CN104447407A - Method of preparing chlorothalonil with hexachlorobenzene content lower than 10ppm - Google Patents
Method of preparing chlorothalonil with hexachlorobenzene content lower than 10ppm Download PDFInfo
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- CN104447407A CN104447407A CN201410740625.1A CN201410740625A CN104447407A CN 104447407 A CN104447407 A CN 104447407A CN 201410740625 A CN201410740625 A CN 201410740625A CN 104447407 A CN104447407 A CN 104447407A
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Abstract
The invention relates to a method of preparing chlorothalonil with hexachlorobenzene content lower than 10ppm. According to the method, modified coconut shell activated carbon is used as a catalyst, the chlorothalonil is prepared on a large scale by virtue of an improved composite bed process, and the content of hexachlorobenzene in a final product is lower than 10ppm. By adopting the method disclosed by the invention, the content of hexachlorobenzene in the final product is reduced to be lower than 10ppm, the conversation ratio of isophthalonitrile is increased to be not smaller than 96%, the purity of the tetrachloroisophthalonitrile product is increased to be not lower than 99%, the yield is increased to be not lower than 93%, the service life of activated carbon is over 600 hours, and the large-scale production of the chlorothalonil with hexachlorobenzene content lower than 10ppm is realized.
Description
Technical field
The present invention relates to pesticide field, relate in particular to and a kind ofly prepare the method for hexachlorobenzene content lower than the m-tetrachlorophthalodinitrile of 10ppm.
Technical background
M-tetrachlorophthalodinitrile, i.e. termil, be a kind of protectiveness wide-spectrum bactericide, it have efficiently, the feature such as low toxicity, low residue, can prevent and treat the fungal disease of multiple kinds of crops, have protection and treatment dual function; And industrially can be used as the mould inhibitor of the things such as coating, electrical equipment, leather, paper, cloth.Take Isophthalodinitrile as raw material production m-tetrachlorophthalodinitrile, production technique the most frequently used at present comprises: fluidized-bed, fixed bed and multiple-hearth.Compare and traditional add the raw material such as aluminum oxide, silicon-dioxide, adding gac is in process of production catalyzer, the decomposition of cyano group under can improving the transformation efficiency of Isophthalodinitrile, reduce temperature of reaction and stoping high temperature; But the consumption of gac is large, expensive, substantially increases production cost simultaneously.US6034264 proposes to complete the Halogenated of cyano-containing aromatics by single fluidized bed production technique, and wherein gac as the condition of catalyzer is: average pore diameter is not less than
pore diameter exists
the pore volume of scope is not less than 0.45ml/g, and specific surface area is not less than 900m
2/ g, the work-ing life of catalyzer can reach 300h.In production process, external ingredient requirement purity >=99.0% used, and the purity of internal sources is difficult to reach this requirement, if use the gac of above-mentioned requirements, there will be residue accumulation in production process too fast, the problems such as catalyzer work-ing life is short, cannot meet actual production requirement.
In addition, superchlorination impurity Perchlorobenzene (HCB) can be formed in m-tetrachlorophthalodinitrile production process, this is a kind of persistence organic pollutant (POPs), existing market requires more and more stricter to m-tetrachlorophthalodinitrile product hexachlorobenzene content, according to up-to-date standard, export requirement is at below 40ppm, and European and American areas then requires below 20ppm.CN200610048783.6 proposition recombining process prepares low hexachlorobenzene, can control the content of Perchlorobenzene lower than 40ppm, can not meet the requirement of European and American areas; there is chlorine consumption large simultaneously; waste gas recovery utilization ratio is low, and industrial scale is little, cannot realize the defects such as large-scale production.
Summary of the invention
In order to overcome the series of problems run in current existing production m-tetrachlorophthalodinitrile, as: dreg accumulation is too fast, and feed stock conversion is low, catalyzer easily blocks, easy to wear in use procedure, degradation under work-ing life, being less than 10ppm to realize impurity hexachlorobenzene content simultaneously, meeting the requirement that outlet is American-European.The invention provides and a kind ofly prepare the method for hexachlorobenzene content lower than the m-tetrachlorophthalodinitrile of 10ppm, described method for catalyzer, on a large scale prepares m-tetrachlorophthalodinitrile by the multiple-hearth technique improved with modification cocoanut active charcoal, and in final product hexachlorobenzene content lower than 10ppm.Specifically, the present invention realizes by following technical solution.
Prepare the method for hexachlorobenzene content lower than the m-tetrachlorophthalodinitrile of 10ppm, it is characterized in that, described method comprises the steps:
The activation of step one, catalyzer: be filled into by modification cocoanut active charcoal in fluidized-bed and fixed bed, under nitrogen protection, is warming up to 120 DEG C and carries out except water treatment to cocoanut active charcoal; After 1h, be warming up to 250 DEG C, pass into chlorine to activate cocoanut active charcoal, without hydrogen chloride gas to tail gas;
Described modification cocoanut active charcoal is containing rare earth Lewis acid Ytterbium trichloride and the muriatic cocoanut active charcoal of traditional Lewis acid, and described traditional Lewis acid muriate is iron(ic) chloride and/or zinc chloride; The addition of described metal chloride is 0.1 ~ 0.5 % by weight of cocoanut active charcoal total amount, and rare earth Lewis acid Ytterbium trichloride and the muriatic mol ratio of traditional Lewis acid are 1:30 ~ 100;
The pre-treatment of step 2, Isophthalodinitrile: raw material Isophthalodinitrile is put in melting device with feeder, raw material is melting at 170 ~ 190 DEG C in melting device; Isophthalodinitrile after melting enters vaporizer, and from the upper charging opening charging of vaporizer, carburettor temperature is 220 ~ 240 DEG C, and bottom is furnished with settling pocket; Nitrogen enters vaporizer from lower opening for feed, takes the raw material of vaporization out of vaporizer from top; Wherein the mol ratio of Isophthalodinitrile and nitrogen is 1:6 ~ 9;
Step 3, chlorination: the amount of required for reaction chlorine is divided into two portions, contain the Isophthalodinitrile gas and vapor permeation of nitrogen in the chlorine of 2/3 and step 2, enter in the fluidized-bed of step a, the temperature of fluidized-bed is 250 ~ 300 DEG C; The gas completing the first step reaction in fluidized-bed is mixed into fixed bed with remaining 1/3 chlorine again and carries out postreaction, and fixed bed temperature is 280 ~ 320 DEG C; The mol ratio wherein entering fixed bed and fluidized-bed chlorine is 1:2.5 ~ 5, and the mol ratio of Isophthalodinitrile and chlorine is 1:7 ~ 10;
Step 4, aftertreatment: reacted gas obtains the crystal powder of termil after cooling; Water, FeCl are used successively to the tail gas that reaction produces
2, Ca (OH)
2absorb.
The granularity of the cocoanut active charcoal in described step one is 6 ~ 30 orders, and specific surface area is not less than 800m
2/ g, pore diameter exists
the pore volume of scope is not less than 0.53ml/g, and wherein diameter is
the ratio of hole be not less than 65%;
The preparation of the cocoanut active charcoal of described step one is: configuration metal chloride solutions, is heated to 80 DEG C, then adds cocoanut active charcoal, after dipping 1-3h, leaches gac, obtains the cocoanut active charcoal through modification after drying; Wherein Cl in dipping solution
-solubility be greater than 0.1mol/L, be preferably 0.15 ~ 0.2mol/L; Dipping time is greater than 24h, is preferably 30 ~ 48h;
Preferably, in described step one, the granularity of the cocoanut active charcoal that fluidized-bed adopts is preferably 10 ~ 30 orders, and pore diameter exists
the pore volume of scope is preferably 0.57 ~ 0.65ml/g; Wherein diameter is
the ratio of hole be 70 ~ 80%;
Preferably, in described step one, the granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 10 orders, and pore diameter exists
the pore volume of scope is preferably 0.6 ~ 0.77ml/g, and wherein diameter is
the ratio of hole be 65 ~ 70%;
Preferably, in described step one, the addition of metal chloride is 0.25 ~ 0.4 % by weight of cocoanut active charcoal total amount;
Preferably, be 1:30 ~ 60 at described step one middle-weight rare earths Lewis acid Ytterbium trichloride and the sour muriatic mol ratio of Lewis;
Preferably, in step 2, the mol ratio of Isophthalodinitrile and nitrogen is for being 1:7 ~ 9;
Preferably, in step 3, the mol ratio entering fixed bed and fluidized-bed chlorine is 1:3 ~ 4;
Preferably, in step 3, the mol ratio of Isophthalodinitrile and chlorine is 1:8 ~ 9.
About adding rare earth Lewis acid Ytterbium trichloride and traditional Lewis acid muriate in cocoanut active charcoal simultaneously, if only add traditional Lewis acid, the addition of metal chloride is large, and catalyst activity is relatively low, and hexachlorobenzene content is high; And only adding rare earth Lewis acid, cost is relatively high; Add rare earth Lewis acid and traditional Lewis acid simultaneously, not only can improve catalyst performance, can also save production cost.
The present invention utilizes diluent gas to reduce the concentration of chlorine in reaction process.
Settling pocket is furnished with bottom the vaporizer selected in the present invention, this is because at high temperature can self-condensation reaction be there is in Isophthalodinitrile, produce from condensation product be liquid at the reaction temperatures, easily stick to the surface of gac, comprise the surface of gac hole, cause gac to bond and pore plugging, the transformation efficiency induced reaction reduces and the work-ing life of gac reduces.Therefore, need before raw material enters reactor reaction, removing melting and vaporescence in produce Isophthalodinitrile from condensation product.
Select specific cocoanut active charcoal in the present invention, because the work-ing life of gac is relevant with the pore volume of gac, the pore volume of gac is larger, and work-ing life is longer; But pore volume is crossed conference and caused catalytic mechanical degradation, finally affect the use of gac.Therefore, need, under the normal service condition ensureing gac, to select the gac that pore volume is as far as possible large.In fluidized-bed reaction process, gac is in suspended state, can collide between gac and between gac and wall of container, so the preferred pore diameter of fluid process exists
the pore volume of scope is the gac of 0.57 ~ 0.65ml/g, and the preferred pore diameter of fixed bed process exists
the pore volume of scope is the gac of 0.6 ~ 0.77ml/g.
In addition, in catalytic process, it is generally acknowledged: macropore (pore diameter is greater than 50nm) plays the effect of transport; Mesopore (pore diameter is 2 ~ 50nm) can adsorbed gas, is also the passage leading to micropore simultaneously; Micropore (pore diameter is less than 2nm) determines the performance of catalyzer; And at the catalytic process mesoporosity diameter of Isophthalodinitrile be
hole contribute maximum in chlorination catalytic process.Therefore the preferred diameter of fluidized-bed is
hole account for 70 ~ 80% gac; The preferred diameter of fixed bed is
hole account for 65 ~ 70% gac.
The granularity of the cocoanut active charcoal selected in the present invention is 6 ~ 30 orders.The maximum fluidization velocity of fluidized-bed, critical flow velocity, the residence time are all relevant with the particle diameter of catalyzer; Particle diameter is excessive, and easily cause reactant in fluidized-bed, react insufficient, and particle diameter is too small, gac is in use easy to wear, causes catalyzer to reduce work-ing life.Therefore the granularity of the cocoanut active charcoal of fluidized-bed employing is preferably 10 ~ 30 orders; And the granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 10 orders.
The present invention adds rare earth Lewis acid in gac: Ytterbium trichloride, and traditional Lewis acid iron(ic) chloride, one or both in zinc chloride.Tradition Lewis acid needs excessive use as catalyzer, and easy in inactivation, and rare earth element has very high coordination ability, electronics generation complexing action can be accepted, have unique electronics and chemical property, therefore, rare earth Lewis acid has more advantage as catalyzer than traditional Lewis acid.Ytterbium element electronic configuration formula is [Xe] 4f
146S
2easily lose the most stable valence state that electronics in two 6s subgrades and 4f subgrade electronics form positive trivalent, in chlorination catalytic process, Yb provides unoccupied orbital for halogen, makes it become strong electrophilic reagent and Isophthalodinitrile forms complex compound, finally obtains HCl and termil.But rare earth Lewis acid is expensive, a large amount of use causes production cost to raise, and therefore adopts the method for simultaneously adding rare earth Lewis acid and traditional Lewis acid in gac, obtains all comparatively ideal catalyzer of selectivity, catalytic activity and stability.Only add traditional Lewis acid, in gac, the content of metal chloride needs to reach more than 20%; And adding rare earth Lewis acid and traditional Lewis acid simultaneously, muriatic content only needs 0.1 ~ 0.5% just can reach identical catalytic effect, substantially reduces the usage quantity of metal chloride, has both reduced production cost, in turn saves resource.According to the kinetics of adsorption of gac to metal chloride, in the modifying process of cocoanut active charcoal, the time that gac floods in metal chloride solutions is greater than 24 hours, is preferably 30 ~ 48h.
The present invention is by passing into the concentration of nitrogen for chlorine in diluting reaction process, temperature of reaction not only can be made to be reduced to 240 ~ 250 DEG C by 300 DEG C, and effectively can form Perchlorobenzene by controls local superchlorination, therefore the mol ratio controlling Isophthalodinitrile and nitrogen is 1:6 ~ 9, is preferably 1:7 ~ 9; Control the ratio of leading to fixed bed and fluidized-bed chlorine simultaneously, the superchlorination of Isophthalodinitrile in fluidized-bed can be avoided, thus improve the yield of raw material, reduce hexachlorobenzene content in product, avoid the refining further of product, cost is reduced greatly, therefore the ratio controlling fixed bed and fluidized-bed chlorine is: 1:2.5 ~ 5, preferred 1:3 ~ 4.
The reacted tail gas of the present invention uses water, FeCl successively
2, Ca (OH)
2absorb, realize tail gas zero release, and the treatment of wastes with processes of wastes against one another, to turn waste into wealth, detailed process is shown in CN201220380340.8.
By the optimization of above-mentioned activated carbon modified and production technique; the content of Perchlorobenzene is made to be reduced to below 10ppm; improve transformation efficiency >=96% of Isophthalodinitrile; improve purity >=99% and productive rate >=93% of termil product; the work-ing life of gac reaches more than 600h, achieves the large-scale production of hexachlorobenzene content lower than the m-tetrachlorophthalodinitrile of 10ppm simultaneously.
Embodiment
Embodiment 1 ~ 5 (activation of catalyzer)
Embodiment 1 (not adding rare earth Lewis acid Ytterbium trichloride)
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 1, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 10 ~ 14 orders, and pore diameter exists
the pore volume of scope is 0.6ml/g, and wherein diameter is
the ratio of hole be 70.4%; The granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 8 orders, and pore diameter exists
the pore volume of scope is preferably 0.62ml/g, and wherein diameter is
the ratio of hole be preferably 67.5%.Above-mentioned cocoanut active charcoal is impregnated into Cl
-solubility be (iron(ic) chloride FeCl in 5mol/L metal chloride solutions
3concentration be 1mol/L, zinc chloride ZnCl
2concentration be 1mol/L), be heated to 80 DEG C, after dipping 30h, leach gac, after drying, obtain the gac (fluidized-bed and fixed bed select gac be designated as gac A1, gac A2 respectively) of modification; Ultimate analysis test result: in gac A1, gac A2, the content of metal chloride is 15.3%, 16.1%.
Embodiment 2 (only adding rare earth Lewis acid Ytterbium trichloride)
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 2, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 10 ~ 14 orders, and pore diameter exists
the pore volume of scope is 0.6ml/g, and wherein diameter is
the ratio of hole be 70.4%; The granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 8 orders, and pore diameter exists
the pore volume of scope is preferably 0.62ml/g, and wherein diameter is
the ratio of hole be preferably 67.5%.Above-mentioned cocoanut active charcoal is impregnated into Cl
-solubility be (Ytterbium trichloride YbCl in 0.06mol/L metal chloride solutions
3concentration be 20mmol/L), be heated to 80 DEG C, after dipping 30h, leach gac, after drying, obtain the gac (fluidized-bed and fixed bed select gac be designated as gac B1, gac B2 respectively) of modification; Ultimate analysis test result: in gac A1, gac A2, the content of metal chloride is 0.2%, 0.16%.
Embodiment 3
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 3, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 10 ~ 14 orders, and pore diameter exists
the pore volume of scope is 0.6ml/g, and wherein diameter is
the ratio of hole be 70.4%; The granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 8 orders, and pore diameter exists
the pore volume of scope is preferably 0.62ml/g, and wherein diameter is
the ratio of hole be preferably 67.5%.Above-mentioned cocoanut active charcoal is impregnated into Cl
-solubility be (wherein Ytterbium trichloride YbCl in 0.15mol/L metal chloride solutions
3concentration be 1.92mmol/L, iron(ic) chloride FeCl
3concentration be 28.85mmol/L, zinc chloride ZnCl
2concentration be 28.85mmol/L), be heated to 80 DEG C, after dipping 30h, leach gac, after drying, obtain the gac (fluidized-bed and fixed bed select gac be designated as gac C1, gac C2 respectively) of modification; Ultimate analysis test result: in gac C1, gac C2, the content of metal chloride is 0.32%, 0.29%; The addition of Ytterbium trichloride is 1.6%, 1.5% of metal chloride total addition level in cocoanut active charcoal.
Embodiment 4
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 4, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 10 ~ 14 orders, and pore diameter exists
the pore volume of scope is 0.6ml/g, and wherein diameter is
the ratio of hole be 70.4%; The granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 8 orders, and pore diameter exists
the pore volume of scope is preferably 0.62ml/g, and wherein diameter is
the ratio of hole be preferably 67.5%.Above-mentioned cocoanut active charcoal is impregnated into Cl
-solubility be (wherein Ytterbium trichloride YbCl in 0.18mol/L metal chloride solutions
3concentration be 1.75mmol/L, iron(ic) chloride FeCl
3concentration be 34.95mmol/L, zinc chloride ZnCl
2concentration be 34.95mmol/L), be heated to 80 DEG C, after dipping 30h, leach gac, after drying, obtain the gac (fluidized-bed and fixed bed select gac be designated as gac D1, gac D2 respectively) of modification; Ultimate analysis test result: in gac D1, gac D2, the content of metal chloride is 0.28%, 0.26%; The addition of Ytterbium trichloride is 1.2%, 1.3% of metal chloride total addition level in cocoanut active charcoal.。
Embodiment 5
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 5, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 14 ~ 18 orders, and pore diameter exists
the pore volume of scope is 0.63ml/g, and wherein diameter is
the ratio of hole be 73.5%; The granularity of the cocoanut active charcoal that fixed bed adopts is preferably 8 ~ 10 orders, and pore diameter exists
the pore volume of scope is preferably 0.68ml/g, and wherein diameter is
the ratio of hole be preferably 68.3%.Above-mentioned cocoanut active charcoal is impregnated into Cl
-solubility be (wherein Ytterbium trichloride YbCl in 0.15mol/L metal chloride solutions
3concentration be 2.83mmol/L, iron(ic) chloride FeCl
3concentration be 28.3mmol/L, zinc chloride ZnCl
2concentration be 28.3mmol/L), be heated to 80 DEG C, after dipping 36h, leach gac, after drying, obtain the gac (fluidized-bed and fixed bed select gac be designated as gac E1, gac E2 respectively) of modification; Ultimate analysis test result: in gac E1, gac E2, the content of metal chloride is 0.35%, 0.33%; The addition of Ytterbium trichloride is 1.5%, 1.6% of metal chloride total addition level in cocoanut active charcoal.。
Embodiment 6
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 6, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 14 ~ 18 orders, and pore diameter exists
the pore volume of scope is 0.63ml/g, and wherein diameter is
the ratio of hole be 73.5%; The granularity of the cocoanut active charcoal that fixed bed adopts is preferably 8 ~ 10 orders, and pore diameter exists
the pore volume of scope is preferably 0.68ml/g, and wherein diameter is
the ratio of hole be preferably 68.3%.Above-mentioned cocoanut active charcoal is impregnated into Cl
-solubility be (wherein Ytterbium trichloride YbCl in 0.18mol/L metal chloride solutions
3concentration be 1.75mmol/L, iron(ic) chloride FeCl
3concentration be 34.95mmol/L, zinc chloride ZnCl
2concentration be 34.95mmol/L), be heated to 80 DEG C, after dipping 36h, leach gac, after drying, obtain the gac (fluidized-bed and fixed bed select gac be designated as gac F1, gac FE2 respectively) of modification; Ultimate analysis test result: in gac F1, gac F2, the content of metal chloride is 0.31%, 0.28%, the addition of Ytterbium trichloride is 1.3%, 1.4% of metal chloride total addition level in cocoanut active charcoal.
Embodiment 7 ~ 14 (technical process of Isophthalodinitrile catalytic chlorination)
Embodiment 7
In fluidized-bed, add 1000kg gac A1, in fixed bed, add 1200kg gac A2, the resistance to air loss of inspection reactor and whole system pipeline, guarantee air tight after, pass into nitrogen and heat raised temperature to 120 DEG C, keeping 120 DEG C of 1h, be then warming up to 250 DEG C, pass into chlorine activated carbon, start to pass into chlorine, until two reactor each point temperature-stables, in tail gas, inspection does not measure HCl, activation terminates, and soak time is generally 3 hours; After catalyst activation terminates, put in melting device with feeder by raw material Isophthalodinitrile, at 170 ~ 190 DEG C, raw material is melting in melting device; Then the Isophthalodinitrile of molten state is from the upper charging opening charging of vaporizer, and be furnished with settling pocket bottom vaporizer, temperature is 220 ~ 240 DEG C; Nitrogen enters vaporizer from lower opening for feed, takes the raw material of vaporization out of vaporizer from top; Wherein the mol ratio of Isophthalodinitrile and nitrogen is 1:6.
The amount of required for reaction chlorine is divided into two portions, by the chlorine of 2/3 and the Isophthalodinitrile gas and vapor permeation containing nitrogen, enter fluidized-bed reaction, the temperature of fluidized-bed is 250 ~ 280 DEG C, and then to be mixed in fixed bed with remaining 1/3 chlorine and to react, the temperature of fixed bed is 280 ~ 300 DEG C; The ratio wherein entering fixed bed and fluidized-bed chlorine is: 1:3, and the mol ratio of Isophthalodinitrile and total chlorine is 1:7 (i.e. theoretical value 1.75 times).Reacted gas obtains the crystal powder of termil after cooling; Water, FeCl are used successively to the tail gas that reaction produces
2, Ca (OH)
2absorb.Interpretation of result: the transformation efficiency of Isophthalodinitrile is 94.3%, the purity of termil product be 98.5% and productive rate be 92.2%, hexachlorobenzene content is 34ppm, and the work-ing life of gac reaches 241h.
Embodiment 8
Implementation process in embodiment 8, with reference to embodiment 7, adds 1000kg gac B1, adds 1200kg gac B2 in fixed bed in fluidized-bed.Interpretation of result: the transformation efficiency of Isophthalodinitrile is 96.8%, the purity of termil product is 99.3%, productive rate is 93.7%, and hexachlorobenzene content is 8ppm, and the work-ing life of gac reaches 634h.
Embodiment 9
Implementation process in embodiment 9, with reference to embodiment 7, adds 1000kg gac C1, adds 1200kg gac C2 in fixed bed in fluidized-bed; The mol ratio of Isophthalodinitrile and nitrogen is 1:8, and the ratio entering fixed bed and fluidized-bed chlorine is: 1:3.5, and the mol ratio of Isophthalodinitrile and total chlorine is 1:8 (i.e. theoretical value 2 times); The temperature of fluidized-bed, fixed bed is 240 ~ 250 DEG C.Interpretation of result: the transformation efficiency of Isophthalodinitrile is 96.5%, the purity of termil product is 99.1%, productive rate is 93.4%, and hexachlorobenzene content is 9ppm, and the work-ing life of gac reaches 610h.In addition, above-mentioned D1, D2 is adopted; E1, E2; F1, F2; Substitute C1 and C2 respectively, obtained product purity is all more than 99%, and the productive rate of product is all more than 93%, and the content of Perchlorobenzene is also all at below 10ppm.
Embodiment 10 (not being furnished with settling pocket bottom vaporizer)
Implementation process in embodiment 10, with reference to embodiment 9, is not furnished with settling pocket bottom vaporizer.Interpretation of result: the transformation efficiency of Isophthalodinitrile is 92.1%, the purity of termil product is 98.2%, productive rate is 91.5%, and the work-ing life of gac reaches 258h.
Embodiment 11 (chlorine all passes into fluidized-bed)
Implementation process in embodiment 11 is with reference to embodiment 9, and chlorine, with certain flow velocity and the Isophthalodinitrile gas and vapor permeation containing nitrogen, enters fluidized-bed reaction, and the mol ratio of Isophthalodinitrile and chlorine is 1:8 (i.e. theoretical value 2 times); Fluidized-bed temperature is 280 ~ 300 DEG C.Interpretation of result: the transformation efficiency of Isophthalodinitrile is 95.5%, the purity of termil product is 98.6%, productive rate is 93.5%, and hexachlorobenzene content is 21ppm, and the work-ing life of gac reaches 597h.
Embodiment 12
Implementation process in embodiment 12, with reference to embodiment 9, adds 1000kg gac D1, adds 1200kg gac D2 in fixed bed in fluidized-bed.Interpretation of result: the transformation efficiency of Isophthalodinitrile is 94%, the purity of termil product is 98.5%, productive rate is 93.2%, and hexachlorobenzene content is 7ppm, and the work-ing life of gac reaches 568h.
Embodiment 13
Implementation process in embodiment 13, with reference to embodiment 9, adds 1000kg gac E1, adds 1200kg gac E2 in fixed bed in fluidized-bed; The mol ratio of Isophthalodinitrile and nitrogen is 1:9, and the ratio entering fixed bed and fluidized-bed chlorine is: 1:3.5, and the mol ratio of Isophthalodinitrile and total chlorine is 1:8 (i.e. theoretical value 2 times).Interpretation of result: the transformation efficiency of Isophthalodinitrile is 96.5%, the purity of termil product is 99.4%, and productive rate is 93.6%, and hexachlorobenzene content is 8ppm, and the work-ing life of gac reaches 640h.
Embodiment 14
Implementation process in embodiment 14, with reference to embodiment 9, adds 1000kg gac F1, adds 1200kg gac F2 in fixed bed in fluidized-bed; The ratio entering fixed bed and fluidized-bed chlorine is: 1:5, and the mol ratio of Isophthalodinitrile and total chlorine is 1:10 (i.e. theoretical value 2.5 times).Interpretation of result: the transformation efficiency of Isophthalodinitrile is 94.7%, the purity of termil product is 98.9%, and productive rate is 92.8%, and hexachlorobenzene content is 13ppm, and the work-ing life of gac reaches 570h.
By embodiment interpretation of result, adopt modified gac gas phase catalysis to produce termil and have the following advantages: the content being reduction of Perchlorobenzene; Two is efficiently solve catalyzer easily to bond, the susceptible to plugging problem of hole; Three is improve catalyzer work-ing life and selectivity of catalyst; Four is the transformation efficiencys that improve Isophthalodinitrile, improves the purity of product.
A kind of hexachlorobenzene content of preparing of the present invention is described by concrete example lower than the method for the m-tetrachlorophthalodinitrile of 10ppm, those skilled in the art can use for reference content of the present invention, the links such as appropriate change raw material, processing condition realize other object corresponding, its relevant change does not all depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included within scope of the present invention.
Claims (10)
1. prepare the method for hexachlorobenzene content lower than the m-tetrachlorophthalodinitrile of 10ppm, it is characterized in that, described method comprises the steps:
The activation of step one, catalyzer: be filled into by modification cocoanut active charcoal in fluidized-bed and fixed bed, under nitrogen protection, is warming up to 120 DEG C and carries out except water treatment to cocoanut active charcoal; After 1h, be warming up to 250 DEG C, pass into chlorine to activate cocoanut active charcoal, without hydrogen chloride gas to tail gas;
Described modification cocoanut active charcoal is containing rare earth Lewis acid Ytterbium trichloride and the muriatic cocoanut active charcoal of traditional Lewis acid, and described traditional Lewis acid muriate is iron(ic) chloride and/or zinc chloride; The addition of described metal chloride is 0.1 ~ 0.5 % by weight of cocoanut active charcoal total amount, and rare earth Lewis acid Ytterbium trichloride and the muriatic mol ratio of traditional Lewis acid are 1:30 ~ 100;
The pre-treatment of step 2, Isophthalodinitrile: raw material Isophthalodinitrile is put in melting device with feeder, raw material is melting at 170 ~ 190 DEG C in melting device; Isophthalodinitrile after melting enters vaporizer, and from the upper charging opening charging of vaporizer, carburettor temperature is 220 ~ 240 DEG C, and bottom is furnished with settling pocket; Nitrogen enters vaporizer from lower opening for feed, takes the raw material of vaporization out of vaporizer from top; Wherein the mol ratio of Isophthalodinitrile and nitrogen is 1:6 ~ 9;
Step 3, chlorination: the amount of required for reaction chlorine is divided into two portions, contain the Isophthalodinitrile gas and vapor permeation of nitrogen in the chlorine of 2/3 and step 2, enter in the fluidized-bed of step a, the temperature of fluidized-bed is 250 ~ 300 DEG C; The gas completing the first step reaction in fluidized-bed is mixed into fixed bed with remaining 1/3 chlorine again and carries out postreaction, and fixed bed temperature is 280 ~ 320 DEG C; The mol ratio wherein entering fixed bed and fluidized-bed chlorine is 1:2.5 ~ 5, and the mol ratio of Isophthalodinitrile and chlorine is 1:7 ~ 10;
Step 4, aftertreatment: reacted gas obtains the crystal powder of termil after cooling; Water, FeCl are used successively to the tail gas that reaction produces
2, Ca (OH)
2absorb.
2. method according to claim 1, is characterized in that, the granularity of the cocoanut active charcoal in described step one is 6 ~ 30 orders, and specific surface area is not less than 800m
2/ g, pore diameter exists
the pore volume of scope is not less than 0.53ml/g, and wherein diameter is
the ratio of hole be not less than 65%.
3. method according to claim 1, is characterized in that, the preparation of the cocoanut active charcoal of described step one is: configuration metal chloride solutions, be heated to 80 DEG C, then add cocoanut active charcoal, after dipping 1-3h, leach gac, after drying, obtain the cocoanut active charcoal through modification; Wherein Cl in dipping solution
-solubility be greater than 0.1mol/L; Dipping time is greater than 24h.
4. method according to claim 1, is characterized in that, in described step one, the granularity of the cocoanut active charcoal that fluidized-bed adopts is 10 ~ 30 orders, and pore diameter exists
the pore volume of scope is 0.57 ~ 0.65ml/g; Wherein diameter is
the ratio of hole be 70 ~ 80%.
5. want the method described in 4 according to right, it is characterized in that, in described step one, the granularity of the cocoanut active charcoal that fixed bed adopts is preferably 6 ~ 10 orders, and pore diameter exists
the pore volume of scope is 0.6 ~ 0.77ml/g, and wherein diameter is
the ratio of hole be 65 ~ 70%.
6. method according to claim 1, is characterized in that, in described step one, the addition of metal chloride is 0.25 ~ 0.4 % by weight of cocoanut active charcoal total amount.
7. method according to claim 1, is characterized in that, described step one middle-weight rare earths Lewis acid Ytterbium trichloride and the muriatic mol ratio of Lewis acid are 1:30 ~ 60.
8. method according to claim 1, is characterized in that, in described step 2, the mol ratio of Isophthalodinitrile and nitrogen is for being 1:7 ~ 9.
9. method according to claim 1, is characterized in that, in described step 3, the mol ratio entering fixed bed and fluidized-bed chlorine is 1:3 ~ 4.
10. according to method according to claim 1, it is characterized in that, in described step 3, the mol ratio of Isophthalodinitrile and chlorine is 1:8 ~ 9.
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|---|---|---|---|---|
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816505A (en) * | 1970-05-18 | 1974-06-11 | Jefferson Chem Co Inc | Preparation of halogenated dicyanobenzenes |
| CN85101963A (en) * | 1985-04-01 | 1986-09-03 | 云南省化工研究所 | The catalyst method for making of preparation termil |
| CN1844090A (en) * | 2006-04-18 | 2006-10-11 | 江阴市苏利精细化工有限公司 | Continuous production method for tetrachloro terephthalonitrile |
| WO2007017900A2 (en) * | 2005-05-26 | 2007-02-15 | Sisir Kumar Mandal | Preparation of para dichlorobenzene from benzene or mono chlorobenzene |
| CN1948278A (en) * | 2006-11-07 | 2007-04-18 | 云南省化工研究院 | Production method of low hexachlorobenzene content chlorothalonil |
| CN101962344A (en) * | 2009-07-23 | 2011-02-02 | 江苏新河农用化工有限公司 | Method for purifying tetrachloroisophthalonitrile crystal |
| CN102718682A (en) * | 2011-03-29 | 2012-10-10 | 张苏侠 | Preparation method for chlorothalonil |
-
2014
- 2014-12-08 CN CN201410740625.1A patent/CN104447407B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816505A (en) * | 1970-05-18 | 1974-06-11 | Jefferson Chem Co Inc | Preparation of halogenated dicyanobenzenes |
| CN85101963A (en) * | 1985-04-01 | 1986-09-03 | 云南省化工研究所 | The catalyst method for making of preparation termil |
| WO2007017900A2 (en) * | 2005-05-26 | 2007-02-15 | Sisir Kumar Mandal | Preparation of para dichlorobenzene from benzene or mono chlorobenzene |
| CN1844090A (en) * | 2006-04-18 | 2006-10-11 | 江阴市苏利精细化工有限公司 | Continuous production method for tetrachloro terephthalonitrile |
| CN1948278A (en) * | 2006-11-07 | 2007-04-18 | 云南省化工研究院 | Production method of low hexachlorobenzene content chlorothalonil |
| CN101962344A (en) * | 2009-07-23 | 2011-02-02 | 江苏新河农用化工有限公司 | Method for purifying tetrachloroisophthalonitrile crystal |
| CN102718682A (en) * | 2011-03-29 | 2012-10-10 | 张苏侠 | Preparation method for chlorothalonil |
Non-Patent Citations (1)
| Title |
|---|
| 陈赛玉: "百菌清生产工艺技改", 《云南化工》 * |
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