CN101869843B - Preparation of metallic carbide on carrier and metallic carbide serving as diethanol amine dehydrogenation catalyst - Google Patents
Preparation of metallic carbide on carrier and metallic carbide serving as diethanol amine dehydrogenation catalyst Download PDFInfo
- Publication number
- CN101869843B CN101869843B CN 201010207501 CN201010207501A CN101869843B CN 101869843 B CN101869843 B CN 101869843B CN 201010207501 CN201010207501 CN 201010207501 CN 201010207501 A CN201010207501 A CN 201010207501A CN 101869843 B CN101869843 B CN 101869843B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- milliliters
- gram
- solution
- reversed phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to preparation of metallic carbide on a carrier and a dehydrogenation catalyst serving as diethanol amine for preparing sodium iminodiacetate, in particular to a preparation method and a preparation process for the metallic carbide on the carrier (such as active carbon, titanium oxide, aluminum oxide or zirconium oxide), and application of the dehydrogenation catalyst serving as the diethanol amine for preparing the sodium iminodiacetate. Metal of the metallic carbide in the catalyst is the metallic carbide formed by combining nano-scale granules and carbon, and is uniformly dispersed on the surface of a carrier material. Because the catalyst has fine metal granules and high dispersion property, the catalyst has high catalytic activity, namely the diethanol amine has high conversion rate and the produced sodium iminodiacetate has high selectivity and quality. The metallic carbide in the catalyst can be firmly combined with the carrier material together, so in the reaction of preparing the sodium iminodiacetate from the diethanol amine, the metallic components in the catalyst do not easily fall, and the service life of the catalyst is prolonged. After filtration and reclamation, the catalyst can be repeatedly used, so the cost for producing the sodium iminodiacetate is lowered.
Description
Technical field
1. the present invention relates at a kind of carrier (activated carbon for example, titanium oxide, aluminium oxide, or zirconia) preparation of upper metal carbide catalyst, be specifically related to preparation method and the process of this metal carbides on carrier, and in diethanolamine method synthesizing glyphosate route as the application of the dehydrogenation of diethanol amine iminodiacetic acid sodium processed.
Background technology
Glyphosate is a kind of wide spectrum, efficient, low toxicity organophosphorus herbicide, since About Monsanto Chemicals in 1971 is succeeded in developing, has become so far the in the world pesticide species of output maximum.The process for synthesizing glyphosate route is a lot of on industrial production both at home and abroad.Synthetic PMIDA, the glyphosate of diethanolamine method is present internationally recognized process for cleanly preparing route.Main feature: raw material is diethanol amine (DEA), under catalyst action, generates iminodiacetic acid sodium (DSIDA), the more acidified iminodiacetic acid (IDA) that just generates with alkali reaction under certain pressure; PMIDA (PMIDA), glyphosate (PMG) that the IDA that is produced by this method goes to synthesize are again approved for the World Food Programme, can export to the western countries such as American-European.Concrete synthetic method:
NH(CH
2CH
2OH)
2+2NaOH→NH(CH
2COONa)
2+4H
2 (I)
NH(CH
2COONa)
2+2HCl→NH(CH
2COOH)
2+2NaCl (II)
NH(CH
2COOH)
2+H
3PO
3+HCHO→(HO)
2P(O)CH
2N(CH
2COOH)
2 (III)
(HO)
2P(O)CH
2N(CH
2COOH)
2+O
2→(HO)
2P(O)CH
2NHCH
2COOH (IV)
In the above in the chemical equation, NH (CH
2CH
2OH)
2Diethanol amine (DEA); NH (CH
2COONa)
2Iminodiacetic acid sodium (DSIDA); NH (CH
2COOH)
2Iminodiacetic acid (IDA); (HO)
2P (O) CH
2N (CH
2COOH)
2PMIDA (PMIDA); (HO)
2P (O) CH
2NHCH
2COOH is glyphosate (PMG).
In diethanolamine method synthesizing glyphosate route, need a dehydrogenation in the iminodiacetic acid sodium reaction processed of first step diethanol amine.Industrial dehydrogenation for alcohol carboxylate processed can be used as the catalyst of diethanol amine iminodiacetic acid sodium processed.For example, Raney nickel, Raney Copper Processing Industry dehydrogenation.United States Patent (USP) 6376708 is described in detail and is used the application of Raney Copper Processing Industry dehydrogenation in diethanol amine iminodiacetic acid sodium processed.Because this is a general dehydrogenation, so DSIDA output is not very high, about 80%.After United States Patent (USP) 7632967 usefulness Pt or Pd improve Raney copper etc., more than the DSIDA output increased to 90%.But the catalyst cost that obtains so high (comprising two step manufacturing costs).On actual industrial production, also useful commercial Pd/Al
2O
3Or Pt/Al
2O
3Catalyst is as the catalyst of diethanol amine iminodiacetic acid sodium processed.But in diethanol amine iminodiacetic acid sodium reaction processed, need a large amount of highly basic (NaOH).Because the existence of highly basic is so that carrier A l
2O
3Malformation, even dissolving.This is easily so that be adsorbed on Al
2O
3Lip-deep metal Pd or Pt come off, and cause noble metal to run off and catalysqt deactivation.
Summary of the invention
Purpose of the present invention is exactly preparation method and the process that a kind of new catalyst is provided for the drawback of the dehydrogenation that overcomes above-mentioned diethanol amine iminodiacetic acid sodium processed.By replacing metal pure on the carrier at the upper preparation of a kind of carrier (for example activated carbon, titanium oxide, aluminium oxide, or zirconia) metal carbides.According to nearest invention, because the energy of the carbon in the metal carbides and carrier combine more closely, for example because the carbon in the noble metal carbide and the carbon on the activity carbon carrier belong to identity element, after high-temperature process, can form the combination of carbon carbon geochemistry, therefore, the noble metal carbide firmly is loaded on the carrier than noble metal is easier, and bullion content runs off and will greatly reduce in the catalyst like this.Catalyst can be repeatedly used, and has reduced the cost of catalyst in the production process.In addition because the adding of the second metal, form stable many metal alloys carbide with noble metal in the noble metal carbide, so that catalyst is more stable.
(1) metallic carbide on carrier catalyst
The iminodiacetic acid sodium dehydrogenation processed of diethanol amine described in the present invention is at a metallic carbide on carrier catalyst.The carrier here is activated carbon, titanium oxide, and aluminium oxide, or in the zirconia one, wherein activated carbon is as the preferential carrier of selecting.The metal of described metal carbides refers to one or more in the following metal: gold, silver, platinum group metal (ruthenium, rhodium, palladium, osmium, iridium, platinum), cobalt, nickel, chromium, vanadium, cadmium, zinc, iron, manganese, copper, tin, titanium, lead, antimony, bismuth and cerium.The tenor scope can be 0.001-75% in the catalyst, and comparatively ideal tenor scope is 0.1-20%, and best tenor scope is 10-15%.The carbon of described metal carbides produces in pyroreaction by carbonization gas and metal.
(2) metallic carbide on carrier catalyst preparation process
The metal appendix can soak by stain to carrier surface, precipitation, and ion-exchange, chemistry or physical absorption, reduction reaction, and the one or more technology in reversed phase micelle (Reverse Micelle) etc. the technology are in conjunction with finishing.The metal appendix to the carrier surface after, with the carbonization gas of dilution under certain carburizing temperature with carrier surface on the metallic carbide reaction and obtain metal carbides.The carburizing temperature scope can be selected from 200 ℃ to 1400 ℃; Comparatively ideal carburizing temperature scope is 450 ℃ to 950 ℃; Best carburizing temperature scope is 600 ℃ to 800 ℃.The used gas of carbonization can be the methane of dilution, ethane, propane, butane, ethene, propylene, butylene, acetylene gas.Consider that from economic factor methane is best carbonization gas.The gas of dilution carbonization gas can be selected hydrogen, nitrogen, helium or argon gas a kind of.Methane can be any concentration in the concentration of diluent gas, but considers that carbonization time and running cost, 15-25% concentration of methane gas are best selections.
The specific embodiment
Following implementation example is further set forth in order to allow technological means of the present invention and preparation method be easy to understand.In metal carbide catalyst embodiment; we only show as carrier and reversed phase micelle technology of preparing and process with activated carbon and describe basic principle of the present invention; other carrier (titanium oxide for example; aluminium oxide; or zirconia) and technology of preparing (for example the stain soak; precipitation, co-precipitation etc. technology) makes metal carbides and be used for all belonging to the claimed scope of the present invention at diethanol amine iminodiacetic acid sodium processed as dehydrogenation.So the present invention is not subjected to the restriction of following specific embodiment, the present invention also can change without departing from the spirit and scope of the present invention, and these variations should belong in the scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent.
Embodiment 1 activity carbon carrier platinum cobalt metal carbide catalyst
Here we prepare the metal carbides carried catalyst with reversed phase micelle (Reverse Micelle) technology.In order to guarantee that all operations carries out under inert environments, we use Xi Laike device (Schlenk line) to finish.5 gram dioctyl sodium sulfosuccinates (AOT), 5 gram butanols-1,12 gram cyclohexanes, and 6 milliliters of 2M CoCl
2Be added on the Xi Laike device in 300 milliliters of three-necked bottles.Stirring at room formed peach reversed phase micelle solution (I) in 30 minutes under inert gas (for example argon gas) atmosphere.5 gram dioctyl sodium sulfosuccinates (AOT), 5 gram butanols-1,12 gram cyclohexanes, and 12 milliliters of 2M NaBH
4Under argon gas atmosphere, be added on the Xi Laike device in 100 milliliters of three-necked bottles.Form colourless reversed phase micelle solution (II).Reversed phase micelle solution (II) in 100 milliliters of three-necked bottles is transferred in the three-necked bottle of 300 milliliters of pink reversed phase micelle solution (I) by at leisure (30 minutes) under argon gas atmosphere, and color changes to grey at leisure by pink.This shows CoCl in solution
2By NaBH
4Be reduced into the cobalt particle of nano-scale:
2CoCl
2+NaBH
4+4H
2O→2Co↓+NaB(OH)
4+4HCl+2H
2↑
Reversed phase micelle solution (III) is by 5 gram dioctyl sodium sulfosuccinates (AOT), 5 gram butanols-1,12 gram cyclohexane and 2 milliliters of 0.5M H
2PtCl
6Form.Under argon gas atmosphere, shift at leisure reversed phase micelle solution (III) in the top cobalt particle solution that comprises nano-scale.Stirring at room forms a new solution after 30 minutes.Another is by 5 gram dioctyl sodium sulfosuccinates (AOT), and 5 gram butanols-1,12 restrain cyclohexanes, and 3 milliliters of 2MNaBH
4The reversed phase micelle solution (IV) that forms is joined in this new soln by at leisure (30 minutes) under argon gas atmosphere.H in new soln
2PtCl
6By NaBH
4During reduction, the color of the solution changes to black at leisure by grey.This shows that the topped platinum cobalt particle in the lip-deep nano-scale of Co of Pt forms in solution:
H
2PtCl
6+NaBH
4+4H
2O→Pt↓+NaB(OH)
4+6HCl+2H
2↑
A certain amount of activity carbon carrier and 50 milliliters of cyclohexanes join in the platinum cobalt particle solution that comprises nano-scale, continue to stir more than 8 hours.In order to break the reversed phase micelle in the solution, 50 milliliters of ethanol are added into rear continuation and stirred 30 minutes.Filter and with after the ethanol water washing in 1: 1, filter cake is dried more than 8 hours at 100-120 ℃.Filter cake 20%CH after the oven dry
4/ H
2Mist formed platinum cobalt metal carbides in 4 hours 700 ℃ of lower carbonizations.Then use argon gas (helium or nitrogen) to be cooled fast to room temperature, with obtaining activity carbon carrier platinum cobalt metal carbide catalyst behind 5-10% air/nitrogen blowing.The weight ratio of platinum cobalt in the catalyst=1: 3.6.The content that the content of platinum cobalt can be adjusted to the platinum cobalt according to the amount that adds activated carbon in the catalyst is 4.0% and 14.4%.
Embodiment 2 activity carbon carrier palladium copper metal carbide catalysts
In embodiment 8, remove with 6 milliliters of 1M CuCl
2Replace 2 milliliters of 1M CoCl
2With 2 milliliters of 0.5M PdCl
2Replace 4 milliliters of 0.5M H
2PtCl
6Outward, the weight ratio of palladium copper=1: 3.6.Other all preparation method is identical with embodiment 1 with process.The content that the content of palladium copper can be adjusted to palladium copper according to the amount that adds activated carbon in the catalyst is 4.0% and 14.4%.
Embodiment 3 diethanol amine iminodiacetic acid sodium processed
With 105 gram diethanol amine, activity carbon carrier palladium copper metal carbide catalyst 40 restrains among the embodiment 2 under nitrogen atmosphere, the 190 gram 50%NaOH aqueous solution, and 160 gram deionized waters are put into 1 liter autoclave.Reaction temperature is controlled at about 160 ℃, and reaction pressure is controlled at 1.0MPa, and mixing speed is 1000rpm.Judge by the hydrogen of measuring the reactor outlet whether reaction finishes.Discharge when the reactor outlet can't detect hydrogen, reaction finishes.Still liquid cool to room temperature, discharging, by filtering, the catalyst of recovery can be reused.
Be full of autoclave with nitrogen, new reaction mass adds next time again and reacts.Table 1 is listed catalyst and is reused ten times result.
Table 1
| Catalyst circulation is used (number of times) | Reaction temperature (℃) | Reaction time (minute) | Diethanol amine conversion ratio % | Iminodiacetic acid sodium yield % |
| 1 | 158 | 126 | 99.5 | 94.6 |
| 2 | 161 | 118 | 99.3 | 95.2 |
| 3 | 160 | 130 | 99.8 | 92.8 |
| 4 | 157 | 136 | 99.2 | 95.6 |
| 5 | 159 | 133 | 99.6 | 93.2 |
| 6 | 160 | 135 | 99.5 | 91.9 |
| 7 | 161 | 138 | 99.1 | 92.8 |
| 8 | 160 | 147 | 99.7 | 94.2 |
| 9 | 159 | 146 | 99.3 | 91.3 |
| 10 | 161 | 142 | 99.6 | 93.8 |
Claims (1)
1. the preparation method of an absorbent charcoal carrier platinum cobalt metal carbide catalyst, it is characterized in that preparing the metal carbides carried catalyst with the reversed phase micelle technology, in order to guarantee that all operations carries out under inert environments, reaction Yong Xi Laike device is finished, 5 gram dioctyl sodium sulfosuccinates, 5 gram butanols-1,12 gram cyclohexanes, and 6 milliliters of 2M CoCl
2Be added on the Xi Laike device in 300 milliliters of three-necked bottles, stirring at room formed peach reversed phase micelle solution I in 30 minutes under argon gas atmosphere; 5 gram dioctyl sodium sulfosuccinates, 5 gram butanols-1,12 gram cyclohexanes, and 12 milliliters of 2M NaBH
4Under argon gas atmosphere, be added on the Xi Laike device in 100 milliliters of three-necked bottles, form colourless reversed phase micelle solution II; In the three-necked bottle through being transferred at leisure 300 milliliters of pink reversed phase micelle solution I in 30 minutes, color changes to grey by pink to reversed phase micelle solution II in 100 milliliters of three-necked bottles at leisure under argon gas atmosphere, and this shows CoCl in solution
2By NaBH
4Be reduced into the cobalt particle of nano-scale;
The reversed phase micelle solution III is by 5 gram dioctyl sodium sulfosuccinates, and 5 gram butanols-1,12 restrain cyclohexane and 2 milliliters of 0.5M H
2PtCl
6Form, shift at leisure the reversed phase micelle solution III under argon gas atmosphere in the above-mentioned cobalt particle solution that comprises nano-scale, stirring at room forms a new solution after 30 minutes, another is by 5 gram dioctyl sodium sulfosuccinates, 5 gram butanols-1,12 gram cyclohexanes, and 3 milliliters of 2M NaBH
4The reversed phase micelle solution IV that forms was joined in this new soln at leisure through 30 minutes under argon gas atmosphere; H in new soln
2PtCl
6By NaBH
4During reduction, the color of the solution changes to black at leisure by grey; This platinum cobalt particle that shows that Pt covers the lip-deep nano-scale of Co forms in solution;
A certain amount of absorbent charcoal carrier and 50 milliliters of cyclohexanes join in the platinum cobalt particle solution that comprises nano-scale, continue to stir more than 8 hours, in order to break the reversed phase micelle in the solution, 50 milliliters of ethanol are added into rear continuation and stirred 30 minutes, after filtering and washing with 1: 1 ethanol water, filter cake is dried more than 8 hours the filter cake 20%CH after the oven dry at 100-120 ℃
4/ H
2Mist formed platinum cobalt metal carbides in 4 hours 700 ℃ of lower carbonizations, then be cooled fast to room temperature with argon gas, with obtaining absorbent charcoal carrier platinum cobalt metal carbide catalyst behind 5-10% air/nitrogen blowing, the weight ratio of platinum cobalt in the catalyst=1: 3.6, the content that the content of platinum cobalt is adjusted to respectively platinum according to the amount that adds activated carbon in the catalyst be 4.0% and the content of cobalt be 14.4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010207501 CN101869843B (en) | 2010-06-24 | 2010-06-24 | Preparation of metallic carbide on carrier and metallic carbide serving as diethanol amine dehydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010207501 CN101869843B (en) | 2010-06-24 | 2010-06-24 | Preparation of metallic carbide on carrier and metallic carbide serving as diethanol amine dehydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101869843A CN101869843A (en) | 2010-10-27 |
| CN101869843B true CN101869843B (en) | 2013-04-24 |
Family
ID=42995039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010207501 Expired - Fee Related CN101869843B (en) | 2010-06-24 | 2010-06-24 | Preparation of metallic carbide on carrier and metallic carbide serving as diethanol amine dehydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101869843B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442120A (en) * | 2017-08-28 | 2017-12-08 | 湘潭大学 | A kind of Cu/ZrO2Catalyst and its production and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6794331B2 (en) * | 2000-02-18 | 2004-09-21 | Degussa Ag | Raney copper |
| CN1827218A (en) * | 2006-03-30 | 2006-09-06 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
| CN1867404A (en) * | 2003-08-14 | 2006-11-22 | 孟山都技术公司 | Transition metal-carbide and nitride containing catalysts, their preparation and use as oxidation and dehydrogenation catalysts |
-
2010
- 2010-06-24 CN CN 201010207501 patent/CN101869843B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6794331B2 (en) * | 2000-02-18 | 2004-09-21 | Degussa Ag | Raney copper |
| CN1867404A (en) * | 2003-08-14 | 2006-11-22 | 孟山都技术公司 | Transition metal-carbide and nitride containing catalysts, their preparation and use as oxidation and dehydrogenation catalysts |
| CN1827218A (en) * | 2006-03-30 | 2006-09-06 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442120A (en) * | 2017-08-28 | 2017-12-08 | 湘潭大学 | A kind of Cu/ZrO2Catalyst and its production and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101869843A (en) | 2010-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9463444B2 (en) | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase CO oxidative coupling to oxalate | |
| CN103007929B (en) | The Pd bases catalyst of colloidal deposition method preparation, preparation method and application | |
| US20160332953A1 (en) | A process for vapor-phase methanol carbonylation to methyl formate, a catalyst used in the process and a method for preparing the catalyst | |
| CN103170349A (en) | Copper catalyst for selective hydrogenation of mixed C4 and preparation method of copper catalyst | |
| CN108993577A (en) | A kind of catalyst and its preparation method and application of prepared from benzene and hydrogen cyclohexyl benzene | |
| CN111389443A (en) | Non-noble metal mercury-free catalyst for acetylene hydrochlorination and preparation method thereof | |
| CN101569859A (en) | Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst | |
| CN101549292A (en) | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof | |
| CN105130821B (en) | It is a kind of to reduce the green synthesis method that ortho-nitraniline prepares o-phenylenediamine | |
| CN106694009A (en) | Method for preparing lower-carbon glycols through alloy catalyst used for carbohydrate catalysis | |
| CN103372453A (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN105859610A (en) | Synthesis method of 2,2'-dipyridine by using supported bimetal nano catalyst | |
| CN109745986A (en) | Hydrotalcite composite transition metal catalyst is for the purposes in cyclohexanol ammonolysis reaction | |
| CN103170335A (en) | Effective carbon dioxide conversion catalyst and preparing method thereof | |
| CN110801841A (en) | Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof | |
| CN107626329A (en) | A kind of platinum/aluminium oxide catalyst and its preparation method and application | |
| CN101289365B (en) | Low-temperature catalytic benzene hydrogenation method and special catalyst thereof | |
| CN108435171A (en) | The preparation method and a kind of method of selective catalytic oxidation glycerine DHA of a kind of bimetallic Pt-Bi catalyst | |
| CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
| CN101869843B (en) | Preparation of metallic carbide on carrier and metallic carbide serving as diethanol amine dehydrogenation catalyst | |
| CN107952490A (en) | A kind of preparation method of silver-raney copper catalyst, catalyst prepared therefrom and application | |
| CN105749913B (en) | The catalyst and acetate preparation of ethanol through hydrogenation method of acetate preparation of ethanol through hydrogenation | |
| CN101862665B (en) | Preparation of metal carbide on carriers and use of metal carbide as N-(Phosphonomethyl) iminodiacetic acid oxidation catalyst | |
| CN102872862A (en) | Carrier type platinum-ruthenium catalyst and application of carrier type platinum-ruthenium catalyst in hydrogenation of aromatic nitro compound | |
| CN102861573A (en) | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130424 Termination date: 20140624 |
|
| EXPY | Termination of patent right or utility model |