CN103143336B - Regeneration method of activated carbon catalyst used for preparing glyphosate - Google Patents
Regeneration method of activated carbon catalyst used for preparing glyphosate Download PDFInfo
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Abstract
The invention discloses a regeneration method of an activated carbon catalyst used for preparing glyphosate. The regeneration method comprises a solvent elution step and/or a heat treatment step, wherein the solvent elution step refers to treating inactivated activated carbon catalyst for 4-24 hours in a refluxing condition by using a water solution with alkaline or reducing inorganic substance or an organic solvent with alkalinity or reducibility; and the heat treatment step refers to high-temperature roasting to-be-treated catalyst for 0.5-24 hours in a reducing gas to obtain regenerated catalyst with activity fully recovered. An object of reuse of waste activated carbon generated in a production process of the glyphosate can be achieved by the method provided by the invention, thereby greatly reducing generation of solid waste in the production process of the glyphosate and simultaneously reducing production cost.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of renovation process of inactivation activated-carbon catalyst, be specifically related to a kind of renovation process preparing glyphosate activated-carbon catalyst.
Background technology
Glyphosate (chemical name: N-((phosphonomethyl)) glycine, English name: glyphosate) is the nonselective high-efficiency broad spectrum herbicide of interior suction after a kind of bud.Along with succeeding in developing and establishing in large scale of glyphosate genetically modified crops, and the popularization of bio-fuel crop that energy crisis causes, glyphosate becomes the maximum and herbicide kind that growth rate is the fastest of current global sales.
Glyphosate synthesis route is numerous, and the route of international mainstream is imido oxalic acid method (i.e. IDA method), and its committed step is PMIDA synthesizing glyphosate by catalytic oxidation.It is catalyst that Hershman discloses with active carbon in US3969398, adopts oxygen-containing gas PMIDA to be oxidized to the method for glyphosate.Although this invention has lot of advantages, catalysqt deactivation is seriously its fatal weakness.To this, the applicant of the application studies preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid process, find that the activated centre of its catalytic process is that activated carbon surface contains pyridine and pyroles functional group, invent a kind of method that specific aim improves activated carbon surface pyridine and pyrroles's functional group content, for glyphosate synthesis process, its catalytic activity is 2 times of US3969398 invention catalyst.This invention has applied for Chinese patent, application number 201010578256.2.Although this catalyst life has good improvement, but still there is slow deactivation prob.
Usually, the way of glyphosate producer solution catalysqt deactivation is: apply mechanically in process and constantly supplement certain quantity of fresh catalyst to delay the life-span.The catalytic amount that this method consumes is comparatively large, and along with applying mechanically increasing of number of times, in reactor, the content of solid glyphosate is more and more higher, cause reactant liquor thickness, production efficiency declines, and the final solid waste produced also increases thereupon, adds the operation cost in glyphosate production process simultaneously.
CN1150118A describes a kind of general renovation process of active carbon: be that regenerative agent carries out activating and regenerating with phosphoric acid, the active carbon properties after activation is recovered.But this method regenerates for the inactivation activated-carbon catalyst of PMIDA catalytic oxidation, poor effect, the regeneration research of the domestic and international inactivation activated-carbon catalyst to preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid at present still belongs to blank.
Summary of the invention
The object of the present invention is to provide a kind of renovation process preparing glyphosate activated-carbon catalyst.The present invention is studied for preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid process especially, find the aobvious alkalescence of pyridine and pyrroles functional group of activated carbon surface, usually such active carbon pH value is between 8-13, in this, as the catalyst of PMIDA oxidizing process, have very high absorption property to highly acid reactant PMIDA, this is convenient to the better contact catalyst Active sites of reactant; Meanwhile, pyridine and pyroles functional group have the effect that selective oxidation tertiary amine changes into secondary amine.Therefore, in glyphosate synthesis process, the activated centre of adsorption site and selective oxidation PMIDA is served as simultaneously by pyridine and pyroles functional group, and the number of such functional group and catalytic performance are almost linear.But, in catalytic oxidation process, pyridine and pyroles functional group self are converted into class amide group after removing the carboxymethyl in PMIDA, the pyridine of aobvious alkalescence originally and pyrroles functional group conversions is made to become to show acid class amide groups, reduce the ability of charcoal absorption PMIDA on the one hand, make on the other hand to possess the class amide groups that the pyridine of catalytic performance and pyrrole group change into non-activity, thus cause inactivation.
Based on above-mentioned deactivation mechanism, renovation process provided by the invention is set about from two aspects: one is the absorption property recovering catalyst, namely recovers the alkalescence of catalyst; Two is recover catalyst surface active center, changes into pyridine and pyroles functional group by class amide groups.Therefore, the renovation process of above-mentioned decaying catalyst focuses in the fracture of amido link, as long as be conducive to the method for the fracture of amido link, all can be used for the regeneration of this catalyst.Condition needed for the fracture of known amido link is the existence of alkali, water, heat, so the proposed by the invention core preparing glyphosate catalyst recovery process is the efficient combination of alkali, water, heat three kinds of conditions.By single condition experiment and the many condition combination of above-mentioned renovation process, the catalyst of partially or completely activity recovery can be obtained.Catalyst after regeneration is consistent with the result of use of fresh catalyst, regeneration cost is far below newly purchasing catalyst, greatly can reduce the solid waste in glyphosate production process and operation cost, thus the renovation process proposed after a kind of preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid activated-carbon catalyst inactivation, achieve object of the present invention.
Technical scheme of the present invention is as follows:
Prepare a renovation process for glyphosate activated-carbon catalyst, comprise solvent elution and/or heat treatment step, each step method of operating is as follows:
1) solvent elution
Under 0.1-10Mpa pressure, adopt aqueous solution of inorganic matter and/or organic solvent to process inactivation activated-carbon catalyst 4-24h at a reflux temperature, filtration washing, to neutral, is dried to constant weight; Described inorganic matter and organic solvent are the material with alkalescence or reproducibility;
2) heat treatment
By through or without the inactivation active carbon of solvent elution process under inert atmosphere protection, be heated to 300-1500 DEG C, pass into reducibility gas roasting 0.5-24h, then be cooled to room temperature in inert atmosphere borehole cooling, obtain regenerating rear activated-carbon catalyst.
Described activated-carbon catalyst refers in particular to the activated-carbon catalyst of the activated-carbon catalyst of preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid or noble metal, transition metal load.The activated-carbon catalyst of the activated-carbon catalyst of inactivation or complete deactivation or noble metal, transition metal load is divided in described inactivation activated-carbon catalyst finger.
The so-called solvent elution that the renovation process of activated-carbon catalyst of the present invention comprises and/or heat treatment step, concrete meaning is: solvent elution and these two steps of heat treatment both can individually use, the catalyst of the two step operational processes inactivations that also can use in order as described above.According to the method described above, first step solvent elution regeneration efficiency can reach 0-60%; Second step thermal process regeneration efficiency can reach 50-100%.
When using alkalescence or reducing inorganic thing aqueous solution process decaying catalyst, the aqueous solution of the hydroxide of preferred as alkali, alkaline-earth metal, ammonium, the sulfide of ammonium, carbonate or bicarbonate; The aqueous solution process inactivation activated-carbon catalyst of one or more inorganic matters above-mentioned can be selected; More preferably the aqueous solution of the hydroxide of alkali metal, ammonium or the sulfide of ammonium.Pending inactivation activated-carbon catalyst and the mass ratio of inorganic matter are 1: 0.02-0.5, preferably 1: 0.05-0.2.The maximum regeneration efficiency that this step is used alone can reach 50%.
When use possesses the organic solvent process decaying catalyst of alkalescence or reproducibility, the organic solvent of alkalescence or reproducibility refers in particular to nitrogenous organic solvent; Preferred pyridines, pyroles, miazines, hydrazine class, amide-type or organic amine compound; One or more organic solvent process inactivation activated-carbon catalysts above-mentioned can be selected; More preferably hydrazine class or amides compound.Pending inactivation activated-carbon catalyst and the mass ratio of organic solvent are 1: 1-10, preferably 1: 2-5.The maximum regeneration efficiency that this step is used alone can reach 60%.
Solvent elution step also can by the aqueous solution of above-mentioned inorganic matter and organic solvent used in combination, wherein the aqueous solution of inorganic matter and the ratio of organic solvent do not limit.Through the catalyst of solvent elution process, constant weight can be dried to according to a conventional method.Such as in 80-150 DEG C, be preferable over 100-120 DEG C of drying.
When using heat treating process process decaying catalyst (this catalyst both can have been crossed without solvent elution process and also can be through solvent elution step process and cross), described reducibility gas is selected from hydrogen sulfide, sulfur dioxide, nitric oxide, nitrogen dioxide, ammonia, carbon monoxide or hydrogen, preferred hydrogen sulfide; Described inert gas is selected from nitrogen, argon gas, helium or carbon dioxide, preferred nitrogen.The maximum regeneration efficiency that this step is used alone can reach 100%.
In heat treatment step, preferred operating condition is further: sintering temperature 400-1200 DEG C, roasting time 1-12h.
Treatment conditions described in the above-mentioned renovation process preparing glyphosate activated-carbon catalyst and the inorganic agent selected can carry out being combined and convert, such as solvent elution step both can select above-mentioned arbitrary material to process decaying catalyst, and any two components or multicomponent also can be selected to be mixed into row relax with arbitrary proportion.User can according to the concrete condition of pending decaying catalyst, determine to adopt renovation process provided by the present invention or only select in two steps one of them.The most preferred assembled scheme recommended exemplifies as follows:
(1) solvent elution: under reflux conditions, adopts hydrazine hydrate, and after airtight stir process inactivation activated-carbon catalyst 4h, filtration washing, to neutral, is dried to constant weight;
(2) heat treatment: by the above-mentioned activated-carbon catalyst being dried to constant weight under hydrogen sulfide atmosphere, 400 DEG C of constant temperature calcining 1h, obtain after cooling regenerating rear activated-carbon catalyst, and heat treated heating, cooling process is carried out under nitrogen atmosphere.
The present invention adopts regeneration efficiency to evaluate the regeneration effect of decaying catalyst, evaluation test adopts following reaction condition to carry out PMIDA and is oxidized the reaction preparing glyphosate: in 250mL autoclave, add 4.175g catalyst to be evaluated (catalyst namely after regeneration), 33.4g PMIDA and 100g water, reaction temperature 65 DEG C, partial pressure of oxygen 0.6Mpa, oxygen flow 150mL/min, speed of agitator 800rpm, reaction time 0.5h.After reaction terminates, filter, the pH value of reactant liquor is adjusted to 7, is settled to 500mL, HPLC analyzes the content of glyphosate and calculated yield (regenerated catalyst yield).Same method adopts fresh catalyst and decaying catalyst to prepare glyphosate respectively, obtains fresh catalyst yield and decaying catalyst yield respectively.Calculate the regeneration efficiency of catalyst as follows:
The regeneration efficiency calculating the inactivation activated-carbon catalyst of above-mentioned Optimum combinational scheme according to above method can reach 101%.
The renovation process tool preparing glyphosate activated-carbon catalyst provided by the invention has the following advantages:
1. regeneration cost is cheap, and far below the price newly purchasing catalyst, the catalyst of holomorphosis is consistent with fresh catalyst result of use, greatly reduces the production cost of glyphosate;
2. catalyst regeneration efficiency is adjustable, is applicable to that existing glyphosate producer is suitable for according to pending catalyst choice, economic regeneration scheme;
3. solve in prior art glyphosate production process and produce solid waste problem, fundamentally solve the difficult problem that catalyst circulation uses.
Detailed description of the invention
Following examples are used for further illustrating the present invention, better to set forth content of the present invention.Following examples are only for example of the present invention is clearly described, and non exhaustive, are also not the restrictions 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 following description.Every belong to technical scheme of the present invention within the scope all contained in the present invention of the apparent change of extending out or variation.Wherein inactivation activated-carbon catalyst is denoted as " De-AC ", and fresh catalyst corresponding is with it denoted as " Fr-AC ".
Embodiment 1 alkalescence or reproducibility organic solvent method of reproduction
Get 4 parts of each 100g of inactivation activated-carbon catalyst in 4 autoclaves, carry out solvent elution with pyridine, hydrazine hydrate, DMF, each 200g of ethylenediamine respectively.Treatment conditions: airtightly in autoclave be warming up to 170 DEG C, after stirring 4h, filter after being down to room temperature under 500rpm rotating speed, be washed to neutrality, 110 DEG C are dried to constant weight, obtain regeneration activity Pd/carbon catalyst, are denoted as successively " Re-1-1, Re-1-2, Re-1-3, Re-1-4 ".Adopt the regeneration effect of preceding method to four regenerated catalysts to evaluate, the results are shown in Table 1.
Table 1 organic solvent is to the regeneration effect of decaying catalyst
| Sample number into spectrum | Regenerative agent | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-1-1 | Pyridine | 62.50 | 50.30 |
| Re-1-2 | Hydrazine hydrate | 67.18 | 59.67 |
| Re-1-3 | DMF | 61.08 | 47.46 |
| Re-1-4 | Ethylenediamine | 40.77 | 6.81 |
Embodiment 2 alkalescence or reducing inorganic thing aqueous solution method of reproduction
Get 5 parts of each 100g of inactivation activated-carbon catalyst in 5 autoclaves, carry out solvent elution with each 200g of the aqueous solution of potassium hydroxide, sodium carbonate, carbonic hydroammonium, ammoniacal liquor, ammonium sulfide (each aqueous solution mass fraction is for 5%) respectively.Treatment conditions, with embodiment 1, obtain regeneration activity Pd/carbon catalyst, are denoted as successively " Re-2-1, Re-2-2, Re-2-3, Re-2-4, Re-2-5 ".Adopt the regeneration effect of preceding method to five regenerated catalysts to evaluate, the results are shown in Table 2.
Table 2 aqueous solution of inorganic matter is to the regeneration effect of decaying catalyst
| Sample number into spectrum | Regenerative agent | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-2-1 | Potassium hydroxide | 67.09 | 59.49 |
| Re-2-2 | Sodium carbonate | 50.25 | 25.78 |
| Re-2-3 | Carbonic hydroammonium | 57.34 | 39.97 |
| Re-2-4 | Ammoniacal liquor | 59.27 | 43.84 |
| Re-2-5 | Ammonium sulfide | 68.84 | 63.00 |
The inorganic organic mixed solution method of reproduction of embodiment 3
Get inactivation activated-carbon catalyst 100g and drop into autoclave, add the ammonium sulfide solution 100g of 5% mass fraction, then add 100g hydrazine hydrate; Separately get inactivation activated-carbon catalyst 100g and drop into autoclave, add the potassium hydroxide aqueous solution 100g of 5% mass fraction, then add 100g DMF.Treatment conditions, with embodiment 1, obtain regeneration activity Pd/carbon catalyst, are denoted as successively " Re-3-1 " and " Re-3-2 ".Adopt the regeneration effect of preceding method to two regenerated catalysts to evaluate, the results are shown in Table 3.
The inorganic organic mixed solution method of reproduction regeneration effect of table 3
Embodiment 4 thermal process regeneration
Get 6 parts of each 100g of inactivation activated-carbon catalyst and put into 6 quartz boats respectively; 5 DEG C/min ramp to 1000 DEG C under inert nitrogen gas protection; pass into the hydrogen sulfide of 100mL/min, sulfur dioxide, nitric oxide, carbon monoxide, hydrogen, ammonia respectively; 1000 DEG C of constant temperature calcining 1h; obtain regeneration activity Pd/carbon catalyst after being down to room temperature, be denoted as successively " Re-4-1, Re-4-2, Re-4-3, Re-4-4, Re-4-5, Re-4-6 ".Adopt the regeneration effect of preceding method to six regenerated catalysts to evaluate, the results are shown in Table 4.
Table 4 different atmosphere hot recycling method regeneration effect
| Sample number into spectrum | Regeneration atmosphere | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-4-1 | Hydrogen sulfide | 76.92 | 79.16 |
| Re-4-2 | Sulfur dioxide | 68.88 | 63.07 |
| Re-4-3 | Nitric oxide | 87.27 | 99.88 |
| Re-4-4 | Carbon monoxide | 76.34 | 78.00 |
| Re-4-5 | Hydrogen | 68.89 | 63.09 |
| Re-4-6 | Ammonia | 70.32 | 65.95 |
Embodiment 5 mixed regeneration method
Get 6 parts of inactivation activated-carbon catalyst 100g respectively through following steps process:
1) respectively get 200g hydrazine hydrate to add and airtightly in autoclave be warming up to 170 DEG C, stir 4h under 500rpm rotating speed, filter after being down to room temperature, 110 DEG C are dried to constant weight;
2) 6 quartz boats put into respectively by above-mentioned dried sample; 5 DEG C/min ramp to 400 DEG C under inert nitrogen gas protection; pass into the atmosphere such as the hydrogen sulfide of 100mL/min, sulfur dioxide, nitric oxide, carbon monoxide, hydrogen, ammonia respectively; 400 DEG C of constant temperature calcining 1h; obtain regenerated carbon after being down to room temperature, be denoted as successively " Re-5-1, Re-5-2, Re-5-3, Re-5-4, Re-5-5, Re-5-6 ".Adopt the regeneration effect of preceding method to six regenerated catalysts to evaluate, the results are shown in Table 5.
Table 5 mixed regeneration method regeneration effect
| Sample number into spectrum | Renovation process | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-5-1 | Hydrazine hydrate+hydrogen sulfide | 88.28 | 101.90 |
| Re-5-2 | Hydrazine hydrate+sulfur dioxide | 86.95 | 99.24 |
| Re-5-3 | Hydrazine hydrate+nitric oxide | 87.34 | 100.00 |
| Re-5-4 | Hydrazine hydrate+carbon monoxide | 85.29 | 95.92 |
| Re-5-5 | Hydrazine hydrate+hydrogen | 87.74 | 100.82 |
| Re-5-6 | Hydrazine hydrate+ammonia | 86.76 | 98.86 |
Claims (4)
1. prepare a renovation process for glyphosate activated-carbon catalyst, comprise solvent elution and heat treatment step, each step method of operating is as follows:
1) solvent elution is under 0.1-10Mpa pressure, and adopt aqueous solution of inorganic matter and organic solvent to process inactivation activated-carbon catalyst 4-24h at a reflux temperature, filtration washing, to neutral, is dried to constant weight; Described inorganic matter and organic solvent are the material with alkalescence or reproducibility;
2) heat treatment is by the inactivation active carbon through solvent elution process under inert atmosphere protection, is heated to 300-1500 DEG C, passes into reducibility gas roasting 0.5-24h, then is cooled to room temperature in inert atmosphere borehole cooling, obtains regenerating rear activated-carbon catalyst;
Step 1) described in inorganic matter be selected from following material one or more: the hydroxide of alkali metal, alkaline-earth metal, ammonium, the sulfide of ammonium, carbonate, bicarbonate; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1:0.02-0.5 of inorganic matter;
Step 1) described in organic solvent be selected from following material one or more: pyridines, pyroles, miazines, hydrazine class, organic amine compound; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1:1-10 of organic solvent;
Step 2) described in reducibility gas be selected from hydrogen sulfide, sulfur dioxide, nitric oxide, nitrogen dioxide, ammonia, carbon monoxide or hydrogen; Described inert gas is selected from nitrogen, argon gas, helium or carbon dioxide.
2., according to renovation process according to claim 1, it is characterized in that: step 1) described in aqueous solution of inorganic matter be selected from the aqueous solution of alkali metal, the hydroxide of ammonium or the sulfide of ammonium; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1:0.05-0.2 of inorganic matter.
3., according to renovation process according to claim 1, it is characterized in that: step 1) described in organic solvent be selected from hydrazine class; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1:2-5 of organic solvent.
4., according to renovation process according to claim 1, it is characterized in that: step 2) described in reducibility gas be selected from hydrogen sulfide; Described inert gas is selected from nitrogen.
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| CN105080521A (en) * | 2015-08-07 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Activated carbon regeneration method |
| CN106512974A (en) * | 2016-11-10 | 2017-03-22 | 中南大学 | Regeneration method of activated carbon |
| SE542156C2 (en) * | 2017-10-01 | 2020-03-03 | Absolent Ab | Method and system for recycling saturated active ccarbon |
| CN108212135A (en) * | 2017-12-29 | 2018-06-29 | 南通泰禾化工股份有限公司 | The recycling and processing device and method of dead catalyst in a kind of Bravo synthesis technology |
| CN108722500A (en) * | 2018-07-03 | 2018-11-02 | 辽宁格瑞凯特科技有限公司 | Glyphosate cleans recycling method after being inactivated with activated-carbon catalyst |
| CN108906138A (en) * | 2018-07-04 | 2018-11-30 | 成都恩承科技股份有限公司 | A kind of regeneration method of active carbon or carbon-supported catalysts |
| CN113262757B (en) * | 2021-06-01 | 2022-07-26 | 上海市固体废物处置有限公司 | Method for preparing furfural simultaneously by regenerating waste activated carbon |
| CN118491571B (en) * | 2024-07-17 | 2024-10-01 | 沈阳开拓利思科技有限公司 | Regeneration method of active carbon catalyst for glyphosate |
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