CN101648143A - Modified Pd/TS-1 catalyst of transition metal element, preparation method and application thereof - Google Patents
Modified Pd/TS-1 catalyst of transition metal element, preparation method and application thereof Download PDFInfo
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- CN101648143A CN101648143A CN200910070473A CN200910070473A CN101648143A CN 101648143 A CN101648143 A CN 101648143A CN 200910070473 A CN200910070473 A CN 200910070473A CN 200910070473 A CN200910070473 A CN 200910070473A CN 101648143 A CN101648143 A CN 101648143A
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Abstract
The invention relates to synthesis of hydrogen peroxide, in particular to a modified Pd/TS-1 catalyst of a transition metal element. The catalyst comprises a carrier and active components, wherein thecarrier is a titanium-silicon molecular sieve (TS-1); the active components comprise Pd and a transition metal element M, wherein the Pd is 0.5-5.0 percent of the mass of the TS-1; the transition metal content is in a mole ratio that M/(Pd+M)=0.05-1.0%; and M is a transition metal of the third period, a La family rare earth metal element or a composition of the two. The catalyst M-Pd/TS-1 is usedfor the reaction of directly compounding hydrogen peroxide by hydrogen and oxygen for the first time, and the reaction pressure in the process of preparing the hydrogen peroxide is normal pressure; the hydrogen partial pressure is lower than 0.02 MPa; the danger in the process of reaction is obviously reduced, and the catalyst expresses higher activity under the proper reaction condition.
Description
Technical field:
The present invention relates to the synthetic of hydrogen peroxide, be specially a kind of transition metal modification Pd/TS-1 catalyst.
Technical background:
Hydrogen peroxide is a kind of green oxidation agent of function admirable.Traditional hydrogen peroxide preparation method also is that at present large-scale hydrogen peroxide manufacture method is anthraquinone, this method long flow path, and the energy consumption height, and environmental pollution is serious relatively.Comparatively speaking, under the effect of catalyst, the method for hydrogen, the direct synthesize hydrogen peroxide of oxygen more meets the theory of atom economy.
In US3 361 533 Pd/SiO is disclosed from nineteen sixty-eight Britain's ICI Imperial Chemical Industries (ICI)
2Under the catalyst action, in acetone and hydrochloric acid and the sulfuric acid medium, since the result of study of hydrogen, the direct synthesize hydrogen peroxide of oxygen, relevant achievement has report repeatly, and catalyst is its key problem in technology.In the existing report, common feature is, catalyst is support type, and Pd or Au be the active load component of main body, second kind of noble metal, and as Pt, Ru, Rh, Os, Ho etc. add the performance that can effectively improve catalyst as the second load component.
Because hydrogen, oxygen are formed explosive mixture, wider range of explosion limit, and along with the rising of operating pressure, the explosion limit scope is further widened, and the consequence that blast causes is more serious, and the danger of operation significantly improves.Existing report, be subjected to the restriction of catalyst activity, for the conversion ratio that improves hydrogen and the selectivity of hydrogen peroxide, big more options reaction under high pressure system, as Dupont (Du Pont) the disclosed EP 0132294 of company, US 4889705, US 5135731 etc., and patent US 6958138, US 7122501 all under high pressure carries out.Exploitation normal pressure, high activated catalyst is significant.The Choudhary of India etc. report in disclosed patent US 7288240, with the Pd/Al of halogenation treatment
2O
3Be catalyst, under the normal pressure, hydrogen partial pressure is 0.05MPa, when total gas flow rate is 5.3mL/min, and reaction 2h, the yield of hydrogen peroxide reaches 53.7%, the concentration of hydrogen peroxide reaches about about 0.48wt%, when total flow is increased to 21.2mL/min, and reaction 1h, the yield of hydrogen peroxide is 18%, and the concentration of hydrogen peroxide reaches about 0.32wt%.Though operate under normal pressure, the author does not add inert component in order to guarantee the dividing potential drop of hydrogen, and reaction is still carried out in the very big hydrogen of explosion hazard, oxygen ratio.Liu etc. are at document (AppliedCatalysis A:General 2008, report is a catalyst with Pt-Pd 339:130-136), under the normal pressure, 10 ℃, hydrogen partial pressure is 0.005MPa, when total gas flow rate is 50mL/min, and reaction 3h, the yield of hydrogen peroxide is about 13.6%, the concentration of hydrogen peroxide reaches about 0.45wt%, and the yield of hydrogen peroxide is not very high, and process is carried out being lower than under 10 ℃ of normal temperature.
Above-mentioned prior art is seen, operates under high hydrogen partial pressure, and process hazard is bigger, and normal pressure is operation down, and the selectivity of hydrogen peroxide is lower.But not the system of modified with noble metals Pd catalyst is not appeared in the newspapers.
Summary of the invention:
The technical problem to be solved in the present invention is: the high hydrogen partial pressure operational danger that exists in the reaction at current direct synthesize hydrogen peroxide is big, the lower problem of catalyst activity under the low hydrogen dividing potential drop, a kind of transition metal modification Pd/TS-1 catalyst is provided, this method for preparing catalyst is simple, good reproducibility, can under low hydrogen dividing potential drop, be used for hydrogen, the direct synthesize hydrogen peroxide of oxygen, have higher activity.
Embodiment of the present invention are:
The M-Pd/TS-1 catalyst of a kind of transition metal M modification, this catalyst is formed and is comprised carrier and active component, wherein carrier is HTS (TS-1), active component is Pd and transition metal M, the set of dispense ratio is: Pd is 0.5～5.0% of a TS-1 quality, levels of transition metals is mol ratio M/ (Pd+M)=0.05～1.0%, and M is that transition metal, the La of period 3 is thulium or their combination.
Above described transition metal M be preferably Ce or La.
Above described transition metal M content preferred 0.1～0.5%.
Above described Pd content be preferably 1.0～4.0% of TS-1 quality,
Above described transition metal modification Pd/TS-1 Preparation of catalysts method, detailed process is as follows:
(1) takes by weighing the TS-1 molecular sieve of required weight, and measure the volume of the required maceration extract of incipient impregnation with deionized water;
(2) the selected load capacity of active component palladium on carrier is: take by weighing palladium bichloride, make active component palladium be the TS-1 molecular sieve carrier quality 0.5～5.0%;
(3) take by weighing nitrate or the chloride of transition metal M, making its consumption is mol ratio M/ (Pd+M)=0.05～1.0%;
(4), be dissolved in wiring solution-forming in the concentrated ammonia liquor of the maceration extract volume of being measured according to (1) with step (2) and (3) palladium bichloride that is taken by weighing and the nitrate of transition metal M or chloride;
(5) in the TS-1 molecular sieve carrier that the solution adding step (1) that step (4) is prepared is taken by weighing, dipping 24h in 100 ℃ of water-baths heating evaporates to dryness, obtains pressed powder then;
(6) pressed powder that step (5) is made moves in the tube furnace, leads to reducibility gas, makes the M-Pd/TS-1 catalyst of required transition metal M modification at 150～350 ℃ of following reductase 12～4h.
The described reducibility gas of step (6) is hydrogen, nitrogen or the mist of the two.
Above the M-Pd/TS-1 Application of Catalyst of described transition metal M modification, be used for the reaction of hydrogen, the direct synthesize hydrogen peroxide of oxygen, may further comprise the steps: the mixture that adds entry and water miscible low carbon solvent in the reactor, add KBr simultaneously, gained catalyst above adding again, make it to be suspended in the liquid phase reaction medium by magnetic agitation, and be about 4 with the pH value of phosphoric acid conditioned reaction medium; Water bath with thermostatic control control reaction temperature is 20～30 ℃ then, and the inert gas replacement system feeds hydrogen, oxygen and inert gas then continuously and reacts, and total gas flow rate is 20～200mL/min, H
2With O
2Mol ratio be 1: 0.5～5, stagnation pressure 0.1MPa, hydrogen partial pressure are 0.001～0.02MPa, the reaction time is 1～3h, unreacted hydrogen, oxygen and inert gas are discharged reactor continuously, the hydrogen peroxide that reaction generates is dissolved in the liquid phase reaction medium.
The volume ratio of wherein low carbon solvent and water is 1: 0.1～9, and catalyst is 0.025～1.0g: 20mL with the ratio of liquid phase medium, and the concentration of KBr is 1mmol/L, and inert gas can select nitrogen, argon gas or helium.
Above described low carbon solvent be acetone, methyl alcohol or ethanol.
Beneficial effect of the present invention is:
Catalyst M-Pd/TS-1 of the present invention, M are that transition metal and the La of period 3 is thulium, and perhaps their combination is used for the reaction of hydrogen, the direct synthesize hydrogen peroxide of oxygen first.
The process reaction pressure of preparation hydrogen peroxide is normal pressure, and hydrogen partial pressure is lower than 0.02MPa, has significantly reduced the danger of course of reaction, and described catalyst shows higher activity under suitable reaction condition.
The specific embodiment:
Embodiment 1
(Hunan Jianchang Petrochemical Co., Ltd, specific area is 390m at first to take by weighing the TS-1 molecular sieve of 1.5g
2/ g, TiO
2Content is 5～10%, SiO
2Content is 90～95% (mol%)), measuring its saturated water adsorptive value with deionized water is 1.6mL.(quality of Pd is 0.060g, and molal quantity is 5.6 * 10 to take by weighing the 0.100g palladium bichloride
-4Mol), be that 25% ammoniacal liquor dissolves under 50 ℃ with 1.6mL concentration; (molal quantity of Ce is 2.8 * 10 to take by weighing the 0.0012g cerous nitrate
-6Mol), join in the above-mentioned Pd solution, stir.1.5g TS-1 molecular sieve is joined in the above-mentioned dipping mother liquor, stir, make its uniform absorption.Leave standstill 24h under the room temperature.The catalyst sample that dipping the is good 20min that in 100 ℃ of water-baths, dewaters.Dry good pressed powder is packed in the quartz boat, is transplanted on tube furnace.At N
2Throughput is 200mL/min, handles 3h down for 160 ℃.Logical then N
2Gas is cooled to room temperature, promptly obtains required catalyst.Wherein, main active component Pd content is 4% (accounting for the percentage by weight of TS-1 molecular sieve), and cerium content is 0.5% (accounting for the molar percentage of the total component of metal).
Embodiment 2
The activity of such catalysts evaluation is to carry out in the 250mL four-hole boiling flask.25 ℃ of reaction temperatures, pressure are normal pressure.At first in the 250mL glass reactor, add the catalyst 0.5g that embodiment 1 makes, add 0.05mmol KBr, 50mL solvent (60% methyl alcohol, 40% water, KBr concentration are 1mmol/L) again, use H
3PO
4Transfer the pH=4 of solution.Raw gas flow 120mL/min, the hydrogen-oxygen ratio is 1: 1, wherein H
2Flow is 18mL/min, and dividing potential drop is 0.015MPa, and stagnation pressure is 0.1MPa, N
2Make diluent, enter by bubbling in the reactant liquor of magnetic agitation and react 3h.The conversion ratio by measuring the cubage hydrogen of hydrogen peroxide in the gas flow of reactor and composition and the reactant liquor and the selectivity and the yield of hydrogen peroxide.Be respectively H
2Conversion ratio be 22.0%, H
2O
2Selectivity be 16.2%, yield is 3.6%, this moment solution in H
2O
2Concentration be 0.35wt%.
The calculating of conversion rate of products, selectivity and yield.Gas chromatographic analysis is into and out of hydrogen, the oxygen content of reactor, and soap film flowmeter is measured the total gas flow rate into and out of reactor.The growing amount of hydrogen peroxide in the iodometric determination liquid phase medium, and then calculate the conversion ratio of hydrogen and the selectivity of hydrogen peroxide.
The conversion ratio of hydrogen
The selectivity of hydrogen peroxide
The yield of hydrogen peroxide
Comparative example 1
(quality of Pd is 0.060g, and molal quantity is 5.6 * 10 to take by weighing the 0.100g palladium bichloride
-4Mol), 1.6mL concentration is that 25% ammoniacal liquor dissolves under 50 ℃, makes the dipping mother liquor.Taking by weighing the 1.5g specific area is 390m
2/ gTS-1 molecular sieve joins in the above-mentioned dipping mother liquor, stirs, and leaves standstill 24h.Then in 100 ℃ of following water bath methods.Dry good pressed powder is packed in the quartz boat, is transplanted in the tube furnace, at N
2Flow is 200mL/min, 160 ℃ of following reduction 3h.Turn off power supply then, continue logical N
2To cool to room temperature, promptly obtaining the palladium load capacity is the Pd/TS-1 catalyst of 4% (percentage by weight).
The Pd/TS-1 catalyst that said method makes carries out activity rating with embodiment 2 described methods.Evaluation result, the conversion ratio of hydrogen are 15.2%, H
2O
2Selectivity and yield be respectively 5.5%, 0.8%, this moment solution in H
2O
2Concentration be 0.10wt%.
Comparative example 2
Repeat the process among the embodiment 1, just the transition metal cerous nitrate is changed into chloroplatinic acid.(the Pt molal quantity is 2.8 * 10 to take by weighing chloroplatinic acid 0.0015g
-6Mol), obtain the Pd/TS-1 catalyst of Pt modification.Wherein, the load capacity of transition metal platinum is 0.5% (accounting for the molar percentage of the total component of metal) on the carrier.
This catalyst adopts the condition identical with embodiment 2 to estimate.Evaluation result, H
2Conversion ratio be 15.7%, H
2O
2Selectivity be 18.1%, yield is 2.8%, this moment solution in H
2O
2Concentration be 0.31wt%.
Embodiment 3
Repeat the process of embodiment 1, just use the transition metal cerous nitrate instead lanthanum nitrate.(molal quantity of La is 2.8 * 10 to take by weighing the 0.0012g lanthanum nitrate
-6Mol), the process among the repetition embodiment 1.Obtain the Pd/TS-1 catalyst of lanthanum modification.Wherein, transition metal lanthanum load capacity is 0.5% (accounting for the molar percentage of the total component of metal) on the carrier.
Above-mentioned catalyst carries out activity rating with embodiment 2 described methods.Evaluation result, H
2Conversion ratio be 19.0%, H
2O
2Selectivity be 16.1%, yield is 3.1%, this moment solution in H
2O
2Concentration be 0.33wt%.
Embodiment 4
Repeat the process of embodiment 1, just use the transition metal cerous nitrate instead cobalt nitrate.(molal quantity of Co is 2.8 * 10 to take by weighing the 0.0008g cobalt nitrate
-6Mol), the process among the repetition embodiment 1.Obtain cobalt improved Pd/TS-1 catalyst.Wherein, the load capacity of transition metals cobalt is 0.5% (accounting for the molar percentage of the total component of metal) on the carrier.
Above-mentioned catalyst carries out activity rating with embodiment 2 described methods.Evaluation result, H
2Conversion ratio be 32.8%, H
2O
2Selectivity be 8.3%, yield is 2.7%.This moment solution in H
2O
2Concentration be 0.30wt%.
Embodiment 5
Repeat the process of embodiment 1, just use the transition metal cerous nitrate instead nickel nitrate.(molal quantity of Ni is 2.8 * 10 to take by weighing the 0.0008g nickel nitrate
-6Mol), the process among the repetition embodiment 1.Obtain the Pd/TS-1 catalyst of nickel modification.Wherein, the load capacity of transiting metal nickel is 0.5% (accounting for the molar percentage of the total component of metal) on the carrier.
Above-mentioned catalyst carries out activity rating with embodiment 2 described methods.Evaluation result, H
2Conversion ratio be 26.8%, H
2O
2Selectivity be 10.1%, yield is 2.7%.This moment solution in H
2O
2Concentration be 0.30wt%.
Embodiment 6
Adopt the catalyst among the embodiment 1, appreciation condition is compared with embodiment 2, does following adjustment, at raw gas flow 120mL/min, H
2Flow 18mL/min, under the constant situation of dividing potential drop 0.015MPa, changing the hydrogen-oxygen ratio is 1: 3.Evaluation result, H
2Conversion ratio be 17.7%, H
2O
2Selectivity be 42.2%, yield is 7.5%, this moment solution in H
2O
2Concentration be 0.74wt%.
Embodiment 7-9
Adopt the catalyst among the embodiment 1, appreciation condition is compared with embodiment 5, does following adjustment, and the unstripped gas total amount is reduced to 60mL/min respectively, 35mL/min and 25mL/min.Activity rating the results are shown in Table 1.
Table 1 changes the influence of raw gas flow to catalyst activity
Embodiment 10
The catalyst that adopts embodiment 1 to make, appreciation condition is compared with embodiment 5, does following adjustment, and total gas flow rate 40mL/min, hydrogen partial pressure are 0.018MPa, and the activity rating result is H
2Conversion ratio be 54.1%, H
2O
2Selectivity be 58.5%, yield is 31.7%, this moment solution in H
2O
2Concentration be 1.04wt%.
Claims (7)
1, the M-Pd/TS-1 catalyst of a kind of transition metal M modification, it is characterized by this catalyst composition and comprise carrier and active component, wherein carrier is HTS (TS-1), active component is Pd and transition metal M, the set of dispense ratio is: Pd is 0.5～5.0% of a TS-1 quality, and levels of transition metals is mol ratio M/ (Pd+M)=0.05～1.0%, and M is that transition metal, the La of period 3 is thulium or their combination.
2, the M-Pd/TS-1 catalyst of transition metal M modification according to claim 1, it is characterized by described transition metal M is Ce or La.
3, the M-Pd/TS-1 catalyst of transition metal M modification according to claim 1, it is characterized by described transition metal M content is 0.1～0.5%.
4, the M-Pd/TS-1 catalyst of transition metal M modification according to claim 1, it is characterized by described Pd content is 1.0～4.0% of TS-1 quality.
5, the M-Pd/TS-1 Preparation of catalysts method of transition metal M modification according to claim 1, it is as follows to it is characterized by step:
(1) takes by weighing the TS-1 molecular sieve of required weight, and measure the volume of the required maceration extract of incipient impregnation with deionized water;
(2) the selected load capacity of active component palladium on carrier is: take by weighing palladium bichloride, make active component palladium be the TS-1 molecular sieve carrier quality 0.5～5.0%;
(3) take by weighing nitrate or the chloride of transition metal M, making its consumption is mol ratio M/ (Pd+M)=0.05～1.0%;
(4), be dissolved in wiring solution-forming in the concentrated ammonia liquor of the maceration extract volume of being measured according to (1) with step (2) and (3) palladium bichloride that is taken by weighing and the nitrate of transition metal M or chloride;
(5) in the TS-1 molecular sieve carrier that the solution adding step (1) that step (4) is prepared is taken by weighing, dipping 24h in 100 ℃ of water-baths heating evaporates to dryness, obtains pressed powder then;
(6) pressed powder that step (5) is made moves in the tube furnace, leads to reducibility gas, makes the M-Pd/TS-1 catalyst of required transition metal M modification at 150～350 ℃ of following reductase 12～4h.
The described reducibility gas of step (6) is hydrogen, nitrogen or the mist of the two.
6, the M-Pd/TS-1 Application of Catalyst of transition metal M modification according to claim 1, it is characterized by and may further comprise the steps: the mixture that adds entry and water miscible low carbon solvent in the reactor, add KBr simultaneously, gained catalyst above adding again, make it to be suspended in the liquid phase reaction medium by magnetic agitation, and be about 4 with the pH value of phosphoric acid conditioned reaction medium; Water bath with thermostatic control control reaction temperature is 20～30 ℃ then, and the inert gas replacement system feeds hydrogen, oxygen and inert gas then continuously and reacts, and total gas flow rate is 20～200mL/min, H
2With O
2Mol ratio be 1: 0.5～5, stagnation pressure 0.1MPa, hydrogen partial pressure are 0.001～0.02MPa, the reaction time is 1～3h, unreacted hydrogen, oxygen and inert gas are discharged reactor continuously, the hydrogen peroxide that reaction generates is dissolved in the liquid phase reaction medium.
The volume ratio of wherein low carbon solvent and water is 1: 0.1～9, and catalyst is 0.025～1.0g: 20mL with the ratio of liquid phase medium, and the concentration of KBr is 1mmol/L, and inert gas can select nitrogen, argon gas or helium.
7, as the M-Pd/TS-1 Application of Catalyst of transition metal M modification as described in the claim 6, it is characterized by described low carbon solvent is acetone, methyl alcohol or ethanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105828938A (en) * | 2013-12-20 | 2016-08-03 | 科莱恩国际有限公司 | Zeolite catalysts containing titanium for the oxidation of methane in exhaust gas streams |
| CN107308982A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | The synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane |
| CN109806861A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of nanometer sandwich structure noble metal catalyst and application in hydrogen peroxide is directly synthesized in hydrogen and oxygen |
| CN116037202A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | CO catalytic oxidation catalyst and preparation method and application thereof |
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2009
- 2009-09-17 CN CN2009100704738A patent/CN101648143B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105828938A (en) * | 2013-12-20 | 2016-08-03 | 科莱恩国际有限公司 | Zeolite catalysts containing titanium for the oxidation of methane in exhaust gas streams |
| CN105828938B (en) * | 2013-12-20 | 2019-04-23 | 科莱恩国际有限公司 | Titanium containing zeolite catalyst for the methane in oxidation gaseous effluent stream |
| CN107308982A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | The synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane |
| CN109806861A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of nanometer sandwich structure noble metal catalyst and application in hydrogen peroxide is directly synthesized in hydrogen and oxygen |
| CN109806861B (en) * | 2017-11-20 | 2020-06-23 | 中国科学院大连化学物理研究所 | Preparation of nano-sandwich structure noble metal catalyst and application of nano-sandwich structure noble metal catalyst in hydrogen and oxygen direct synthesis of hydrogen peroxide |
| CN116037202A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | CO catalytic oxidation catalyst and preparation method and application thereof |
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