CN104148088A - Catalyst for synthesizing dimethyl oxalate from CO and ultrasonic dispersion preparation method of catalyst - Google Patents
Catalyst for synthesizing dimethyl oxalate from CO and ultrasonic dispersion preparation method of catalyst Download PDFInfo
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- CN104148088A CN104148088A CN201410298664.0A CN201410298664A CN104148088A CN 104148088 A CN104148088 A CN 104148088A CN 201410298664 A CN201410298664 A CN 201410298664A CN 104148088 A CN104148088 A CN 104148088A
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Abstract
The invention discloses a catalyst for synthesizing dimethyl oxalate from CO and an ultrasonic dispersion preparation method of the catalyst. A chemical general formula of the catalyst provided by the invention is Pd-M/Al2O3, wherein the mass percent of palladium serving as an active component is 0.1 to 1%, M is one of Fe, Cu or Zn, and the specific surface area of the catalyst is 1 to 10 m<2>/g; an adopted carrier is a-type spherical aluminum oxide with the particle diameter of 1 to 5 mm; the dispersion degree of the active component of the catalyst is 20 to 27%. The preparation method of the catalyst provided by the invention has the characteristic that the catalyst is prepared by soaking in an ultrasonic condition; according to the catalyst prepared by using the method, the dispersion degree of precious metal as the active component is obviously changed, and the precious metal in the catalyst is low in using amount; in the process of synthesizing dimethyl oxalate, at low bed temperature, the stability of the active component of the catalyst is guaranteed, in addition, the high catalytic activity and the space-time yield of dimethyl oxalate are guaranteed, and the utilization ratio of the precious metal is increased.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for the reaction of Oxidation of Carbon Monoxide coupling synthesizing dimethyl oxalate, mainly comprise Pd-M/Al prepared by employing ultrasonic immersing-precipitation method
2o
3the correlation technique of loaded catalyst, wherein M is auxiliary agent.
Technical background
Dimethyl oxalate is important industrial chemicals, due to its unique structure and purposes and as the intermediate of various organic syntheses widely, has been subject to extensive concern and research.At present, domestic oxalic acid and the alcohol generation esterification of still adopting carried out, and has the shortcomings such as high, the seriously polluted and raw material availability of cost is low.The patent JP8242.656 of Ube Industries Ltd. openly speciallys permit and has reported a kind of employing load type palladium catalyst, utilizes the technological process of CO and methyl nitrite normal pressure synthesizing dimethyl oxalate.The advantages such as this technique Atom economy is good, reaction condition is gentle, less energy consumption, three-waste free discharge, good product quality, are subject to domestic and international extensive concern and attention subsequently.A lot of by adding different auxiliary agents as Zr, Ce, Ti, La, Ir, Ni, MO subsequently
xdeng the Patents that improves the space-time yield of oxalate, also arise at the historic moment.Although the space-time yield of oxalate has raising to a certain extent after introducing auxiliary agent, the consumption of major catalyst Pd is more higher (consumption of industrial Pd is even up to 1%～2%) still.Some patent reports high-dispersion loading type metallic catalyst preparation method's progress, patent (CN02108585.4) has reported that a kind of liquid-phase reduction prepares the method for high dispersive carrier metal catalyst, but the method does not have ultrasonic dispersion and calcination steps, metal is only difficult to be distributed to equably carrier surface under stirring action, and the catalyst of roasting does not cause less stable a little less than because of its Support-metal strong interaction; Patent (CN200810236524.5) has been reported the carbon-supported metal hydrogenation Catalysts and its preparation method of a kind of ruthenium.
This patent does not still have ultrasonic dispersion and calcination steps, is more difficult to get high dispersive and long-life catalyst.
At present, mostly the catalyst of patent report is to adopt alumina support or other metal oxides Powdered, non-moulding, in activity rating process, the consumption of catalyst is only in 1ml left and right, if be applied to industrial applications, catalyst need to be squeezed into solid shape and there is certain mechanical strength.In order to reduce the production cost of catalyst, improve active component Pd utilization rate, accelerate process of industrialization, the preparation method who develops a kind of CO gas phase coupling synthesizing dimethyl oxalate catalyst of the moulding with low noble metal load capacity, high stability, high space-time yield is the consistent direction of current all circles.
Summary of the invention
The object of the invention is to have all problems for current catalyst, provide a kind of by the standby CO synthesizing dimethyl oxalate catalyst of ultrasonic immersing legal system, the prepared catalyst of the method significantly changes the decentralization of noble metal active component, and catalyst activity significantly improves.
Its chemical general formula of catalyst prepared by the inventive method is Pd-M/Al
2o
3, wherein active component palladium content is the 0.1-1% of carrier quality, and wherein M represents one of Fe, Cu, Zn, and M content is the 0.15-0.60% of carrier quality, and the specific area of catalyst is 1-10m
2/ g; The carrier adopting is a type ball-aluminium oxide of particle diameter 1-5mm, and specific area is 1-10m
2/ g; The decentralization of this catalyst activity component is 20-27%, is preferably 23-27%.
The present invention be take palladium bichloride as palladium source, the alumina balls of take through high-temperature roasting are carrier, in preparation, adopt ultrasonic wave dispersion technology that active component palladium is loaded on alumina support with the state of more optimizing, form a kind of efficient, low heat release and stable catalyst for synthesizing oxalic ester.
The preparation method of catalyst of the present invention is:
A. palladium bichloride and auxiliary agent M salt are dissolved in and in hydrochloric acid solution, prepare dipping solution, according to every batch of consumption that needs the quality of impregnated carrier and the Pd content of required catalyst and M content to determine palladium bichloride and auxiliary agent M salt in dipping solution; Again by the addition of definite hydrochloric acid solution of every gram of carrier preparation 1mL dipping solution;
In described predetermined catalyst, Pd content is the 0.1-1% of carrier quality, and M content is the 0.15-0.60% of carrier quality; Described M salt is ferric nitrate, copper nitrate or zinc nitrate, and the concentration of described hydrochloric acid solution depends on the pH environment of prepared catalyst needs, and pH is 0～6;
B. the carrier in steps A is immersed in maceration extract; Ultrasonic processing 1～15min under Ultrasound Instrument medium frequency 20～59Hz and ultrasonic power 50～100W, the good ultrasonic processing time is 1-5min, then at 40～60 ℃ standing 6～24h; Put into baking oven dry 12～24h at 100～200 ℃; By deionized water, fully wash again; In baking oven, 150 ℃ are fully dried; Described carrier is a type ball-aluminium oxide of particle diameter 1-5mm, and specific area is 1-10m
2/ g.
C. by dried catalyst precarsor at H
2or in CO atmosphere, reduce 4～8h at 150～400 ℃, obtain Pd-M/Al
2o
3catalyst.
From the study on the stability curve map of 100 hours catalyst of Fig. 1, can find out, the yield of catalyst is substantially consistent in evaluation procedure in 100 hours, and the good stability of catalyst is described.From Fig. 2-6 and table 1, can obtain by observation and analysis, through the ratio of ultrasonic processing, do not have the active component decentralization of catalyst of ultrasonic processing all high, and dispersing uniformity is better; Growth along with ultrasonic time, the metal dispersity of catalyst increases to some extent, and the activity of catalyst also improves thereupon, but excessive ultrasonic cause catalyst particle size have the trend of reuniting and growing up, the metal dispersity of catalyst reduces gradually, and the activity of catalyst also decreases.By table 2, found out, the catalyst of the ultrasonic processing of process is for CO oxidative coupling synthesizing dimethyl oxalate course of reaction, and dimethyl oxalate yield obviously improves than undressed catalyst.
The advantage of Catalysts and its preparation method of the present invention is: catalyst activity component high degree of dispersion prepared by the present invention, and in the lower situation of the load capacity of Pd, the activity of catalyst is better; Based on being better applied to industrialized amplification and production, what carrier adopted is the spherical a type aluminium oxide of moulding, and specific area is 1-10m
2/ g, in carrier quality, active component palladium content is the 0.1%-1% of carrier quality; Catalyst finished particle diameter 1-5mm, in adaptive response technique, catalyst has many-sided requirements such as certain hardness and caloic heat transfer.The prepared catalyst noble metal dosage of this preparation method is low and thermal discharge is little, under lower bed temperature condition, not only guaranteed the stability of catalyst activity component, also guarantee higher activity and the space-time yield of dimethyl oxalate simultaneously, improved the utilization rate of noble metal.
Accompanying drawing explanation
Fig. 1 is the life-span investigation figure of the catalyst of preparation in embodiment 1.
Fig. 2 is the transmission electron microscope photo of the A0 catalyst of preparation in embodiment 1.
Fig. 3 is the transmission electron microscope photo of the A1 catalyst of preparation in embodiment 1.
Fig. 4 is the transmission electron microscope photo of the A2 catalyst of preparation in embodiment 1.
Fig. 5 is the transmission electron microscope photo of the A3 catalyst of preparation in embodiment 1.
Fig. 6 is the transmission electron microscope photo of the A4 catalyst of preparation in embodiment 1.
The concrete example mode of implementing
With example, further illustrate the present invention below, but the invention is not restricted to example.
Embodiment 1:
(1) preparation of catalyst
0.075g palladium bichloride and 0.40g auxiliary agent ferric nitrate are dissolved in the hydrochloride buffer that pH=1.1 volume is 15ml, by 15g alumina balls (the diameter 2mm through 1300 ℃ of calcination process, rotating disc type rolling ball method obtains) add in buffer solution, under the ultrasound condition of frequency 25Hz, after ultrasonic 2min, place at ambient temperature 12h, then put into drying box at 100 ℃ of dry 12h, then be dried 12h at 150 ℃; At 60 ℃, with 5 times of volumes of deionized water washing 10 times, every minor tick 2～3h, outwells after the solution soaking for the last time, put into 100 ℃ of baking ovens continuation and be dried 12h, by gained load the alumina balls of palladium pass into CO:N
2for the gas of 1:4 reduces 4h at 150～400 ℃, obtain Pd-Fe/Al
2o
3catalyst finished product.Pd content is wherein 0.3% of carrier quality, and auxiliary agent iron content is 0.60% of carrier quality.
(2) application performance evaluation and life-span are investigated
Adopt fixed bed reactors, reaction tube diameter 15mm, two sections of temperature controls.Add catalyst 10ml (stacking volume), upper strata is inertia porcelain bead rectification preheating, with 150ml/min, 100ml/min, 150ml/min, pass into carbon monoxide, methyl nitrite, nitrogen respectively, control heating-up temperature 120-140 ℃, at bed temperature 130-165 ℃, react and investigate yield, stable reaction started timing after one hour, successive reaction two hours, obtain dimethyl oxalate product 17.4g, amounting to yield is 870g (DMO)/l (cat) h.
Above-mentioned catalyst has been carried out to 100 hour life-span simultaneously and investigated, active situation is shown in Fig. 1.
Embodiment 2
(1) preparation of catalyst
0.075g palladium bichloride and 0.20g auxiliary agent ferric nitrate are dissolved in the hydrochloride buffer that pH=1.1 volume is 15ml, 15g alumina balls through calcination process are added in buffer solution, under the ultrasound condition of frequency 25Hz, after ultrasonic 3min, place at ambient temperature 12h, then put into drying box at 100 ℃ of dry 12h, then be dried 12h at 150 ℃; At 60 ℃, with 5 times of volumes of deionized water washing 10 times, every minor tick 2～3h, outwells after the solution soaking for the last time, put into 100 ℃ of baking ovens continuation and be dried 12h, by gained load the alumina balls of palladium pass into CO:N
2for the gas of 1:4 reduces 4h at 150～400 ℃, obtain Pd-Fe/Al
2o
3catalyst finished product.Pd content is wherein 0.3% of carrier quality, and auxiliary agent iron content is 0.30% of carrier quality.
(2) application performance evaluation
Employing is evaluated with the condition of embodiment 1, and successive reaction obtains dimethyl oxalate product 16.6g in two hours, and amounting to yield is 830g (DMO)/l (cat) h.
Embodiment 3
(1) preparation of catalyst
0.075g palladium bichloride and 0.27g auxiliary agent copper nitrate are dissolved in the hydrochloride buffer that pH=1.1 volume is 15ml, 15g alumina balls through calcination process are added in buffer solution, under the ultrasound condition of frequency 25Hz, after ultrasonic 2min, place at ambient temperature 12h, then put into drying box at 100 ℃ of dry 12h, then be dried 12h at 150 ℃; At 60 ℃, with 5 times of volumes of deionized water washing 10 times, every minor tick 2～3h, outwells after the solution soaking for the last time, put into 100 ℃ of baking ovens continuation and be dried 12h, by gained load the alumina balls of palladium pass into CO:N
2for the gas of 1:4 reduces 4h at 150～400 ℃, obtain Pd-Cu/Al
2o
3catalyst finished product.Pd content is wherein 0.3% of carrier quality, and Cu additives content is 0.60% of carrier quality.
(2) application performance evaluation
Employing is evaluated with the condition of embodiment 1, and successive reaction obtains dimethyl oxalate product 15.8g in two hours, and amounting to yield is 790g (DMO)/l (cat) h.
Embodiment 4
(1) preparation of catalyst
0.125g palladium bichloride and 0.30g auxiliary agent ferric nitrate are dissolved in the hydrochloride buffer that pH=1.1 volume is 15ml, 15g alumina balls through calcination process are added in buffer solution, under the ultrasound condition of frequency 25Hz, after ultrasonic 2min, place at ambient temperature 12h, then put into drying box at 100 ℃ of dry 12h, then be dried 12h at 150 ℃; At 60 ℃, with 5 times of volumes of deionized water washing 10 times, every minor tick 2～3h, outwells after the solution soaking for the last time, put into 100 ℃ of baking ovens continuation and be dried 12h, by gained load the alumina balls of palladium pass into CO:N
2for the gas of 1:4 reduces 4h at 150～400 ℃, obtain Pd-Cu/Al
2o
3catalyst finished product.Pd content is wherein 0.5% of carrier quality, and auxiliary agent iron content is 0.40% of carrier quality.
(2) application performance evaluation
Employing is evaluated with the condition of embodiment 1, and successive reaction obtains dimethyl oxalate product 19.6g in two hours, and amounting to yield is 980g (DMO)/l (cat) h.
Embodiment 5
Ultrasonic time in catalyst preparation in embodiment 1 is decided to be respectively to 0min, 1.5min, 5min, 10min, 15min, obtains five samples of A0-A4.The TEM phenogram of five samples of A0-A4 is shown in Fig. 2～6, and its decentralization test data is in Table 1,
Table 1. decentralization test result
| Sample title | Metal dispersity (%) | Metallic particle diameter (nm) |
| A0 | 17.2582 | 6.49242 |
| A1 | 26.6005 | 4.21222 |
| A2 | 23.5622 | 4.7540 |
| A3 | 22.1255 | 5.0632 |
| A4 | 20.1356 | 5.5638 |
By table 1 and Fig. 2-6, can be found out, reasonably ultrasonic time contributes to increasing substantially of decentralization, but along with the ultrasonic time increases, phase anticatalyst start to reunite grow up, decentralization reduces gradually.
Employing is carried out application performance evaluation with the application performance appreciation condition of embodiment 1 to five samples of A0-A4, and dimethyl oxalate yield is in Table 2:
The dimethyl oxalate yield of the different samples of table 2.
Have table 2 to find out, the dimethyl oxalate yield of the catalyst of the ultrasonic processing of process is improved than undressed catalyst, and ultrasonic time is that the catalyst effect of 1.5-5 minute is better.
Claims (4)
1. a CO synthesizing dimethyl oxalate catalyst, its chemical general formula is Pd-M/Al
2o
3, wherein active component palladium content is the 0.1-1% of carrier quality, and wherein M represents one of Fe, Cu, Zn, and M content is the 0.15-0.60% of carrier quality; The specific area of catalyst is 1-10m
2/ g; Carrier is that particle diameter is a type ball-aluminium oxide of 1-5mm.
2. CO synthesizing dimethyl oxalate catalyst according to claim 1, is characterized in that active component palladium content is the 0.2-0.6% of carrier quality, and M content is the 0.3-0.6% of carrier quality, and the decentralization of this catalyst activity component is 23-27%.
3. prepare a method for catalyst for CO synthesizing dimethyl oxalate claimed in claim 1, concrete steps are as follows:
A. palladium bichloride and auxiliary agent M salt are dissolved in and in hydrochloric acid solution, prepare dipping solution, according to every batch of consumption that needs the quality of impregnated carrier and the Pd content of required catalyst and M content to determine palladium bichloride and auxiliary agent M salt in dipping solution; Again by the addition of definite hydrochloric acid solution of every gram of carrier preparation 1mL dipping solution;
In described predetermined catalyst, Pd content is the 0.1-1% of carrier quality, and M content is the 0.15-0.60% of carrier quality; Described M salt is ferric nitrate, copper nitrate or zinc nitrate;
B. the maceration extract ultrasonic processing 1-20 minute in Ultrasound Instrument that steps A has been added to carrier, supersonic frequency is 20-59Hz, ultrasonic power is 50-100W; Standing 6-24h at 40-60 ℃ again; Put into baking oven dry 12-24h at 100-200 ℃; By deionized water, fully wash again; In baking oven, 150 ℃ are fully dried;
C. by dried catalyst precarsor at H
2or in CO atmosphere, reduce 4-8h at 150-400 ℃, obtain Pd-M/Al
2o
3catalyst.
4. the preparation method of catalyst for CO synthesizing dimethyl oxalate according to claim 3, it is characterized in that described in steps A that active component Pd content is the 0.2-0.6% of carrier quality, concentration of hydrochloric acid solution depends on the pH environment of prepared catalyst needs, pH is 0-6, M content is the 0.3-0.6% of carrier quality, and the ultrasonic processing time described in step B is 1-5 minute.
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Cited By (6)
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| CN105536815A (en) * | 2015-12-10 | 2016-05-04 | 大连瑞克科技有限公司 | Catalyst for preparing dimethyl oxalate from methyl nitrite and preparation method of catalyst |
| CN105597743A (en) * | 2016-03-01 | 2016-05-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate |
| CN105688934A (en) * | 2014-11-27 | 2016-06-22 | 上海华谊能源化工有限公司 | Catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate and preparation method and application thereof |
| CN105797717A (en) * | 2015-09-07 | 2016-07-27 | 中国科学院福建物质结构研究所 | Catalyst used for synthesis of dimethyl oxalate and preparation method thereof |
| CN108993518A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | A kind of heterogeneous lightwave CATV catalyst of nanocomposite and its preparation and application |
| CN110947399A (en) * | 2019-12-27 | 2020-04-03 | 宁波中科远东催化工程技术有限公司 | Palladium catalyst, preparation method thereof and dimethyl oxalate synthesis method |
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Cited By (8)
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| CN105688934A (en) * | 2014-11-27 | 2016-06-22 | 上海华谊能源化工有限公司 | Catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate and preparation method and application thereof |
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| CN105597743A (en) * | 2016-03-01 | 2016-05-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate |
| CN108993518A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | A kind of heterogeneous lightwave CATV catalyst of nanocomposite and its preparation and application |
| CN108993518B (en) * | 2018-08-16 | 2021-01-12 | 南京工业大学 | Nano composite material heterogeneous light Fenton catalyst and preparation and application thereof |
| CN110947399A (en) * | 2019-12-27 | 2020-04-03 | 宁波中科远东催化工程技术有限公司 | Palladium catalyst, preparation method thereof and dimethyl oxalate synthesis method |
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Application publication date: 20141119 |