CN104190415A - Anion regulation and control adopted method for preparing Pd/alpha-Al2O3 catalyst - Google Patents
Anion regulation and control adopted method for preparing Pd/alpha-Al2O3 catalyst Download PDFInfo
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- CN104190415A CN104190415A CN201410435876.9A CN201410435876A CN104190415A CN 104190415 A CN104190415 A CN 104190415A CN 201410435876 A CN201410435876 A CN 201410435876A CN 104190415 A CN104190415 A CN 104190415A
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Abstract
The invention discloses an anion regulation and control adopted method for preparing a Pd/alpha-Al2O3 catalyst and belongs to the technical field of dimethyl oxalate preparation. The catalyst takes alpha-Al2O3 as a carrier and takes precious metal Pd nanoparticles as an active ingredient, wherein the content (by weight) of the active ingredient Pd in the catalyst is 0.05-1%. The dispersion degree and distribution area of the active ingredient of the catalyst in the carrier can be controlled in a certain range; the metal dispersion degree of the catalyst prepared by the method is high, CO gas-phase carbonylation can be efficiently catalyzed at relatively low temperature and low precious metal load, so as to synthesize dimethyl oxalate, the selectivity of oxalate is high, the amount of decomposition of methyl nitrite is small, and the space-time yield of dimethyl oxalate reaches up to 1,000g/L/h (the space velocity is 2,400/h).
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, particularly a kind of employing anion regulation and control preparation Pd/ α-Al
2o
3the preparation method of catalyst.
Background technology
The current production method of ethylene glycol mainly generates oxirane by ethene through the gaseous oxidation on silver catalyst, then carries out the hydration of liquid phase on-catalytic and make ethylene glycol product.What this technique was walked is petroleum path, and China is the oily country less of coal more than, so the synthetic method of utilizing Coal Chemical Industry and natural gas produces the route of ethylene glycol and traditional ethene route has obvious competitive advantage, can alleviate to a certain extent the pressure to the confession quantity not sufficient of the dependence of oil and ethene, there is long-range strategic importance.
Synthesis gas synthesizing glycol can be divided into directly to be sent out and indirect method, and direct method is because the higher synthesis pressure of needs (50MPa) and higher reaction temperature (230～260 ℃) have been limited to it in industrial application; The process conditions of the CO oxidative coupling synthesizing dimethyl oxalate method in indirect method are relatively simple and reaction condition is gentleer, entered the industrial applications stage, and obtained good economic benefit.But this step of CO coupling synthesizing dimethyl oxalate needs the participation of catalyst, and the load capacity of catalyst P d relatively high (industrial up to 2%), along with a large amount of consumption of noble metal in industrial catalyst and jewelry industry, cause Precious Metals Resources shortage gradually, in order further to reduce the production cost of catalyst, the consumption of precious metals pd be need to reduce, and the high stability of catalyst and the space-time yield of oxalate kept simultaneously.At present domestic in succession report added the patent of space-time yield that different auxiliary agents improve the oxalate of catalyst, but the consumption of the Pd in catalyst is all in 1% left and right, patent CN201110241310.9, CN201110415823.7 has provided the method for preparing catalyst that Pd content is 0.5-2%, but need in alkali-free liquid phase environment, use structure directing reagent and protective agent to reduce in the method, preparation method is complicated, the content of Pd is also higher, therefore a kind of research and development of CO oxidative coupling synthesizing dimethyl oxalate of new and effective low noble metal Pd load capacity have important strategic importance.
Summary of the invention
For solving above-mentioned one or more problem, the invention provides a kind of employing anion regulation and control preparation Pd/ α-Al
2o
3the preparation method of catalyst, the steps include:
(1) precursor of the precursor of palladium and auxiliary agent is dissolved in the solution of certain pH value and makes maceration extract;
(2) by the α-Al through calcination process
2o
3ball adds in the prepared maceration extract of step (1), in maceration extract, adds appropriate ion salt, then at 40～60 ℃ standing 6～24h;
(3) by the α-Al after step (2) processing
2o
3ball, puts into baking oven dry 12～24h at 100～200 ℃;
(4) α-Al after step (3) processing
2o
3ball, fully washs by deionized water;
(5) α-Al after washing
2o
3ball is fully dry in baking oven;
(6) dry rear gained catalyst precarsor is in hydrogen or carbon monoxide atmosphere, and 4～the 8h that reduces at 150～400 ℃ obtains catalyst of the present invention,
Its active component of described catalyst is the palladium of high dispersive form, α-Al that carrier is inertia
2o
3ball, is mainly used in the reaction of CO oxidative coupling synthesizing dimethyl oxalate, has excellent catalytic activity and selective.
That is to say, the invention provides a kind of method of carrying out Kaolinite Preparation of Catalyst by add specific ion salt and suitable content in maceration extract, the prepared catalyst of the method significantly changes the distribution of the dispersed of noble metal active component and noble metal active component, thereby guarantees to be issued to good catalytic activity effect in the condition of extremely low noble metal dosage.The present invention be take palladium bichloride as palladium source, the ball-aluminium oxide of take (has certain mechanical strength as carrier, diameter range is at 1-10mm), in preparation, adopt the mode of adding ion salt 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.
Accompanying drawing explanation
Fig. 1 is the life-span investigation figure of the M4 catalyst prepared in one embodiment of the present of invention;
Fig. 2 is the transmission electron microscope photo of the M0 catalyst prepared in one embodiment of the present of invention;
Fig. 3 is the transmission electron microscope photo of the M4 catalyst prepared in one embodiment of the present of invention;
Fig. 4 is the section optical microscope photograph of the M0 catalyst prepared in one embodiment of the present of invention;
Fig. 5 is the section optical microscope photograph of the M1 catalyst prepared in one embodiment of the present of invention;
Fig. 6 is the section optical microscope photograph of the M2 catalyst prepared in one embodiment of the present of invention;
Fig. 7 is the section optical microscope photograph of the M3 catalyst prepared in one embodiment of the present of invention;
Fig. 8 is the section optical microscope photograph of the M4 catalyst prepared in one embodiment of the present of invention;
Fig. 9 is the section optical microscope photograph of the M5 catalyst prepared in one embodiment of the present of invention.
The specific embodiment
The invention discloses a kind of employing anion regulation and control preparation Pd/ α-Al
2o
3the preparation method of catalyst, the steps include:
(1) precursor of the precursor of palladium and auxiliary agent is dissolved in the solution of certain pH value and makes maceration extract;
(2) by the α-Al through calcination process
2o
3ball adds in the prepared maceration extract of step (1), in maceration extract, adds appropriate ion salt, then at 40～60 ℃ standing 6～24h;
(3) by the α-Al after step (2) processing
2o
3ball, puts into baking oven dry 12～24h at 100～200 ℃;
(4) α-Al after step (3) processing
2o
3ball, fully washs by deionized water;
(5) α-Al after washing
2o
3ball is fully dry in baking oven;
(6) dry rear gained catalyst precarsor is in hydrogen or carbon monoxide atmosphere, and 4～the 8h that reduces at 150～400 ℃ obtains catalyst of the present invention,
Its active component of described catalyst is the palladium of high dispersive form, α-Al that carrier is inertia
2o
3ball, is mainly used in the reaction of CO oxidative coupling synthesizing dimethyl oxalate, has excellent catalytic activity and selective.
From the 100h study on the stability curve map of Fig. 1, can find, the yield of catalyst is substantially consistent in 100h evaluation procedure, illustrates that the stability of catalyst is better.The dispersion that can observe catalyst from the TEM photo of Fig. 2 and Fig. 3 is more even, and grain size is less.From Fig. 4, to 9 observations, can find, the active component of catalyst is at the certain spatial distribution state of having of carrier inside, and the difference of distribution also can cause that the performance of catalyst changes.
Comprehensive, catalyst activity component high degree of dispersion prepared by the inventive method, active component is specific spatial distribution state in carrier granular, catalyst finished particle diameter 1-10mm, and 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.
In another embodiment, the precursor of the palladium described in step (1) adopts: any one or more any combination in palladium bichloride, palladium nitrate, palladium and acetylacetone,2,4-pentanedione, in final gained catalyst, the content of palladium is counted 0.05%～1.0% of vehicle weight with palladium element.
In another embodiment, the ion salt adding in step (2) adopts: one or more in chlorate, sulfate and nitrate.
In another embodiment, described ion salt adopts NaCl, NaBr, Na
2sO
4.
In another embodiment, the concentration of described ion salt is 0～200g/L.
In another embodiment, described in step (1), solution is the acid solutions such as hydrochloric acid solution, salpeter solution, and its pH is between 0～6.
With example, further illustrate the present invention below, but the invention is not restricted to example.
Example 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, 15g alumina balls through calcination process are added in 15ml maceration extract, place at ambient temperature 12h, then put into drying box dry 12h at 100 ℃, then at 150 ℃, be dried 12h; 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
2be that the gas of 1: 4 reduces 4h at 150～400 ℃, obtain catalyst finished product.Pd content is wherein 0.3% of carrier quality, and auxiliary agent iron content is 0.6% of carrier quality.
(2) 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 13.6g, amounting to yield is 680g (DMO)/l (cat) h.
Example 2:
In example 1, the ion salt quality adding in catalyst preparation is respectively: 0g, 0.5g, 1g, 1.5g, 2g, 2.5g, make that the concentration of ion salt in maceration extract is 0,33.3g/L, 66.7g/L, 100g/L, 130g/L, 167g/L, i.e. cost example sample M0-M5.
Performance evaluation condition is with example 1, and dimethyl oxalate yield is respectively as following table:
M4 catalyst has been carried out to the life-span of 100h and investigated, active situation is shown in Fig. 1.
Sample characterization:
By TEM picture (seeing Fig. 2～3) and section optical microscope photograph (seeing Fig. 4～9), can find out, anion add impregnating depth and the thickness that has changed catalyst sample active component, thereby affect the degree of decomposition of catalyst to the selective and methyl nitrite of dimethyl oxalate.Yet test (seeing the following form) by decentralization, find, the introducing of anion does not cause the significant change of decentralization.
| Sample title | Metal?Dispersion(％) | Crystallite?Size(nm) |
| M0 | 28.5320 | 3.9254 |
| M1 | 28.0127 | 3.9981 |
| M2 | 27.9956 | 4.0006 |
| M3 | 28.3258 | 3.9541 |
| M4 | 28.4650 | 3.9346 |
| M5 | 28.3320 | 3.9531 |
Above disclosed is only preferred embodiment of the present invention, certainly can not limit with this interest field of the present invention, and the equivalent variations of therefore doing according to the claims in the present invention, still belongs to the scope that the present invention is contained.
Claims (6)
1. one kind adopts anion regulation and control preparation Pd/ α-Al
2o
3the preparation method of catalyst, the steps include:
(1) precursor of the precursor of palladium and auxiliary agent is dissolved in the solution of certain pH value and makes maceration extract;
(2) by the α-Al through calcination process
2o
3ball adds in the prepared maceration extract of step (1), in maceration extract, adds appropriate ion salt, then at 40～60 ℃ standing 6～24h;
(3) by the α-Al after step (2) processing
2o
3ball, puts into baking oven dry 12～24h at 100～200 ℃;
(4) α-Al after step (3) processing
2o
3ball, fully washs by deionized water;
(5) α-Al after washing
2o
3ball is fully dry in baking oven;
(6) dry rear gained catalyst precarsor is in hydrogen or carbon monoxide atmosphere, and 4～the 8h that reduces at 150～400 ℃ obtains catalyst of the present invention,
Its active component of described catalyst is the palladium of high dispersive form, α-Al that carrier is inertia
2o
3ball, is mainly used in the reaction of CO oxidative coupling synthesizing dimethyl oxalate, has excellent catalytic activity and selective.
2. preparation method as claimed in claim 1, it is characterized in that: the precursor of the palladium described in step (1) adopts: any one or more any combination in palladium bichloride, palladium nitrate, palladium and acetylacetone,2,4-pentanedione, in final gained catalyst, the content of palladium is counted 0.05%～1.0% of vehicle weight with palladium element.
3. preparation method as claimed in claim 1, is characterized in that: the ion salt adding in step (2) adopts: one or more in chlorate, sulfate and nitrate.
4. preparation method as claimed in claim 3, is characterized in that: preferred, described ion salt adopts NaCl, NaBr, Na
2sO
4deng.
5. the preparation method as described in claim 3 or 4, is characterized in that: the concentration of described ion salt is 0～200g/L.
6. preparation method as claimed in claim 1, is characterized in that: described in step (1), solution is the acid solutions such as hydrochloric acid solution, salpeter solution, and its pH is between 0～6.
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| CN201410435876.9A CN104190415B (en) | 2014-08-29 | 2014-08-29 | A kind of anion that adopts regulates and controls preparation Pd/ α-Al 2o 3the preparation method of catalyst |
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| CN104190415B CN104190415B (en) | 2016-04-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492794A (en) * | 2016-10-10 | 2017-03-15 | 中国科学院福建物质结构研究所 | Sodium sulfite reduction prepares Pd/a Al2O3Catalyst and its preparation method and application |
| WO2018053690A1 (en) * | 2016-09-20 | 2018-03-29 | 高化学技术株式会社 | Catalyst carrier and catalyst comprising same |
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| JPS5218154A (en) * | 1975-08-01 | 1977-02-10 | Hitachi Ltd | Frequency addition circuit |
| CN101612580A (en) * | 2009-07-22 | 2009-12-30 | 西南化工研究设计院 | A kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling and preparation method thereof |
| CN102600862A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for synthesizing dimethyl oxalate from CO |
| CN102649057A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
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2014
- 2014-08-29 CN CN201410435876.9A patent/CN104190415B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5218154A (en) * | 1975-08-01 | 1977-02-10 | Hitachi Ltd | Frequency addition circuit |
| CN101612580A (en) * | 2009-07-22 | 2009-12-30 | 西南化工研究设计院 | A kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling and preparation method thereof |
| CN102649057A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
| CN102600862A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for synthesizing dimethyl oxalate from CO |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018053690A1 (en) * | 2016-09-20 | 2018-03-29 | 高化学技术株式会社 | Catalyst carrier and catalyst comprising same |
| RU2697704C1 (en) * | 2016-09-20 | 2019-08-19 | Хайкем Текнолоджи Ко., Лтд | Catalyst support and catalyst containing it |
| CN106492794A (en) * | 2016-10-10 | 2017-03-15 | 中国科学院福建物质结构研究所 | Sodium sulfite reduction prepares Pd/a Al2O3Catalyst and its preparation method and application |
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| CN104190415B (en) | 2016-04-27 |
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Effective date of registration: 20180117 Address after: 562300 Guizhou Province, Xingren Buyi and Miao Autonomous Prefecture Xingren County Economic Development Zone (Industrial Park) Patentee after: Guizhou Xin alcohol science and Technology Development Co., Ltd. Address before: Yang Qiao Road, Gulou District of Fuzhou city of Fujian Province, No. 155 350002 Patentee before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
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Denomination of invention: A preparation method of Pd/a-Al2o3catalyst by anionic control Effective date of registration: 20200525 Granted publication date: 20160427 Pledgee: Guizhou Xinchun Energy Co., Ltd Pledgor: Guizhou Xin alcohol science and Technology Development Co., Ltd. Registration number: Y2020110000003 |
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