CN102139205A - Method for preparing special carbon oxidation catalyst for glyphosate - Google Patents
Method for preparing special carbon oxidation catalyst for glyphosate Download PDFInfo
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- CN102139205A CN102139205A CN2011100283399A CN201110028339A CN102139205A CN 102139205 A CN102139205 A CN 102139205A CN 2011100283399 A CN2011100283399 A CN 2011100283399A CN 201110028339 A CN201110028339 A CN 201110028339A CN 102139205 A CN102139205 A CN 102139205A
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- glyphosate
- active carbon
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- catalysts
- char combustion
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 43
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title abstract description 10
- 238000007254 oxidation reaction Methods 0.000 title abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000003610 charcoal Substances 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000012545 processing Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000002485 combustion reaction Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- -1 wooden Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229910021386 carbon form Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 17
- 238000013461 design Methods 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 8
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000005080 plant death Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Abstract
The invention provides a method for preparing a special carbon oxidation catalyst for glyphosate with low production cost. Active carbon is sequentially subjected to modification treatment and thermal treatment to form the special carbon oxidation catalyst for the glyphosate. Compared with the traditional technology, the production process has the advantages that: 1, the whole reaction time is short, the average energy consumption is low, the probability that the active groups are embedded on the surface of the active carbon is high, the production cost can be saved for a production enterprise, and the competiveness of the enterprise is improved; and 2, the product produced by the process can improve the conversion rate of the glyphosate and increase the yield of the glyphosate.
Description
Technical field
The present invention relates to a kind of special-purpose char combustion Preparation of catalysts of glyphosate method that can reduce the glyphosate production cost.
Background technology
Glyphosate is the chronic wide spectrum steriland herbicide of inner sucting conduction type, the main interior enol acetonyl shikimene phosphate synthase of object that suppresses, thereby suppress the conversion of shikimene, make synthetic being interfered of protein cause plant death to phenylalanine, cruel propylhomoserin and tryptophan.Glyphosate is transmitted to each position of plant after absorbing by cauline leaf, can prevent and kill off the plant of sections more than 40 such as unifacial leaf and dicotyledonous, annual and perennial, draft and shrub.Combine with metal ions such as iron, aluminium and lose activity very soon after glyphosate buries, seed and edaphon hiding in the soil are had no adverse effects.
At present common on the market glyphosate is many to be made by the PMIDA oxidation, generally needs to add oxidation catalyst in course of reaction.It is that U.S. Monsanto Company and Dow AgroSciences propose the earliest that the char combustion catalyst is applied on the glyphosate synthesis and production process.Monsanto Company the patent 85102099 of China and 0380600000 and other United States Patent (USP)s in many articles that relate to the oxidant preparation and use are also arranged.And many patents that relate to oxidation catalyst are arranged also in the Chinese patent.
In general, oxidation catalyst is divided to make raw material, can be summarized as three classes: be the catalyst that raw material is made with metal or inorganic matter 1; 2, be carrier with active carbon or inorganic matter, the catalyst of carried metal or metal oxide; 3, simple is the catalyst of raw material with the charcoal.Wherein simple charcoal is that raw material is made catalyst, can realize that the glyphosate cost of manufacture is low, the advantage that conversion ratio is high.And can be that raw material is made catalyst with simple charcoal really at present, and realize industrialized have only Monsanto Company and two families of our company, it is the catalyst of raw material with the charcoal that the oxidation catalyst that production makes in 0380600000 the patent does not belong to simple, in the process of Preparation of Catalyst, add noble metal or transition metal, improved production cost.
In other words, at present simple is that the catalyst of raw material has only Monsanto Company a kind of at the patent 85102099 disclosed catalyst of China with the charcoal; All (at Chinese patent: general step 8510209) is as follows: 1, with oxidant charcoal is handled simultaneously at (800-1200) ℃ high temperature carbon removal oxide on surface that goes down, as NH for Meng Shan
3, H
2O, CO, NO
X, O
2, NH
3/ H
2O; 2, cracking charcoal under (800-1200) ℃ high temperature; 3 under oxygen or carrier of oxygen tertiary amine oxide or secondary amine, conversion ratio is lower.Need under the environment of higher temperature, react in the course of reaction, while tertiary amine oxide or secondary amine under oxygen or carrier of oxygen, conversion ratio is lower, thereby has improved the cost of producing catalyst.
On the other hand: in diethanolamine method synthesizing glyphosate technology, need to adopt oxidation catalyst in the reaction of PMIDA synthesizing glyphosate to shorten the reaction time and to improve product yield.At present, the method for PMIDA oxidation synthesizing glyphosate is a lot of, and in the application practice, the reaction time is many more than 5 hours, and product yield is generally between 88-92%.Reaction time is long and yield is low, makes the three wastes of mother liquor formation of glyphosate products many, subsequent treatment difficulty, cost height.The reaction time has been shortened in the research and development and the application of high performance catalyst of the present invention, and improving product yield is that present glyphosate industry reduces cost the active demand of improving the competitiveness.
Summary of the invention
The object of the present invention is to provide a kind of special-purpose char combustion Preparation of catalysts of glyphosate method of low production cost.
The object of the present invention is achieved like this: it is active carbon to be handled by modification processing and thermal technology successively make active carbon form the special-purpose char combustion catalyst of glyphosate.
Described active carbon is a raw material for adopting fiber, resin, petroleum coke, pitch, wooden, coal, shell, produces the product of the graininess or the powdery form of formation by traditional chemical method or physics method, and the specific area of active carbon is 800-1800m
2/ g; Iodine sorption value 800-1500mg/g; The order number is the active carbon charcoal material of 4-325 purpose graininess or powdery form.Active carbon is 1200 ~ 1800 m with specific area
2/ g; Iodine sorption value is the figure of merit for 1200-1500 mg/g.
Described modification is treated to:
(1), active carbon and surface modifier are mixed, active carbon was soaked 30-300 minute in surface modifier, soak time is good with 60-90 minute effect;
(2), will activated carbon filtration through directed change after, adopt the clear water rinsing, the active carbon pH after the rinsing should be good with pH4-5 between 2-9;
(3), should dry, the moisture content of oven dry back charcoal base material should be controlled between the 2-15% through the active carbon after the rinsing, among being the best less than 5%; The charcoal material pH of oven dry should be controlled between the 2-9 bake out temperature with in the 150-300 ℃ of scope for good.
(4), the heat treatment of consolidating the oxygen-containing functional group on the charcoal atomic surface of the active carbon after the rinsing oven dry, heat treatment is carried out in industrial furnace, the temperature of processing is 100-300 ℃, the time is 30-300 minute; Treatment temperature is advisable with 200-300 ℃, and the time was good with 200-250 minute.
Surface modifier comprises sulfuric acid solution, salpeter solution, liquor natrii hypochloritis, liquor potassic permanganate, hydrogen peroxide solution.Be that 15% nitric acid or concentration are 10% the clorox or the liquor potassic permanganate of concentration 5% wherein with concentration.
Described thermal technology is treated to:
(1), the active carbon that modulation process is crossed is placed in the heating furnace; in temperature is 600 ~ 1200 ℃ heating furnace; wherein temperature is the figure of merit with 1100 ℃; react with the activator that excites catalytic activity that inputs in the heating furnace; reaction time is 30-720 minute; the concrete time was good with 400 minutes, was reflected at vacuum or contains under the situation of protective gas to carry out.
(2), will carry out the grinding processing through the active carbon that step (1) is handled and obtain the special-purpose char combustion catalyst of glyphosate.
Described activator comprises melamine, urea, ammonia, diethylamine, methane, ethane, propane, butane, aliphatic hydrocarbon, is good with melamine, urea effect.The addition weight ratio is 3-15%, is good with 10%.Described protective gas is nitrogen, ammonia; With nitrogen is good; The pressure of protective gas in heating furnace is 0.2-5KPa.The mode of heating of heating furnace is the microwave irradiation heating.When described grinding is handled, pulverize after need removing the solid sinter, pulverizer is selected for use and is adopted the classification pulverizer, and according to different application demands, adjustable product order number is the 80-325 order.The ratio that this order is counted range product is for good between the 60-90%.
The present invention has the following advantages:
1, compare conventional art, this production technology W-response time is short, and it is low on average to consume energy, and active group is embedded in the probability height of activated carbon surface, can save production cost for manufacturing enterprise, improves enterprise competitiveness.
2, the product of this explained hereafter can improve the conversion ratio of PMIDA, increases the output of glyphosate.
The specific embodiment:
Embodiment 1:
Select spheric active carbon 1000g for use, its specific area 1400m
2/ g, iodine number 1200mg/g, order count the 40-80 order, dry processing as base material.It is 1% o'clock that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, 70 ℃ soak 90 minutes after filter do, make the pH value reach 4.5 with the clear water flushing, put in the thermostatic drying chamber, 160 ℃ of temperature are set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 250 ℃ of temperature are set, and the processing of finalizing the design of 200 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1100 ℃, and gas flow is set at 2L/min, and pressure is set at 0.4KPa, and time set is 400 minutes.Protective gas is selected nitrogen for use.Obtain product 850g, this product after measured the reaction time be 3 hours, the glyphosate products yield is 97.5%.
Embodiment 2
Select shell (cocoanut shell) active carbon 1000g for use, its specific area 1350m
2/ g, iodine number 1300mg/g, order count the 30-60 order, dry processing as base material.It is 1% that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, soaks to filter after 90 minutes and does, and makes the pH value reach 4.5 with the clear water flushing, puts in the thermostatic drying chamber, 160 ℃ of temperature is set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 250 ℃ of temperature are set, and the processing of finalizing the design of 200 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1100 ℃, and shield gas flow rate is set at 2L/min, and pressure is set at 0.4KPa, and time set is 400 minutes.Protective gas is selected nitrogen for use.Obtain product 875g, this product after measured the reaction time be 4.8 hours, the glyphosate products yield is 93.5%.
Embodiment 3
The wooden broken active carbon 1000g that selects for use the physics method to produce, its specific area 1200m
2/ g, iodine number 1100mg/g, order count the 20-40 order, dry processing as base material.It is 1% that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, soaks to filter after 90 minutes and does, and makes the pH value reach 4.5 with the clear water flushing, puts in the thermostatic drying chamber, 160 ℃ of temperature is set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 250 ℃ of temperature are set, and the processing of finalizing the design of 200 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1100 ℃, and gas flow is set at 2L/min, and pressure is set at 0.4KPa, and time set is 400 minutes.Protective gas is selected nitrogen for use.Obtain product 835g, this product after measured the reaction time be 5.6 hours, the glyphosate products yield is 94.2%.
Embodiment 4
Select the broken active carbon 1000g of ature of coal for use, its specific area 1100m
2/ g, iodine number 980mg/g, order count the 40-60 order, dry processing as base material.It is 1% that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, soaks to filter after 90 minutes and does, and makes the pH value reach 4.5 with the clear water flushing, puts in the thermostatic drying chamber, 160 ℃ of temperature is set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 250 ℃ of temperature are set, and the processing of finalizing the design of 200 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1100 ℃, and gas flow is set at 2 L/min, and pressure is set at 0.4KPa, and time set is 400 minutes.Protective gas is selected nitrogen for use.Obtain product 890g, this product after measured the reaction time be 6.5 hours, the glyphosate products yield is 89%.
Embodiment 5
Select chemical method granular activated carbon 1000g for use, its specific area 1200m
2/ g, iodine number 1100mg/g, order count the 20-40 order, dry processing as base material.It is 1% that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, soaks to filter after 90 minutes and does, and makes the pH value reach 4.5 with the clear water flushing, puts in the thermostatic drying chamber, 160 ℃ of temperature is set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 250 ℃ of temperature are set, and the processing of finalizing the design of 200 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1100 ℃, and gas flow is set at 2L/min, and pressure is set at 0.4KPa, and time set is 400 minutes.Protective gas is selected nitrogen for use.Obtain product 880g, this product after measured the reaction time be 4.2 hours, the glyphosate products yield is 95.3%.
Embodiment 6:
Select spheric active carbon 1000g for use, its specific area 1800m
2/ g, iodine number 800mg/g, order count the 4-42 order, dry processing as base material.It is 1% o'clock that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, 70 ℃ soak 30 minutes after filter do, make the pH value reach 2 with the clear water flushing, put in the thermostatic drying chamber, 160 ℃ of temperature are set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 150 ℃ of temperature is set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 100 ℃ of temperature are set, and the processing of finalizing the design of 300 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 600 ℃, and gas flow is set at 2L/min, and pressure is set at 0.4KPa, and time set is 720 minutes.Protective gas is selected nitrogen for use.Obtain product 736g, this product after measured the reaction time be 5.6 hours, the glyphosate products yield is 84.6%.
Embodiment 7
Select chemical method powdered activated carbon 1000g for use, its specific area 1350m
2/ g, iodine number 1050mg/g, order count the 80-120 order, dry processing as base material.It is 1% that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, soaks to filter after 90 minutes and does, and makes the pH value reach 4.5 with the clear water flushing, puts in the thermostatic drying chamber, 160 ℃ of temperature is set, 180 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 250 ℃ of temperature are set, and the processing of finalizing the design of 200 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1100 ℃, and gas flow is set at 2L/min, and pressure is set at 0.4KPa, and time set is 400 minutes.Protective gas is selected nitrogen for use.Obtain product 830g, this product after measured the reaction time be 5.2 hours, the glyphosate products yield is 93.8%.
Embodiment 8:
Select spheric active carbon 1000g for use, its specific area 800m
2/ g, iodine number 1500mg/g, order count the 260-325 order, dry processing as base material.It is 1% o'clock that its moisture content of back is handled in oven dry, adds 15% salpeter solution 3000ml, 60 ℃ soak 300 minutes after filter do, make the pH value reach 9 with the clear water flushing, put in the thermostatic drying chamber, 300 ℃ of temperature are set, 60 minutes drying times.Dried charcoal base material moisture content is less than 1%, this charcoal base material is put in the micro-wave oven heat-treated, and 300 ℃ of temperature are set, and the processing of finalizing the design of 30 minutes time is set.Cause burning for fear of the charcoal base material in heating process, the nitrogen that can lead to 15L/min is protected.Typing is cooled to room temperature with the charcoal base material after finishing, and dislocation activates processing in microwave atmosphere protection stove.Treatment temperature is set at 1200 ℃, and gas flow is set at 2 L/min, and pressure is set at 0.4KPa, and time set is 30 minutes.Protective gas is selected nitrogen for use.Obtain product 890g, this product after measured the reaction time be 6.5 hours, the glyphosate products yield is 89%.
Claims (10)
1. the special-purpose char combustion Preparation of catalysts of a glyphosate method is characterized in that: active carbon is handled successively making active carbon form the special-purpose char combustion catalyst of glyphosate by modification processing and thermal technology.
2. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 1 method, it is characterized in that: described active carbon is raw material for adopting in fiber, resin, petroleum coke, pitch, wooden, coal, the shell any one, produce the product of the graininess or the powdery form of formation by traditional chemical method or physics method, the specific area of active carbon is 800-1800m
2/ g; Iodine sorption value 800-1500mg/g; The order number is the active carbon charcoal material of 4-325 purpose graininess or powdery form.
3. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 2 method, it is characterized in that: described active carbon is 1200 ~ 1800 m with specific area
2/ g; Iodine sorption value is 1200-1500 mg/g.
4. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 1 method, it is characterized in that: described modification is treated to:
(1), active carbon and surface modifier are mixed, active carbon was soaked 30-300 minute in surface modifier;
(2), will activated carbon filtration through directed change after, adopt the clear water rinsing, the active carbon pH value after the rinsing should be between 2-9;
(3), should dry, the moisture content of oven dry back charcoal base material should be controlled between the 2-15% through the active carbon after the rinsing; The charcoal material pH value of oven dry should be controlled between the 2-9 bake out temperature 150-300 ℃;
(4), the heat treatment of consolidating the oxygen-containing functional group on the charcoal atomic surface of the active carbon after the rinsing oven dry, heat treated temperature is 100-300 ℃, the time is 30-300 minute.
5. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 4 method, it is characterized in that: described surface modifier comprises sulfuric acid solution, salpeter solution, liquor natrii hypochloritis, liquor potassic permanganate, hydrogen peroxide solution.
6. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 1 method, it is characterized in that: described thermal technology is treated to:
(1), the active carbon that modulation process is crossed is placed in the heating furnace, in temperature is 600 ~ 1200 ℃ heating furnace, react with the activator that excites catalytic activity that inputs in the heating furnace, the reaction time is 30-720 minute, is reflected at vacuum or contains under the situation of protective gas to carry out;
(2), will carry out the grinding processing through the active carbon that step (1) is handled and obtain the special-purpose char combustion catalyst of glyphosate.
7. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 6 method is characterized in that: described activator comprises that melamine, urea, ammonia, diethylamine, methane, ethane, propane, butane, aliphatic hydrocarbon are a kind of; The addition weight ratio is 3-15%.
8. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 6 method, it is characterized in that: described protective gas is nitrogen or ammonia; The pressure of protective gas in heating furnace is 0.2-5KPa.
9. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 6 method is characterized in that: the mode of heating of heating furnace is the microwave irradiation heating.
10. the special-purpose char combustion Preparation of catalysts of glyphosate according to claim 6 method, it is characterized in that: before described grinding is handled, pulverize after need removing the solid sinter, pulverizer is selected the classification pulverizer for use, according to different application demands, adjustable product order number is the 80-325 order.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627277A (en) * | 2012-04-11 | 2012-08-08 | 太原理工大学 | Modified active carbon and method for removing ammonia gas in intensive livestock farm |
| CN103495419A (en) * | 2013-10-23 | 2014-01-08 | 林天安 | Activated carbon used for three-dimensional electrode, preparation of activated carbon and application of activated carbon to treatment of waste water containing non-biodegradable organic matter |
| CN106319570A (en) * | 2015-06-24 | 2017-01-11 | 沈阳铝镁设计研究院有限公司 | Method for preparing anode surface antioxidation protective agent used for carbon-base aluminum |
| CN106319569A (en) * | 2015-06-24 | 2017-01-11 | 沈阳铝镁设计研究院有限公司 | Process for preparing anode surface anti-oxidant used for aluminum and usage method thereof |
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| CN101508701A (en) * | 2008-12-10 | 2009-08-19 | 上海泰禾(集团)有限公司 | Method for preparing glyphosate by oxidizing N-(Phosphonomethyl)iminodiacetic acid with active carbon as catalyst oxygen |
| CN101804341A (en) * | 2010-04-22 | 2010-08-18 | 浙江大学 | Method for preparing modified activated carbon for catalytic decomposition of hydrogen iodide through high-temperature heat treatment |
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| CN101508701A (en) * | 2008-12-10 | 2009-08-19 | 上海泰禾(集团)有限公司 | Method for preparing glyphosate by oxidizing N-(Phosphonomethyl)iminodiacetic acid with active carbon as catalyst oxygen |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627277A (en) * | 2012-04-11 | 2012-08-08 | 太原理工大学 | Modified active carbon and method for removing ammonia gas in intensive livestock farm |
| CN102627277B (en) * | 2012-04-11 | 2013-08-14 | 太原理工大学 | Modified active carbon and method for removing ammonia gas in intensive livestock farm |
| CN103495419A (en) * | 2013-10-23 | 2014-01-08 | 林天安 | Activated carbon used for three-dimensional electrode, preparation of activated carbon and application of activated carbon to treatment of waste water containing non-biodegradable organic matter |
| CN103495419B (en) * | 2013-10-23 | 2016-01-06 | 林天安 | Three-diemsnional electrode active carbon and preparation method thereof and the application on refractory organic waste water treatment |
| CN106319570A (en) * | 2015-06-24 | 2017-01-11 | 沈阳铝镁设计研究院有限公司 | Method for preparing anode surface antioxidation protective agent used for carbon-base aluminum |
| CN106319569A (en) * | 2015-06-24 | 2017-01-11 | 沈阳铝镁设计研究院有限公司 | Process for preparing anode surface anti-oxidant used for aluminum and usage method thereof |
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| CN102139205B (en) | 2015-10-28 |
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