CN103418382A - Preparation method of copper-zirconium catalyst used for synthesizing iminodiacetic acid - Google Patents
Preparation method of copper-zirconium catalyst used for synthesizing iminodiacetic acid Download PDFInfo
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- CN103418382A CN103418382A CN2012101519971A CN201210151997A CN103418382A CN 103418382 A CN103418382 A CN 103418382A CN 2012101519971 A CN2012101519971 A CN 2012101519971A CN 201210151997 A CN201210151997 A CN 201210151997A CN 103418382 A CN103418382 A CN 103418382A
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Abstract
The invention belongs to the field of catalyst preparation, and relates to a preparation method of a copper-zirconium catalyst used for synthesizing iminodiacetic acid. The method comprises the steps that: an organic solvent and deionized water are added into copper-zirconium precipitate particles prepared with a precipitation method; heating and refluxing are carried out; and the above mixture is cooled, and is subjected to separation, drying, roasting, reducing, and the like, such that the catalyst is prepared. When the catalyst is applied in a reaction for preparing iminodiacetic acid from diethanolamine, reaction time can be substantially reduced, reaction yield can be improved, production cost can be reduced, and industrial production requirement can be satisfied.
Description
Technical field
The invention belongs to the catalyst preparation field, relate to a kind of method that improves the Cu-Zr catalyst activity, be specifically related to the preparation method of a kind of synthesis of iminodiacetic acid with Cu-Zr catalyst.
Background technology
Iminodiacetic acid (IDA), have another name called the N-(carboxymethyl) glycine, molecular formula C
4H
7NO
4, white crystalline powder or white monoclinic crystal.At present, the iminodiacetic acid of China more than 90% be for the production of herbicide glyphosate, and all the other are for agricultural chemicals, dyestuff, medicine, chemical industry, food additives, water treatment, the field such as electric.Along with technological progress and development, the application that iminodiacetic acid is new is developed gradually and is expanded.
The IDA preparation method has three approach: (1) chloroactic acid method; (2) hydrogen cyanide method; (3) diethanolamine method.In recent years, along with country, to the raising of environmental requirement and the continuous rise in price of natural gas, make chloroactic acid method, hydrogen cyanide method be restricted to a certain extent, diethanolamine method will become main flow technique gradually.It is a catalytic dehydrogenating reaction that diethanol amine prepares iminodiacetic acid, and its key is the performance of catalyst.Patent US4782183, US5220055, US529293, US533939 have introduced the process with the standby iminodiacetic acid of thunder Buddhist nun copper, and wherein the conversion ratio of diethanol amine is all higher than 97.5%, Iminodiacetate selectively higher than 95.7%.These patents are mainly in Lei Nitong, to add noble metal to change the internal structure of thunder Buddhist nun copper as second, third component, or change between catalyst and raw material the catalytic performance such as absorption affinity, the catalyst of preparation can not only improve repeat usage thus, and has greatly reduced accessory substance.But added noble metal in catalyst, increased the catalyst cost.On the other hand, there is the characteristics such as easy oxidation, difficult moulding due to Lei Nitong, can not realize serialization production, limited to a certain extent the development of this technique.Cu-Zr catalyst is the advantages such as preparation process is simple, preparation cost is low, easy-formation because having, and preparation method and the catalytic performance thereof of this catalyst have been done to a large amount of research work both at home and abroad.Introduce in patent US4782183 and take the copper catalyst that zirconium dioxide is carrier, 5h is carried out in reaction under 170 ℃, the conversion ratio 97.7% of diethanol amine, the yield 93.2% of Iminodiacetate, relatively long reaction time power consumption is larger, and this is that people do not expect.The disclosed Cu-Zr catalyst of patent CN1537844A prepares the method for IDA, adopt fixed bed evaluation method catalyst is estimated, feed stock conversion reaches 95%, product yield reaches 93.2%, still has the defect that catalyst activity is poor, reaction yield is lower.
Summary of the invention
Prepare IDA and have long, the problem such as energy consumption is large, catalyst activity is low of reaction time in order to overcome the Cu-Zr catalyst used in prior art, the present invention is devoted to the study on the modification of Cu-Zr catalyst, to reach Reaction time shorten, reduce energy consumption, improve reaction yield, thereby reach the purpose that reduces production costs, meets demand of industrial production.
The inventor is by a large amount of condition experiments, established a kind of method that diethanol amine prepares Cu-Zr catalyst performance used in iminodiacetic acid technique that improves: in the known process for preparing Cu-Zr catalyst, add organic solvent reflow treatment step, can unexpectedly obtain fast, the selective high Cu-Zr catalyst of a kind of reaction rate, realize thus purpose of the present invention.
Technical scheme of the present invention is as follows:
The preparation method of Cu-Zr catalyst for a kind of synthesis of iminodiacetic acid, comprise: in the copper zirconium deposit seed prepared to the precipitation method, add organic solvent and deionized water, add hot reflux, after mixture is cooling, through separation, drying, roasting, reduction, make catalyst; Described organic solvent is selected from alcohols or amine solvent, and consumption of organic solvent and zirconium ion amount are mole to count (0.1～32): 1, and adding deionized water to regulate copper zirconium ion concentration in the recirculate mixing thing is 0.05～1.2mol/L..
The comparatively preferred technical scheme of the present invention is to operate according to the following steps:
1) precipitation operation
By nitrate trihydrate copper { Cu (NO
3)
23H
2O} and eight water zirconium oxychloride (ZrOCl
28H
2O) be configured to by deionized water the hybrid metal solution that copper zirconium ion concentration sum is 0.1～0.4mol/L, wherein the mol ratio of copper nitrate and zirconium oxychloride is 1:2.Configuration concentration be 1.0～4.5mol/L sodium hydroxide solution as precipitant solution, under stirring operation, above-mentioned sodium hydroxide solution is dropped in copper zirconium hybrid metal solution, when pH value of solution=10～12, precipitation completes, and stops dripping, and obtains copper zirconium deposit seed.The copper zirconium deposit seed that precipitation is obtained washs extremely without chlorine by deionized water.
2) reflux operation
Add organic solvent and deionized water in the copper zirconium deposit seed prepared to step 1), add hot reflux 1～24h, be cooled to room temperature, filtration (for example centrifuge filtration), obtain copper zirconium solid particle.
3) drying and roasting
Copper zirconium solid particle for example,, in 105 ℃ of dryings (in drying box dry 12～24h to constant weight), then, in 450～750 ℃ of roasting 3～6h, is obtained to catalyst precursor (roasting can be carried out in chamber type electric resistance furnace).
4) reduction
Catalyst precursor, under hydrogen atmosphere, in 200～260 ℃ of reduction 4～6h, obtains Cu-Zr catalyst.Reduction can be carried out in tube electric furnace, after the Cu-Zr catalyst obtained is cooling under oxygen barrier atmosphere, is stored in deoxygenated water standby.
The further preferred technical scheme of the present invention is:
Described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine, polyethylene glycol, methylamine, ethamine, propylamine, butylamine or ethylenediamine; Further preferred methylamine, ethamine, propylamine, butylamine or ethylenediamine; Preferred ethamine further.
In described organic solvent reflux operation, consumption of organic solvent and zirconium ion consumption are mole to count (1～16): 1, and adding deionized water to regulate copper zirconium ion concentration in the recirculate mixing thing is 0.1～0.6mol/L.
In described organic solvent reflux operation, reflux temperature is difference according to the organic solvent used; By repeatedly, repetition test confirms, under above-mentioned suitable condition, the copper zirconium deposit seed that the precipitation method the are prepared 1～24h that refluxes in solvent and deionized water, can improve the activity of catalyst greatly, improves the reaction rate of diethanol amine legal system iminodiacetic acid.
The present invention finds first and discloses Cu-Zr catalyst prepared by the precipitation method and carries out the organic solvent backflow, thereby prepares the more excellent catalyst of catalytic performance.Use it for diethanol amine and prepare in the iminodiacetic acid (salt) acid reaction, compare with existing catalyst, the present invention has the following advantages: (1) strengthens the reactivity of catalyst system and catalyzing, thereby the accelerated reaction process reaches the purpose of Reaction time shorten; (2) improve reaction yield, improved raw material availability, reduced production cost.
The specific embodiment
Following examples are for further illustrating the present invention, in order to better set forth content of the present invention.But the present invention only limits to absolutely not these embodiment.Wherein chemical raw material used is commercially available industrial goods.
Embodiment 1-2
1) by 13.4g Cu (NO
3)
23H
2O and 48.3g ZrOCl
28H
2O is configured to the metallic solution that copper zirconium ion concentration sum is 0.3mol/L.Under stirring, the sodium hydroxide solution that is 4.5mol/L by concentration drops in copper zirconium hybrid metal solution, and when pH value of solution=12, precipitation completes, and stops dripping, and obtains copper zirconium deposit seed; The copper zirconium deposit seed that precipitation is obtained washs extremely without chlorine by deionized water;
2) add ethanol (embodiment 1) or the ethamine (embodiment 2) that is equivalent to 4 times of zirconium moles in copper zirconium deposit seed, adding deionized water to regulate copper zirconium ion concentration sum in mixture is 0.3mol/L, and the heating said mixture is to boiling, backflow 12h, reflux complete, be cooled to room temperature;
3) centrifuge filters, and the solid particle obtained is dried to constant weight in the drying box of 105 ℃; 500 ℃ of roasting 4h in chamber type electric resistance furnace, obtain catalyst precursor again;
4) catalyst precursor after roasting, under hydrogen atmosphere, after reduction 5h, obtains catalyst in the tube electric furnace of 220 ℃;
5) activity rating and interpretation of result: evaluating catalyst carries out in the autoclave of 250ml, the 51.8g diethanol amine feeds intake at every turn, 41.5g NaOH, 5.2g catalyst, 96.5g deionized water, under the condition of 170 ℃ of reaction temperatures, reaction pressure 1.6MPa, reaction, to without γ-ray emission, is reacted and is finished.Adopt potentiometric titration to analyze and measure the iminodiacetic acid (salt) acid content, with Pb (NO
3)
2As cushioning liquid, titration end-point pH=5.10.Principle is: in the aqueous solution of pH=5.10, the 1mol/L iminodiacetic acid can discharge 2mol H+ with 1mol Pb2+ complexing, therefore just can calculate the content of iminodiacetic acid by the amount of measuring the H+ be displaced in solution.
Embodiment 1-2 makes catalyst (CZ-1) and reactivity worth test result (CZ-2) is listed in table 1.
Embodiment 3-4
1) preparation of copper zirconium deposit seed is same as embodiment 1;
2) to adding the ethamine (embodiment 3) that is equivalent to 2 times of zirconium moles or the ethamine (embodiment 4) of 8 times of moles in copper zirconium deposit seed, adding deionized water to regulate copper zirconium ion concentration sum in mixture is 0.3mol/L, the heating said mixture is to boiling, backflow 12h, reflux complete, be cooled to room temperature;
The 3rd)-5) the step operation is same as embodiment 1.
Embodiment 3-4 makes catalyst (CZ-3) and reactivity worth test result (CZ-4) is listed in table 1.
Embodiment 5-6
1) preparation of copper zirconium deposit seed is same as embodiment 1;
2) add the ethamine that is equivalent to 4 times of zirconium moles in copper zirconium deposit seed, add deionized water to regulate copper zirconium ion concentration sum in mixture and be respectively 0.2mol/L(embodiment 5) or 0.6mol/L(embodiment 6), the heating said mixture is to boiling, backflow 12h, reflux complete, be cooled to room temperature;
The 3rd)-5) the step operation is same as embodiment 1.
Embodiment 5-6 makes catalyst (CZ-5) and reactivity worth test result (CZ-6) is listed in table 1.
Embodiment 7-8
1) preparation of copper zirconium deposit seed is same as embodiment 1;
2) add the ethamine that is equivalent to 4 times of zirconium moles in copper zirconium deposit seed, adding deionized water to regulate copper zirconium ion concentration sum in mixture is 0.3mol/L, and the heating said mixture is to boiling, backflow 4h(embodiment 7) or 16h(embodiment 8), reflux complete, be cooled to room temperature;
The 3rd)-5) the step operation is same as embodiment 1.
Embodiment 7-8 makes catalyst (CZ-7) and reactivity worth test result (CZ-8) is listed in table 1.
The comparative example
The addition of reaction condition and operation, raw material and catalyst all is same as embodiment 1, just at catalyst without the organic solvent reflow treatment, make catalyst (CZ).Contrast and experiment is listed in table 1.
The reactivity worth test result of the different preparation process catalyst of table 1
Obviously, the above embodiment of the present invention is only for example of the present invention clearly is described, and non exhaustive, thereby is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Every belong to the spiritual scope that apparent variation that technical scheme of the present invention extends out or change all contain in the present invention within.
Claims (7)
1. the preparation method of Cu-Zr catalyst for a synthesis of iminodiacetic acid, comprise: in the copper zirconium deposit seed prepared to the precipitation method, add organic solvent and deionized water, add hot reflux, after mixture is cooling, through separation, drying, roasting, reduction, make catalyst; Described organic solvent is selected from alcohols or amine solvent, and consumption of organic solvent and zirconium ion amount are mole to count 0.1～32:1, and adding deionized water to regulate copper zirconium ion concentration in the recirculate mixing thing is 0.05～1.2mol/L.
2. method according to claim 1 is characterized in that operating according to the following steps:
1) precipitation operation
Nitrate trihydrate copper and eight water zirconium oxychlorides are configured to the hybrid metal solution that copper zirconium ion concentration sum is 0.1～0.4mol/L by deionized water, and wherein the mol ratio of copper nitrate and zirconium oxychloride is 1:2; The sodium hydroxide solution that is 1.0～4.5mol/L by concentration drops in copper zirconium hybrid metal solution, when pH value of solution=10～12, stops dripping, and obtains copper zirconium deposit seed, with the deionized water washing to without chlorine;
2) reflux operation
Add organic solvent and deionized water in the copper zirconium deposit seed prepared to step 1), add hot reflux 1～24h, be cooled to room temperature, filtration, obtain copper zirconium solid particle;
3) drying and roasting
Copper zirconium solid particle is dried to constant weight in 105 ℃; In 450～750 ℃ of roasting 3～6h, obtain catalyst precursor again;
4) reduction
Catalyst precursor under hydrogen atmosphere, in 200～260 ℃ the reduction 4～6h, obtain Cu-Zr catalyst, cooling under oxygen barrier atmosphere after, be stored in deoxygenated water standby.
3. method according to claim 1 and 2, it is characterized in that: described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine, polyethylene glycol, methylamine, ethamine, propylamine, butylamine or ethylenediamine.
4. method according to claim 3, it is characterized in that: described organic solvent is selected from methylamine, ethamine, propylamine, butylamine or ethylenediamine.
5. method according to claim 4, it is characterized in that: described organic solvent is selected from ethamine.
6. method according to claim 1 and 2 is characterized in that: in reflux operation, consumption of organic solvent and zirconium ion amount are mole to count 1～16:1.
7. method according to claim 1 and 2 is characterized in that: in reflux operation, adding deionized water to regulate copper zirconium ion concentration in the recirculate mixing thing is 0.1～0.6mol/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349922A (en) * | 2017-07-28 | 2017-11-17 | 湘潭大学 | A kind of copper/zirconium oxide graphene composite carrier catalyst and preparation method and application |
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|---|---|---|---|---|
| CN107442120A (en) * | 2017-08-28 | 2017-12-08 | 湘潭大学 | A kind of Cu/ZrO2Catalyst and its production and use |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782183A (en) * | 1983-10-05 | 1988-11-01 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for manufacture of amino-carboxylic acid salts |
| CN101733100A (en) * | 2008-11-17 | 2010-06-16 | 浙江师范大学 | Amorphous state copper-zirconium catalyst for use in preparation of iminodiacetic acid |
-
2012
- 2012-05-16 CN CN201210151997.1A patent/CN103418382B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782183A (en) * | 1983-10-05 | 1988-11-01 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for manufacture of amino-carboxylic acid salts |
| CN101733100A (en) * | 2008-11-17 | 2010-06-16 | 浙江师范大学 | Amorphous state copper-zirconium catalyst for use in preparation of iminodiacetic acid |
Non-Patent Citations (2)
| Title |
|---|
| 叶洪平: ""用于二乙醇胺催化脱氢制备亚氨基二乙酸盐的Cu/ZrO2催化剂的制备与研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 * |
| 肖进兵: ""乙胺-水体系中制备纳米二氧化锆"", 《鞍山科技大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349922A (en) * | 2017-07-28 | 2017-11-17 | 湘潭大学 | A kind of copper/zirconium oxide graphene composite carrier catalyst and preparation method and application |
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