2 mg into, and other step is with embodiment 7.The content of palladium in catalyst is 0.025 wt %, and the hydrogenation efficiency of catalyst is 8.8 g (H
2o
2) L
-1.
Embodiment 13
By aluminium oxide, silica and molecular sieve in mass ratio 8:1:1 mix and to roll into the ball type carrier that diameter is 8 mm, heap is than being 0.31 g ml
-1.Measure above-mentioned carrier 50 ml and be immersed in 250 ml containing 0.01 mol L
-1sodium vanadate and 0.17 mol L
-1in the mixed solution of glucose, flood 10 h.Isolate carrier, 300
oc is dried 0.5 h.Then under argon gas atmosphere in 1500
oc roasting 0.3 h, obtains the carrier that vanadium carbide is modified.In the 250 ml platinum acid chloride solutions that it is 5.0 that the carrier that vanadium carbide is modified is immersed in containing 80 mg platinum, pH, stir 5 h.Isolate carrier, water is cleaned to carrier to neutral, 150
oc is dried 1 h, obtains catalyst finished product.The content of platinum in catalyst is 0.5 wt %, and the hydrogenation efficiency of catalyst is 9.3 g (H
2o
2) L
-1.
Embodiment 14
By aluminium oxide, silica and molecular sieve in mass ratio 8:1:1 mix and to roll into the ball type carrier that diameter is 2 mm, heap is than being 0.43 g ml
-1.Measure above-mentioned carrier 50 ml and be immersed in 250 ml containing 0.1 mol L
-1ammonium vanadate and 1.7 mol L
-1in the mixed solution of glucose, flood 5 h.Isolate carrier, 100
oc is dried 5 h.Then under argon gas atmosphere in 1000
oc roasting 1 h, obtains the carrier that vanadium carbide is modified.In the 250 ml platinum acid chloride solutions that it is 5.0 that the carrier that vanadium carbide is modified is immersed in containing 7 mg platinum, pH, stir 5 h.Isolate carrier, water is cleaned to carrier to neutral, 150
oc is dried 1 h, obtains catalyst finished product.The content of platinum in catalyst is 0.03 wt %, and the hydrogenation efficiency of catalyst is 9.1 g (H
2o
2) L
-1.
Embodiment 15
By aluminium oxide, silica, zirconia and molecular sieve in mass ratio 7:1:1:1 mix and to be squeezed into the butterfly carrier that cross section maximum gauge is 2 mm, heap is than being 0.49 g ml
-1.Measure above-mentioned carrier 40 ml and be immersed in 40 ml containing 0.014 mol L
-1ammonium metatungstate, 0.1 mol L
-1positive ammonium molybdate, 0.1 mol L
-1ammonium vanadate and 1.0 mol L
-1in the mixed solution of glucose, flood 10 h.Isolate carrier, 100
oc is dried 5 h.Then under nitrogen atmosphere in 1000
oc roasting 3 h, obtain the carrier that tungsten carbide, molybdenum carbide and vanadium carbide are modified.By in gained carrier 400 ml chlorine palladium acid and chloroplatinic acid mixed solution that to be immersed in containing 3 mg palladiums and 3 mg platinum, pH be 5.0, flood 5 h.Isolate carrier, water is cleaned to carrier to neutral, 100
oc is dried 5 h, obtains catalyst finished product.Palladium and the platinum total content in catalyst is 0.03 wt %, and the hydrogenation efficiency of catalyst is 9.8 g (H
2o
2) L
-1.
The catalyst making according to above embodiment, not only can be for the hydrogenation technique of process for prepairng hydrogen peroxide by anthraquinone, also can be for organic hydrogenation technique of other type.
Claims (8)
1. the noble metal anthraquinone hydrogenation catalyst preparation method that carbide promotes, is characterized in that carrying out according to following step:
1) first support material is mixed, be squeezed into bar shaped or rolling balling shape carrier that cross section is polygon row;
2) by the carrier impregnation of moulding in the aqueous solution of carbide precursor, stir;
3) by step 2) dipping carrier drying afterwards, high-temperature process under controlled atmosphere, obtains the composite carrier that carbide is modified;
4) step 3) gained composite carrier be impregnated in the solution of precious metal salt, stir;
5) the composite carrier water after step 4) dipping is cleaned and is dried, obtain the carried noble metal hydrogenation catalyst that carbide promotes.
2. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 1 promotes, it is characterized in that above-mentioned steps 1) described carrier material is aluminium oxide, and doped with one or more the mixture in silica, titanium oxide, zirconia or molecular sieve; The cross-sectional diameter of bar shaped carrier is 0.3-8 mm; The diameter of ball type carrier is 0.3-8 mm.
3. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 1 promotes, is characterized in that above-mentioned steps 2) described carbide precursor is the mixture of carbonaceous material and slaine; Wherein carbonaceous material is glucose, sucrose, polyethylene glycol, polyvinyl alcohol, and slaine is one or more mixtures in tungsten salt, molybdenum salt, vanadic salts; Tungsten salt is ammonium or alkali-metal tungstates, preferably ammonium metatungstate and sodium tungstate; Molybdenum salt is the molybdate of ammonium, alkali metal or magnesium, preferably positive ammonium molybdate and sodium molybdate; Vanadic salts is ammonium or alkali-metal vanadate, preferably ammonium metavanadate; In tungsten, molybdenum or vanadic salts solution, the atomic concentration sum of tungsten, molybdenum or vanadium is 0.001-5 mol L
-1, preferred 0.01-1 mol L
-1; In carbonaceous material, the mol ratio of carbon atom and above-mentioned metallic atom is 1-100:1, preferably 2-50:1.
4. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 1 promotes, is characterized in that above-mentioned steps 2) the described solution of carbide precursor and the volume ratio of carrier be 0.8-5:1; The hybrid infusion time is 0.3-10 hour.
5. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 1 promotes, is characterized in that above-mentioned steps 3) described baking temperature is 50-300
oc, be 0.5-24 hour drying time; Indifferent gas is nitrogen or argon gas; Sintering temperature is 700-2000
oc; Roasting time is 0.3-10 hour;
Described carbide is tungsten carbide, molybdenum carbide, one or more mixtures in vanadium carbide.
6. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 1 promotes, is characterized in that above-mentioned steps 4) described precious metal salt solution is chloroplatinic acid, the acid of chlorine palladium or the mixed solution of the two, pH value is 1-5; Platinum, palladium or the content of the mixture of the two in catalyst are 0.01-0.5 wt %; The volume ratio of precious metal solution and complex carrier is 0.8-5:1, and complex carrier dip time in acid solution is 0.3-5 hour.
7. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 1 promotes, is characterized in that above-mentioned steps 5) described baking temperature is 50-150
oc, be 1-24 hour drying time.
8. the noble metal anthraquinone hydrogenation catalyst preparation method that a kind of carbide according to claim 3 promotes, is characterized in that above-mentioned steps 2) described tungsten salt is ammonium metatungstate or sodium tungstate; Molybdenum salt is positive ammonium molybdate or sodium molybdate; Vanadic salts is ammonium metavanadate; The atomic concentration sum 0.01-1 mol L of tungsten, molybdenum or vanadium in tungsten, molybdenum or vanadic salts solution
-1; In carbonaceous material, the mol ratio of carbon atom and above-mentioned metallic atom is 2-50:1.
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| CN108067274A (en) * | 2016-11-10 | 2018-05-25 | 中国科学院大连化学物理研究所 | It is a kind of to prepare hydrogen peroxide modified with noble metals carbide catalyst and its preparation and application |
| CN108079934A (en) * | 2017-11-30 | 2018-05-29 | 山东大学 | A kind of composite material and preparation method thereof |
| CN109894131A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of dimethyl terephthalate (DMT) (DMT) hydrogenation catalyst and preparation method thereof |
| CN110420637A (en) * | 2019-08-06 | 2019-11-08 | 北京化工大学 | A kind of W modified support carried metal Pd prepares the method and its application of composite catalyst |
| CN115672315A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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| CN108067274A (en) * | 2016-11-10 | 2018-05-25 | 中国科学院大连化学物理研究所 | It is a kind of to prepare hydrogen peroxide modified with noble metals carbide catalyst and its preparation and application |
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| CN109894131B (en) * | 2017-12-07 | 2022-03-08 | 中国科学院大连化学物理研究所 | Dimethyl terephthalate (DMT) hydrogenation catalyst and preparation method thereof |
| CN110420637A (en) * | 2019-08-06 | 2019-11-08 | 北京化工大学 | A kind of W modified support carried metal Pd prepares the method and its application of composite catalyst |
| CN115672315A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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