CN102139205B - The preparation method of the special char combustion catalyst of glyphosate - Google Patents
The preparation method of the special char combustion catalyst of glyphosate Download PDFInfo
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- CN102139205B CN102139205B CN201110028339.9A CN201110028339A CN102139205B CN 102139205 B CN102139205 B CN 102139205B CN 201110028339 A CN201110028339 A CN 201110028339A CN 102139205 B CN102139205 B CN 102139205B
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- active carbon
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- combustion catalyst
- char combustion
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 38
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 229910021386 carbon form Inorganic materials 0.000 claims abstract description 3
- 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 36
- 238000001035 drying Methods 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 230000001681 protective effect Effects 0.000 claims description 14
- 230000035484 reaction time 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
- 239000003607 modifier Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-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
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 3
- -1 wooden Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 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
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000011295 pitch 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
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 16
- 238000001994 activation Methods 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 229920000877 Melamine resin Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- 150000001338 aliphatic hydrocarbons Chemical class 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
- 239000001273 butane Substances 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 239000003112 inhibitor 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 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
- 239000001294 propane Substances 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
- 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
- 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 kind of preparation method of the special char combustion catalyst of glyphosate of low production cost.It makes active carbon form the special char combustion catalyst of glyphosate by modification and thermal technology's process successively active carbon.Compare conventional art, this production technology has 1, the W-response time is short, average power consumption is low, and the probability that active group is embedded in activated carbon surface is high, can save production cost for manufacturing enterprise, raising enterprise competitiveness.2, the product of this explained hereafter can improve the conversion ratio of PMIDA, increases the output of glyphosate.
Description
Technical field
The present invention relates to a kind of preparation method that can reduce the special char combustion catalyst of glyphosate of glyphosate production cost.
Background technology
Glyphosate is the chronic wide spectrum steriland herbicide of inner sucting conduction type, enolpyruvyl shikimene phosphate synthase in major inhibitor body, thus suppress shikimene to the conversion of phenylalanine, cruel propylhomoserin and tryptophan, the synthesis of protein is interfered and causes Plant death.Glyphosate is transmitted to plant parts after being absorbed by cauline leaf, can prevent and kill off the plant of the sections more than 40 such as unifacial leaf and dicotyledonous, annual and perennial, herbs and shrubs.Be combined with the metal ion such as iron, aluminium and lose activity very soon after glyphosate buries, seed hiding in soil and edaphon are had no adverse effects.
The many oxidation by PMIDA of glyphosate common on the market at present obtains, and generally needs to add oxidation catalyst in course of reaction.Char combustion catalyst application is that About Monsanto Chemicals and Dow AgroSciences propose the earliest in glyphosate synthesis production technology.Also there are many articles relating to oxidant preparations and applicatio in Monsanto Company in the patent 85102099 and 0380600000 and other United States Patent (USP)s of China.And in Chinese patent, also have many patents relating to oxidation catalyst.
In general, oxidation catalyst, to manufacture raw material to divide, can be summarized as three classes: 1, with the catalyst that metal or inorganic matter are made for raw material; 2, with active carbon or inorganic matter for carrier, the catalyst of carried metal or metal oxide; 3, simple take charcoal as the catalyst of raw material.Wherein simple charcoal is that catalyst made by raw material, can realize glyphosate cost of manufacture low, the advantage that conversion ratio is high.And at present can really can with simple charcoal for catalyst made by raw material, and realize industrializedly only having Monsanto Company and our company two, producing obtained oxidation catalyst in the patent of 0380600000, not belong to simple take charcoal as the catalyst of raw material, in the process of catalyst preparing, with the addition of noble metal or transition metal, improve production cost.
In other words, at present simple with charcoal for the catalyst of raw material only has Monsanto Company's catalyst disclosed in the patent 85102099 of China a kind of; Meng Shan is (at Chinese patent: general step 8510209) is as follows: 1, process charcoal with oxidant, as NH at (800-1200) DEG C high temperature carbon removal oxide on surface that goes down simultaneously
3, H
2o, CO, NO
x, O
2, NH
3/ H
2o; 2, cracking charcoal under (800-1200) DEG C high temperature; 3 under oxygen or carrier of oxygen tertiary amine oxide or secondary amine, conversion ratio is lower.Need in course of reaction to react under the environment of higher temperature, simultaneously tertiary amine oxide or secondary amine under oxygen or carrier of oxygen, conversion ratio is lower, thus improves the cost producing catalyst.
On the other hand: in diethanolamine method synthesizing glyphosate technique, need in the reaction of PMIDA synthesizing glyphosate adopt oxidation catalyst with Reaction time shorten and improve product yield.At present, the method for PMIDA oxidative synthesis glyphosate is a lot of, and in 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, and the three wastes that the mother liquor of glyphosate products is formed are many, and subsequent treatment difficulty, cost is high.Research and development and the application of high performance catalyst of the present invention shorten the reaction time, and improving product yield is that current glyphosate industry reduces costs, the active demand of improving the competitiveness.
Summary of the invention
The object of the present invention is to provide the preparation method of the special char combustion catalyst of a kind of glyphosate of low production cost.
The object of the present invention is achieved like this: it makes active carbon form the special char combustion catalyst of glyphosate by modification and thermal technology's process successively active carbon.
Described active carbon for adopting fiber, resin, petroleum coke, pitch, wooden, coal, shell be raw material, carry out by traditional chemical method or Physical the product producing graininess or the powder form formed, the specific area of active carbon is 800-1800m
2/ g; Iodine sorption value 800-1500mg/g; Order number is the active carbon charcoal material of 4-325 object graininess or powder form.Active carbon take specific area as 1200-1800m
2/ g; Iodine sorption value is 1200-1500mg/g is the figure of merit.
Described modification is:
(1), by active carbon and surface modifier mixing, make active carbon soak 30-300 minute in surface modifier, soak time is good with 60-90 minute effect;
(2), by after the activated carbon filtration that soaked, adopt clear water rinsing, the active carbon pH after rinsing should, between 2-9, be good with pH4-5;
(3) active carbon, after rinsing should be dried, and dried charcoal base material moisture content is for being less than 1%; It is good that the charcoal material pH of drying should control bake out temperature between 2-9 within the scope of 150-300 DEG C.
(4), rinsing dry after active carbon carry out the heat treatment of the oxygen-containing functional group consolidated on charcoal atomic surface, heat treatment is carried out in industrial furnace, and the temperature of process is 100-300 DEG C, and the time is 30-300 minute; Treatment temperature is advisable with 200-300 DEG C, and the time was good with 200-250 minute.
Described surface modifier comprise in sulfuric acid solution, salpeter solution, liquor natrii hypochloritis, liquor potassic permanganate, hydrogen peroxide solution any one.Wherein with concentration be 15% nitric acid or concentration be the clorox of 10% or the liquor potassic permanganate of concentration 5%.
Described thermal technology is treated to:
(1), the active carbon that modification is crossed is placed in heating furnace; in the heating furnace that temperature is 600-1200 DEG C; wherein temperature with 1100 DEG C for the figure of merit; react with the activator of catalytic activity that excites inputed in heating furnace; reaction time is 30-720 minute; the concrete time was good with 400 minutes, reacted and carried out in vacuum or containing when protective gas.
(2), the active carbon processed through step (1) is carried out grinding process and obtain the special char combustion catalyst of glyphosate.
Described activator comprises melamine, urea, ammonia, diethylamine, methane, ethane, propane, butane, aliphatic hydrocarbon, is good with melamine, urea effect.Addition weight ratio is 3-15%, is good with 10%.Described protective gas is nitrogen; The pressure of protective gas in heating furnace is 0.2-5KPa.The mode of heating of heating furnace is microwave irradiation heating.During described grinding process, pulverize after need removing solid sinter, employing grade grinder selected by pulverizer, and according to different application demands, adjustable product order number is 80-325 order.The ratio of this order number range product is for good between 60-90%.
The present invention has the following advantages:
1, compare conventional art, this production technology W-response time is short, and average power consumption is low, and the probability that active group is embedded in activated carbon surface is high, 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.
Detailed description of the invention
Embodiment 1:
Select spheric active carbon 1000g, its specific area 1400m
2/ g, iodine number 1200mg/g, order number 40-80 order, carries out drying and processing as base material.When its moisture content is 1% after drying and processing, add the salpeter solution 3000ml of 15%, be filtered dry after soaking 90 minutes at 70 DEG C, rinse with clear water and make pH value reach 4.5, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 250 DEG C, setup times carries out heat treatment in 200 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1100 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 400 minutes.Protective gas selects nitrogen.Obtain product 850g, the reaction time is 3 hours to this product after measured, and glyphosate products yield is 97.5%.
Embodiment 2
Select shell (cocoanut shell) active carbon 1000g, its specific area 1350m
2/ g, iodine number 1300mg/g, order number 30-60 order, carries out drying and processing as base material.After drying and processing, its moisture content is 1%, adds the salpeter solution 3000ml of 15%, soaks and is filtered dry after 90 minutes, rinses and makes pH value reach 4.5, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times with clear water.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 250 DEG C, setup times carries out heat treatment in 200 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1100 DEG C, and shield gas flow rate is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 400 minutes.Protective gas selects nitrogen.Obtain product 875g, the reaction time is 4.8 hours to this product after measured, and glyphosate products yield is 93.5%.
Embodiment 3
The wooden crushing activated carbon 1000g selecting Physical to produce, its specific area 1200m
2/ g, iodine number 1100mg/g, order number 20-40 order, carries out drying and processing as base material.After drying and processing, its moisture content is 1%, adds the salpeter solution 3000ml of 15%, soaks and is filtered dry after 90 minutes, rinses and makes pH value reach 4.5, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times with clear water.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 250 DEG C, setup times carries out heat treatment in 200 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1100 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 400 minutes.Protective gas selects nitrogen.Obtain product 835g, the reaction time is 5.6 hours to this product after measured, and glyphosate products yield is 94.2%.
Embodiment 4
Select ature of coal crushing activated carbon 1000g, its specific area 1100m
2/ g, iodine number 980mg/g, order number 40-60 order, carries out drying and processing as base material.After drying and processing, its moisture content is 1%, adds the salpeter solution 3000ml of 15%, soaks and is filtered dry after 90 minutes, rinses and makes pH value reach 4.5, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times with clear water.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 250 DEG C, setup times carries out heat treatment in 200 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1100 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 400 minutes.Protective gas selects nitrogen.Obtain product 890g, the reaction time is 6.5 hours to this product after measured, and glyphosate products yield is 89%.
Embodiment 5
Select chemical method granular activated carbon 1000g, its specific area 1200m
2/ g, iodine number 1100mg/g, order number 20-40 order, carries out drying and processing as base material.After drying and processing, its moisture content is 1%, adds the salpeter solution 3000ml of 15%, soaks and is filtered dry after 90 minutes, rinses and makes pH value reach 4.5, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times with clear water.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 250 DEG C, setup times carries out heat treatment in 200 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1100 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 400 minutes.Protective gas selects nitrogen.Obtain product 880g, the reaction time is 4.2 hours to this product after measured, and glyphosate products yield is 95.3%.
Embodiment 6:
Select spheric active carbon 1000g, its specific area 1800m
2/ g, iodine number 800mg/g, order number 4-42 order, carries out drying and processing as base material.When its moisture content is 1% after drying and processing, add the salpeter solution 3000ml of 15%, be filtered dry after soaking 30 minutes at 70 DEG C, rinse with clear water and make pH value reach 2, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times.This charcoal base material, for being less than 1%, being put in micro-wave oven and is heat-treated, set temperature 150 DEG C, 180 minutes drying times by dried charcoal base material moisture content.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 100 DEG C, setup times carries out heat treatment in 300 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 600 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 720 minutes.Protective gas selects nitrogen.Obtain product 736g, the reaction time is 5.6 hours to this product after measured, and glyphosate products yield is 84.6%.
Embodiment 7
Select chemical method powdered activated carbon 1000g, its specific area 1350m
2/ g, iodine number 1050mg/g, order number 80-120 order, carries out drying and processing as base material.After drying and processing, its moisture content is 1%, adds the salpeter solution 3000ml of 15%, soaks and is filtered dry after 90 minutes, rinses and makes pH value reach 4.5, put in thermostatic drying chamber, set temperature 160 DEG C, 180 minutes drying times with clear water.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 250 DEG C, setup times carries out heat treatment in 200 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1100 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 400 minutes.Protective gas selects nitrogen.Obtain product 830g, the reaction time is 5.2 hours to this product after measured, and glyphosate products yield is 93.8%.
Embodiment 8:
Select spheric active carbon 1000g, its specific area 800m
2/ g, iodine number 1500mg/g, order number 260-325 order, carries out drying and processing as base material.When its moisture content is 1% after drying and processing, add the salpeter solution 3000ml of 15%, be filtered dry after soaking 300 minutes at 60 DEG C, rinse with clear water and make pH value reach 9, put in thermostatic drying chamber, set temperature 300 DEG C, 60 minutes drying times.Dried charcoal base material moisture content is for being less than 1%, and put in micro-wave oven by this charcoal base material and heat-treat, set temperature 300 DEG C, setup times carries out heat treatment in 30 minutes.In order to avoid charcoal base material causes burning in heating process, the nitrogen that can lead to 15L/min is protected.After sizing terminates, charcoal base material is cooled to room temperature, dislocation carries out activation process in microwave atmosphere protection stove.Treatment temperature is set as 1200 DEG C, and gas flow is set as 2L/min, and pressure setting is 0.4KPa, and the time is set as 30 minutes.Protective gas selects nitrogen.Obtain product 890g, the reaction time is 6.5 hours to this product after measured, and glyphosate products yield is 89%.
Claims (6)
1. a preparation method for the special char combustion catalyst of glyphosate, is characterized in that: make active carbon form the special char combustion catalyst of glyphosate by modification and thermal technology's process successively active carbon;
Described modification is:
(1), by active carbon and surface modifier mixing, active carbon is made to soak 30-300 minute in surface modifier;
(2), by after the activated carbon filtration that soaked, adopt clear water rinsing, the active carbon pH value after rinsing should between 2-9;
(3) active carbon, after rinsing should be dried, and dried charcoal base material moisture content is for being less than 1%; The charcoal material pH value of drying should control between 2-9, bake out temperature 150-300 DEG C;
(4), rinsing dry after active carbon carry out the heat treatment of the oxygen-containing functional group consolidated on charcoal atomic surface, heat treated temperature is 100-300 DEG C, and the time is 30-300 minute;
Described surface modifier comprise in sulfuric acid solution, salpeter solution, liquor natrii hypochloritis, liquor potassic permanganate, hydrogen peroxide solution any one;
Described thermal technology is treated to:
(1), the active carbon that modification is crossed is placed in heating furnace, in the heating furnace that temperature is 600-1200 DEG C, react with the activator of catalytic activity that excites inputed in heating furnace, reaction time is 30-720 minute, reacts and carries out in vacuum or containing when protective gas;
(2), the active carbon processed through step (1) is carried out grinding process and obtain the special char combustion catalyst of glyphosate;
Described activator is ammonia.
2. the preparation method of the special char combustion catalyst of glyphosate according to claim 1, it is characterized in that: described active carbon be adopt in fiber, resin, petroleum coke, pitch, wooden, coal, shell any one be raw material, carry out by traditional chemical method or Physical the product producing graininess or the powder form formed, the specific area of active carbon is 800-1800m
2/ g; Iodine sorption value 800-1500mg/g; Order number is the active carbon charcoal material of 4-325 object graininess or powder form.
3. the preparation method of the special char combustion catalyst of glyphosate according to claim 2, is characterized in that: described active carbon take specific area as 1200-1800m
2/ g; Iodine sorption value is 1200-1500mg/g.
4. the preparation method of the special char combustion catalyst of glyphosate according to claim 1, is characterized in that: described protective gas is nitrogen; The pressure of protective gas in heating furnace is 0.2-5KPa.
5. the preparation method of the special char combustion catalyst of glyphosate according to claim 1, is characterized in that: the mode of heating of heating furnace is microwave irradiation heating.
6. the preparation method of the special char combustion catalyst of glyphosate according to claim 1, it is characterized in that: before described grinding process, pulverize after need removing solid sinter, grade grinder selected by pulverizer, according to different application demands, adjustable product order number is 80-325 order.
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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 |
| 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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