CN105688934A - Catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate and preparation method and application thereof - Google Patents
Catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate. The catalyst comprises a carrier, a metal palladium active component which accounts for 0.1-1.5% of the weight of the carrier and a transition metal additive which accounts for 0.05-0.8% of the weight of the carrier. A step-by-step impregnation-precipitation method is adopted during the preparation process. Dispersion and distribution state of the active component in the carrier is optimized, and stability and reducibility of the active component palladium are raised. In addition, interaction between the additive and the carrier is optimized. Thus, low-temperature activity of the catalyst and high selectivity of the target product are raised.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for carbon monoxide gas-phase catalytic synthesizing dimethyl oxalate and application, belong to field of catalyst preparation。
Background technology
China's oil resource is nervous, and external dependence degree keeps high-order for a long time。Along with the fast development of national economy, fly to surge for the ethylene glycol product consumption figure of polyester consumption is prominent。2012, China's ethylene glycol consumption figure 10,700,000 tons, the overwhelming majority was from petroleum path, and wherein 8,000,000 tons depend on from external import。From the development of the coal-ethylene glycol technology of CO, improve coal resources comprehensive utilization ratio, be possible not only to alleviate the nervous situation of petroleum resources, and be conducive to promoting the development of Coal Chemical Industry, C1 Chemical Engineering Technology。
Currently mainly by oil ethylene route synthesizing glycol, and China is the country of rich coal oil less, thus, Development of Coal preparing ethylene glycol is possible not only to effectively alleviate the imbalance between supply and demand of ethylene glycol, and can promote the level of coal resources high-efficiency cleaning trans-utilization。Oxalate is as wherein important coal-ethylene glycol intermediate product, and the strategic objective for realizing coal-ethylene glycol is significant。Additionally, dimethyl oxalate. is also a kind of important Organic Chemicals, can be used for preparing the intermediate of oxalic acid, oxalyl chloride, oxamides, ethylene glycol, some drugs, dyestuff and solvent。
Report CO gas-phase dimethyloxalate synthesis patent in, cold operation by CH3It can be 95% that ONO generates the selectivity of dimethyl oxalate., but yield is relatively low, it is impossible to meet industrialized economy requirement。The Pd-Mo/Al of US4,384,433 report2O3And Pd-Ni/Al2O3Catalyst, at normal pressure, 110 DEG C and air speed 2000h-1, unstripped gas composition (volumetric concentration): CH3ONO:15%, CO:20%, CH3OH:15%, NO:3% and N2: reacting under 47% condition, the space-time yield of dimethyl oxalate. is about 400g/L.h, by CH3It is 95% that ONO generates the selectivity of dimethyl oxalate.。The Pd-Ti/Al of US4507494 report2O3Catalyst is at 2.5kgf/cm2 pressure, 115 DEG C-120 DEG C and air speed 3000h-1, unstripped gas composition (volumetric concentration): CH3ONO:10%, CO:20%, CH3OH:4%, NO:3% and N2: reacting under 63% condition, the space-time yield of dimethyl oxalate. is about 429-462g/L.h, CH3It is more than 95% that ONO generates the selectivity of dimethyl oxalate.。
For oxalate synthesis catalyst, the catalyst adopted on existing commercial plant is Pd-Fe/Al2O3Catalyst, precious metals pd content is 1.2%～1.5%, and performance indications are DMO yield 750g/L h。Adopting traditional dipping method to prepare, there is noble metal dosage height, disperse uneven, and in the reaction thus caused, easy temperature runaway causes the deficiencies such as reunion and the catalysqt deactivation of active component, the technology of preparing that is further improved reduces cost to improve usefulness。
Summary of the invention
It is an object of the invention to overcome the defect of prior art, the preparation method that a kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester is provided, by optimized fabrication condition, the aspects such as inorganic ion are removed mainly by step impregnation, alkali precipitation and abundant washing, optimize active component dispersion in the carrier and distribution, thus improve the catalytic performance of catalyst。
The present invention is achieved by the following technical solutions:
A kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester, including carrier, accounting for the Metal Palladium active component of vehicle weight 0.1%～1.5% and account for the transition metal promoter of vehicle weight 0.05%～0.8%, wherein Metal Palladium is with Pd (OH)2Form load on carrier。
Preferably, the content of described Metal Palladium active component accounts for the 0.2%～1.0% of carrier total amount。
Preferably, the content of described transition metal promoter accounts for the 0.1%～0.4% of vehicle weight。
Preferably, described carrier is α-Al2O3, the specific surface area of carrier is 3～30m2/ g, the best is 5～20m2/ g；Pore volume is 0.01～0.5cm3/ g；Average pore size is at 2～50nm。
Preferably, described transition metal promoter is one or both in the transition metal such as lanthanum, magnesium, ferrum, cobalt, nickel or copper, more preferably lanthanum, ferrum。
The preparation method of a kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester, comprises the following steps:
(1) dipping of transition metal promoter: the aqueous solution of the soluble-salt of preparation transition metal promoter, then by carrier impregnation wherein, after the aqueous solution loaded body crossing metal promoter soluble-salt described in excessively fully absorbs load, the mode being vapored away moisture by Ultrasonic Heating is dried, then roasting, standby；
(2) dipping of Metal Palladium active component；The aqueous solution of the soluble-salt of preparing metal palladium, then the carrier impregnation being loaded with transition metal promoter step (1) prepared is wherein, after the aqueous solution loaded body of the soluble-salt of described Metal Palladium fully absorbs load, the mode being vapored away moisture by Ultrasonic Heating is dried；
(3) precipitation: the soluble-salt being loaded with Metal Palladium prepare step (2) and the carrier of transition metal promoter are placed in alkali liquor and soak, make Metal Palladium precipitation load on carrier, then deionized water wash removes remaining acid ion, afterwards then through dry, roasting, namely obtain the described catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester。
Wherein,
Preferably, in step (1), in the aqueous solution of the soluble-salt of described transition metal promoter, the concentration of transiting metal component is 0.1～2wt%。
Preferably, in step (1), the aqueous solution of the soluble-salt of described transition metal promoter and the relative usage of carrier, under the premise that the load percentage of transition metal promoter Yu carrier is certain, enable the aqueous solution loaded body absorbing load completely of transition metal promoter soluble-salt, as absorbing load can be carried out according to the two about mass ratio 1:2。
Preferably, in step (1), the time of described dipping is 0.5-4 hour。
Preferably, in step (1), described Ultrasonic Heating purpose is to vapor away moisture, heats 4 hours at general 95 DEG C。
Preferably, in step (1), the temperature of described roasting is 300-600 DEG C, and the time of roasting is 2-8 hour。
Preferably, in step (2), the soluble-salt of described Metal Palladium is selected from Palladous nitrate., Palladous chloride. and palladium sulfate etc., more preferably Palladous chloride.。Wherein PdCl2Impregnation liquid system owing to forming stable [PdCl in the solution4]2-Complex structure, makes to regulate and control more easy to active component dispersion on alumina and distribution in catalyst preparation process。
Preferably, in step (2), in the aqueous solution of the soluble-salt of described Metal Palladium, the concentration of Metal Palladium is 0.1-3.0wt%。
Preferably, in step (2), the pH value regulating the aqueous solution of the soluble-salt of described Metal Palladium is 1.0～2.0。As used hydrochloric acid to carry out the adjustment of acidity。
Preferably, in step (2), the relative usage of the carrier of the carrying transition metal auxiliary agent that the aqueous solution of the soluble-salt of described Metal Palladium is prepared with step (1), under the premise that the load percentage of Metal Palladium Yu carrier is certain, require that the aqueous solution loaded body enabling the soluble-salt of Metal Palladium fully absorbs load, as absorbing load can be carried out according to the two about mass ratio 1:2。
Preferably, in step (2), the time of described dipping is 0.5-2 hour。
Preferably, in step (2), described Ultrasonic Heating purpose is to vapor away moisture, heats 4 hours at general 95 DEG C。
Preferably, in step (3), described alkali liquor is selected from the aqueous solution of sodium hydroxide, sodium carbonate, ammonium carbonate；Concentration is 0.5-2.0wt%。
Preferably, in step (3), the soluble-salt being loaded with Metal Palladium and the carrier of transition metal promoter that step (2) prepares are 1:1～1:4 with the mass ratio of described alkali liquor。
In step (3), in immersion process, when the pH value of alkali liquor no longer changes, namely can determine whether that the complete precipitating load of Metal Palladium is on carrier。
Preferably, in step (3), described dry temperature is 100～200 DEG C, and drying time is 2 10 hours。
Preferably, in step (3), the temperature of described roasting is 300～600 DEG C, roasting 28 hours。
Invent the using method of described catalyst:
Described catalyst before use, adopts hydrogen or the reduction of other reducibility gas, and reducing gases air speed is 10～50ml/min.gcat, and reduction temperature is 100 DEG C～250 DEG C, and the recovery time is 2～4 hours。
The reaction of dimethyl oxalate. vapor-phase synthesis adopts fixed bed reactors, unstripped gas carbon monoxide and nitrites nitrogen or carbon dioxide dilute, unstripped gas and catalyst contact time are 0.2～4 second, reaction temperature controls at 110～130 DEG C, reaction pressure controls at normal pressure～0.6MPa, in unstripped gas, the volume content of CO is 10%～30%, CH3The volume content of ONO is 5%～20%。
Technique effect and the advantage of the present invention are in that:
Catalyst preparation process adopts the step impregnation sedimentation method。First promoter metal salt is impregnated on carrier, after drying and roasting, then dip loading palladium metal salt, carry out the structure of catalyst modifying improvement by adding metal promoter, and make winner active component Pd with Pd (OH) by follow-up alkali precipitation2Form load at carrier surface, optimize active component dispersion in the carrier and distribution, improve the stability of active component palladium and easy reproducibility simultaneously, and the interaction between itself and auxiliary agent and carrier reaches optimization, thus improve the low temperature active of catalyst and generating the selectivity of target product。
Detailed description of the invention
Below by way of specific instantiation, technical scheme is described。Should be understood that one or more method steps that the present invention mentions do not repel before and after described combination step, there is also additive method step or additive method step can also be inserted between these steps specifically mentioned；Should also be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention。And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention。
Embodiment 1
Weigh 100 grams of α-Al2O3Carrier, by 0.3wt%Pd-0.16wt%Fe/ α-Al2O3Content prepares catalyst, first weighs 1.14g nine liquid glauber salt acid dissolved ferric iron in 50g deionized water, the α-Al that will weigh up2O3Carrier is put into dipping 30min in the iron nitrate solution configured and is fully absorbed load to the complete loaded body of solution, then ultrasonic dry 4h at 95 DEG C, roasting 2h in 600 DEG C of Muffle furnaces；Weighing 0.50g Palladous chloride. solid again, be dissolved in 50g hydrochloric acid solution, the pH value controlling solution is 1.2～1.3, the sample of above-mentioned roasting be impregnated in 30min in palladium chloride solution until solution loaded body fully absorbs load, again 95 DEG C of ultrasonic dry 4h；Preparation 1wt% concentration sodium carbonate liquor 150g, above-mentioned drying sample is dipped in alkali liquor to pH value constant after, carry out washing until can't detect Cl with deionized water-Till, 120 DEG C of dry 8h, 500 DEG C of roasting 6h, obtain 0.3wt%Pd 0.16wt%Fe/ α-Al2O3Catalyst。
Embodiment 2
Weigh 100 grams of α-Al2O3Carrier, by 0.3wt%Pd-0.08wt%Fe/ α-Al2O3Content prepares catalyst, first weighs 0.57g nine liquid glauber salt acid dissolved ferric iron in 50g deionized water, the α-Al that will weigh up2O3Carrier is put into and is impregnated 30min in the iron nitrate solution configured to the complete loaded body absorbing load of solution, then ultrasonic dry 4h at 95 DEG C, roasting 6h in 300 DEG C of Muffle furnaces；Weighing 0.50g Palladous chloride. solid again, be dissolved in 50g hydrochloric acid solution, the pH value controlling solution is 2.0；The sample of above-mentioned roasting is put into dipping 30min in palladium chloride solution and fully absorbs load to solution loaded body, then 95 DEG C of ultrasonic dry 4h；Preparation 0.5wt% concentration sodium hydroxide solution 100g, above-mentioned dried sample is dipped in alkali liquor to pH value constant after, carry out washing until can't detect Cl with deionized water-Till, 120 DEG C of dry 8h, 300 DEG C of roasting 8h, obtain 0.3%Pd 0.08%Fe/ α-Al2O3Catalyst。
Embodiment 3
Weigh 100 grams of α-Al2O3Carrier, by 1.5wt%Pd-0.05wt%Ni/ α-Al2O3Content prepares catalyst, first weighs 0.248g six water nickel nitrate and is dissolved in 50g deionized water, the α-Al that will weigh up2O3Carrier is put into and is impregnated 4h in the nickel nitrate solution configured to the complete loaded body absorbing load of solution, then ultrasonic dry 4h at 95 DEG C, subsequently roasting 4h in 500 DEG C of Muffle furnaces；Weighing 2.50g Palladous chloride. solid again, be dissolved in 50g hydrochloric acid solution, the pH value controlling solution is 1.0, is put into by the sample of above-mentioned roasting and impregnates 30min in palladium chloride solution to the complete loaded body absorbing load of solution, then 95 DEG C of ultrasonic dry 4h；The sodium hydroxide solution 200g of compound concentration 1.0wt%, above-mentioned dried sample is dipped in alkali liquor to pH value constant after, carry out washing until can't detect Cl with deionized water-Till, 200 DEG C of dry 4h, 500 DEG C of roasting 6h, namely make 1.5wt%Pd-0.05wt%Ni/ α-Al2O3Catalyst。
Embodiment 4
Weigh 100 grams of α-Al2O3Carrier, by 0.5wt%Pd-0.3wt%Fe-0.3wt%La/ α-Al2O3Content prepares catalyst, first weighs 2.17g nine water ferric nitrate and 0.94g lanthanum nitrate hexahydrate is dissolved in 50g deionized water, the α-Al that will weigh up2O3Carrier is put into and is impregnated 4h in the mixing salt solution configured to the complete loaded body absorbing load of solution, then ultrasonic dry 4h at 95 DEG C, subsequently roasting 4h in 500 DEG C of Muffle furnaces；Weighing 0.83g Palladous chloride. solid again, be dissolved in 50g hydrochloric acid solution, the pH value controlling solution is 1.5, is put into by the sample of above-mentioned roasting and impregnates 30min in palladium chloride solution to the complete loaded body absorbing load of solution, then 95 DEG C of ultrasonic dry 4h；Preparation 2.0wt% concentration sodium hydroxide solution 150g, above-mentioned dried sample is dipped in alkali liquor to pH value constant after, carry out washing until can't detect Cl with deionized water-Till, 120 DEG C of dry 6h, 400 DEG C of roasting 8h, namely make 0.5wt%Pd-0.3wt%Fe-0.3wt%La/ α-Al2O3Catalyst。
Embodiment 5
Weigh 100 grams of α-Al2O3Carrier, by 1.0wt%Pd-0.8wt%La/ α-Al2O3Content prepares catalyst, first weighs 2.49g lanthanum nitrate hexahydrate and is dissolved in 50g deionized water, the α-Al that will weigh up2O3Carrier is put into and is impregnated 4h in the Lanthanum (III) nitrate saline solution configured to the complete loaded body absorbing load of solution, then ultrasonic dry 4h at 95 DEG C, subsequently roasting 4h in 500 DEG C of Muffle furnaces；Weighing 1.67g Palladous chloride. solid again, be dissolved in 50g hydrochloric acid solution, the pH value controlling solution is 1.0, is put into by the sample of above-mentioned roasting and impregnates 30min in palladium chloride solution to the complete loaded body absorbing load of solution, then ultrasonic dry 4h at 95 DEG C；Preparation 2.0wt% concentration sodium hydroxide solution 150g, above-mentioned dried sample is dipped in alkali liquor to pH value constant after, carry out washing until can't detect Cl with deionized water-Till, 120 DEG C of dry 6h, 400 DEG C of roasting 8h, namely make 1.0wt%Pd-0.8wt%La/ α-Al2O3Catalyst。
Embodiment 6
Catalyst performance in synthesizing dimethyl oxalate reacts is evaluated by fixed bed reactors。Reactor inside diameter is 10mm, the built-in thermocouple sheath of reactor, and loaded catalyst is 2ml。Catalyst is cooled to desired reaction temperature after being warming up to 250 DEG C of reduction activations in hydrogen atmosphere。Unstripped gas passes through beds, and product dimethyl oxalate. is discharged by reactor bottom。Reaction gas CH3ONO concentration is 15v%, CO and CH3The volume flow ratio of ONO is 2, NO concentration is 6%, and all the other are N2, air speed GHSV is 3000h-1, reaction pressure 0.4MPa。
The catalyst of preparation in above-described embodiment 1-5 is used for carbon monoxide coupling and prepares dimethyl oxalate., and investigate 0.5wt%Pd-0.3wt%Fe-0.3wt%La/ α-Al2O3Catalyst is the long-term stable experiment of catalyst under the reaction temperature of 125 DEG C, and concrete catalyst activity result is shown in table 1 and table 2。
The each catalyst performance evaluation result of table 1
The performance change situation that table 2 catalyst long period is evaluated
Claims (9)
1. the catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester, including carrier, accounting for the Metal Palladium active component of vehicle weight 0.1%～1.5% and account for the transition metal promoter of vehicle weight 0.05%～0.8%, wherein Metal Palladium is with Pd (OH)2Form load on carrier。
2. a kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester as claimed in claim 1, it is characterised in that described carrier is α-Al2O3, the specific surface area of carrier is 3～30m2/ g, pore volume is 0.01～0.5cm3/ g, average pore size is at 2～50nm。
3. a kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester as claimed in claim 1, it is characterised in that described transition metal promoter is one or both in lanthanum, magnesium, ferrum, cobalt, nickel or copper。
4. a preparation method for a kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester as described in as arbitrary in claim 1-3, comprises the following steps:
(1) dipping of transition metal promoter: the aqueous solution of the soluble-salt of preparation transition metal promoter, then by carrier impregnation wherein, after the aqueous solution loaded body crossing metal promoter soluble-salt described in excessively fully absorbs load, the mode being vapored away moisture by Ultrasonic Heating is dried, then roasting, standby；
(2) dipping of Metal Palladium active component；The aqueous solution of the soluble-salt of preparing metal palladium, then the carrier impregnation being loaded with transition metal promoter step (1) prepared is wherein, after the aqueous solution loaded body of the soluble-salt of described Metal Palladium fully absorbs load, the mode being vapored away moisture by Ultrasonic Heating is dried；
(3) precipitation: the soluble-salt being loaded with Metal Palladium prepare step (2) and the carrier of transition metal promoter are placed in alkali liquor and soak, make Metal Palladium precipitation load on carrier, then deionized water wash removes remaining acid ion, afterwards then through dry, roasting, namely obtain the described catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester。
5. preparation method as claimed in claim 4, it is characterised in that step (1) also includes any one in following characteristics or multinomial:
1. in the aqueous solution of described transition metal promoter soluble-salt, the concentration of transiting metal component is 0.1-2wt%；
2. the temperature of described roasting is 300-600 DEG C, and the time of roasting is 2-8 hour。
6. preparation method as claimed in claim 4, it is characterised in that step (2) also includes any one in following characteristics or multinomial:
1. the soluble-salt of described Metal Palladium is selected from Palladous nitrate., Palladous chloride. and palladium sulfate；
2. in the aqueous solution of the soluble-salt of described Metal Palladium, the concentration of Metal Palladium is 0.1-3.0wt%；
3. the pH value regulating the aqueous solution of the soluble-salt of described Metal Palladium is 1.0～2.0。
7. preparation method as claimed in claim 4, it is characterised in that step (3) also includes any one in following characteristics or multinomial:
1. described alkali liquor is selected from the aqueous solution of sodium hydroxide, sodium carbonate, ammonium carbonate；Concentration is 0.5-2.0wt%；
2. step (2) prepares the soluble-salt being loaded with Metal Palladium and the carrier of transition metal promoter are 1:1～1:4 with the mass ratio of described alkali liquor；
3. described dry temperature is 100～200 DEG C, and drying time is 2 10 hours；
4. the temperature of described roasting is 300～600 DEG C, roasting 28 hours。
8. the application of a kind of catalyst for catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester as described in as arbitrary in claim 1-3, it is characterized in that, described catalyst is before use, adopt hydrogen or the reduction of other reducibility gas, reducing gases air speed is 10～50ml/min.gcat, reduction temperature is 100 DEG C～250 DEG C, and the recovery time is 2～4 hours。
9. apply as claimed in claim 8, it is characterized in that, the reaction of dimethyl oxalate. vapor-phase synthesis adopts fixed bed reactors, unstripped gas carbon monoxide and nitrites nitrogen or carbon dioxide dilute, unstripped gas and catalyst contact time are 0.2～4 second, and reaction temperature controls at 110～130 DEG C, and reaction pressure controls at normal pressure～0.6MPa, in unstripped gas, the volume content of CO is 10%～30%, CH3The volume content of ONO is 5%～20%。
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| CN109926066A (en) * | 2019-04-01 | 2019-06-25 | 北京化工大学 | Double auxiliary agent nano Pd catalyst Preparation method and uses |
| CN111939929A (en) * | 2020-09-08 | 2020-11-17 | 安徽师范大学 | Binary metal nano Pd/alumina catalyst and preparation method thereof, and method for preparing dimethyl oxalate through CO coupling oxidation |
| CN114433081A (en) * | 2022-02-25 | 2022-05-06 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO-production of carbonic ester and formic ester by synthesizing oxalate with CO |
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