CN104447407B - A kind of method preparing the hexachlorobenzene content Bravo less than 10ppm - Google Patents
A kind of method preparing the hexachlorobenzene content Bravo less than 10ppm Download PDFInfo
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- CN104447407B CN104447407B CN201410740625.1A CN201410740625A CN104447407B CN 104447407 B CN104447407 B CN 104447407B CN 201410740625 A CN201410740625 A CN 201410740625A CN 104447407 B CN104447407 B CN 104447407B
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Abstract
The present invention relates to a kind of method preparing the hexachlorobenzene content Bravo less than 10ppm.Described method, with modified cocoanut active charcoal as catalyst, is prepared hexachlorobenzene content in Bravo, and end product on a large scale by the multiple-hearth technique improved and is less than 10ppm.The method using the present invention; the content of Perchlorobenzene in final products is made to be reduced to below 10ppm; improve conversion ratio >=96% of isophthalodinitrile; improve purity >=99% and productivity >=93% of termil product; the service life of activated carbon reaches more than 600h, is simultaneously achieved the large-scale production of the hexachlorobenzene content Bravo less than 10ppm.
Description
Technical field
The present invention relates to pesticide field, relate in particular to a kind of prepare the hexachlorobenzene content Bravo less than 10ppm
Method.
Technical background
Bravo, i.e. termil, be a kind of protectiveness wide-spectrum bactericide, and it has efficiently, low toxicity, low
The features such as residual, 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 antifungus agent of the things such as coating, electrical equipment, leather, paper, cloth.With isophthalodinitrile for raw material production hundred bacterium
Clearly, the most the most frequently used production technology includes: fluid bed, fixed bed and multiple-hearth.Compare traditional addition oxidation
The raw material such as aluminum, silicon dioxide, adding activated carbon in process of production is catalyst, can improve turning of isophthalodinitrile
The decomposition of cyano group under rate, reduction reaction temperature and prevention high temperature；But the consumption of activated carbon is big, expensive simultaneously,
Substantially increase production cost.US6034264 proposes to complete cyano-containing aromatic series by single fluidized bed production technology
Compound Halogenated, wherein activated carbon as the condition of catalyst is: average pore diameter is not less thanHole is straight
Footpath existsThe pore volume of scope is not less than 0.45ml/g, and specific surface area is not less than 900m2/ g, the use of catalyst
Life-span can reach 300h.In production process, external ingredient requirement purity >=99.0% used, and internal sources is pure
Degree is extremely difficult to this requirement, if using the activated carbon of above-mentioned requirements, there will be residue accumulation too fast in production process,
The problem such as catalyst service life is short, it is impossible to meet actual production requirement.
Additionally, can form superchlorination impurity Perchlorobenzene (HCB) in Bravo production process, this is that a kind of persistency has
Organic pollutants (POPs), Bravo product hexachlorobenzene content is required increasingly stricter, according to up-to-date by existing market
Standard, export requirement is at below 40ppm, and European and American areas then requires below 20ppm.CN200610048783.6 carries
Go out and prepare low hexachlorobenzene with combination process, the content of Perchlorobenzene can be controlled less than 40ppm, it is impossible to meet European and American areas
Requirement, there is chlorine consumption big simultaneously, waste gas recovery utilization rate is low, and production scale is little, it is impossible to realize extensive
The defects such as metaplasia product.
Summary of the invention
In order to overcome the series of problems run in current existing production Bravo, such as: dreg accumulation is too fast, raw material
Conversion ratio is low, and catalyst easily blocks, easy to wear during use, degradation under service life, simultaneously in order to realize impurity
Hexachlorobenzene content is less than 10ppm, meets the requirement that outlet is American-European.The present invention provides one to prepare hexachlorobenzene content and is less than
The method of the Bravo of 10ppm, described method is with modified cocoanut active charcoal as catalyst, by the multiple-hearth work improved
Skill is prepared hexachlorobenzene content in Bravo, and end product on a large scale and is less than 10ppm.Specifically, the present invention passes through
Following technical scheme realizes.
A kind of prepare the hexachlorobenzene content method of Bravo less than 10ppm, it is characterised in that described method include as
Lower step:
Step one, the activation of catalyst: be filled in fluid bed and fixed bed by modification cocoanut active charcoal, protect at nitrogen
Protect down, be warming up to 120 DEG C and cocoanut active charcoal carried out except water processes；After 1h, it is warming up to 250 DEG C, is passed through chlorine
Activation cocoanut active charcoal, without hydrogen chloride gas to tail gas；
Described modified cocoanut active charcoal is containing rare earth Lewis acid Ytterbium trichloride and traditional Lewis muriatic coconut husk of acid
Activated carbon, described traditional Lewis acid chloride is iron chloride and/or zinc chloride；The addition of described metal chloride
For 0.1～0.5 weight % of cocoanut active charcoal total amount, rare earth Lewis acid Ytterbium trichloride is muriatic with traditional Lewis acid
Mol ratio is 1:30～100；
Step 2, the pretreatment of isophthalodinitrile: raw material isophthalodinitrile is put in melting device with feeder,
Raw material is melted at 170～190 DEG C in melting device；Isophthalodinitrile after Rong Rong enters carburator, from carburator
Upper charge door feeds, and carburettor temperature is 220～240 DEG C, and bottom is furnished with expansion chamber；Nitrogen enters vapour from lower charging aperture
Change device, take the raw material of vaporization out of carburator from top；Wherein isophthalodinitrile is 1:6～9 with the mol ratio of nitrogen；
Step 3, chlorination: the amount of required for reaction chlorine is divided into two parts, in the chlorine of 2/3 and step 2, contains nitrogen
The isophthalodinitrile gas mixing of gas, enters in the fluid bed of step a, and the temperature of fluid bed is 250～300 DEG C；?
Fluid bed completes the gas of first step reaction be mixed into fixed bed again with remaining 1/3 chlorine and carry out supplementing anti-
Should, fixed bed temperature is 280～320 DEG C；The mol ratio wherein entering fixed bed and fluid bed chlorine is 1:2.5～5,
Benzene dicarbonitrile is 1:7～10 with the mol ratio of chlorine；
Step 4, post processing: reacted gas obtains the crystal powder of termil after cooling；To instead
The tail gas that should produce is successively with water, FeCl2、Ca(OH)2Absorb.
The granularity of the cocoanut active charcoal in described step one is 6～30 mesh, and specific surface area is not less than 800m2/ g, hole
Diameter existsThe pore volume of scope is not less than 0.53ml/g, the most a diameter ofThe ratio of hole the least
In 65%；
The preparation of the cocoanut active charcoal of described step one is: configuration metal chloride solutions, is heated to 80 DEG C, then
Add cocoanut active charcoal, after dipping 1-3h, leach activated carbon, obtain the cocoanut active charcoal being modified after drying；Its
Cl in middle dipping solution-Solubility more than 0.1mol/L, preferably 0.15～0.2mol/L；Dip time is more than 24h,
It is preferably 30～48h；
Preferably, in described step one, the granularity of the cocoanut active charcoal that fluid bed uses is preferably 10～30 mesh, and hole is straight
Footpath existsThe pore volume of scope is preferably 0.57～0.65ml/g；The most a diameter ofThe ratio of hole be
70～80%；
Preferably, in described step one, the granularity of the cocoanut active charcoal that fixed bed uses is preferably 6～10 mesh, and hole is straight
Footpath existsThe pore volume of scope is preferably 0.6～0.77ml/g, the most a diameter ofThe ratio of hole be
65～70%；
Preferably, in described step one, the addition of metal chloride is 0.25～0.4 weight of cocoanut active charcoal total amount
Amount %；
Preferably, at described step one middle rare earth Lewis acid Ytterbium trichloride with the muriatic mol ratio of Lewis acid it is
1:30～60；
Preferably, in step 2, isophthalodinitrile is 1:7～9 with the mol ratio of nitrogen；
Preferably, in step 3, the mol ratio entering fixed bed and fluid bed chlorine is 1:3～4,；
Preferably, in step 3, isophthalodinitrile is 1:8～9 with the mol ratio of chlorine.
About adding rare earth Lewis acid Ytterbium trichloride and tradition Lewis acid chloride in cocoanut active charcoal simultaneously, if only
Adding tradition Lewis acid, the addition of metal chloride is big, and catalyst activity is the lowest, and hexachlorobenzene content is high；And
Only adding rare earth Lewis acid, cost is relatively high；Add rare earth Lewis acid and tradition Lewis acid, not only simultaneously
Catalyst performance can be improved, moreover it is possible to save production cost.
The present invention utilizes diluent gas to reduce the concentration of chlorine in course of reaction.
It is furnished with expansion chamber, this is because isophthalodinitrile at high temperature can occur certainly bottom the carburator selected in the present invention
Condensation reaction, the product that self condenses of production is liquid at the reaction temperatures, is easily adhered the surface at activated carbon, including
The surface of activated carbon hole, causes activated carbon bonding and pore plugging, causes the conversion ratio of reaction to reduce and activated carbon
Service life reduce.Accordingly, it would be desirable to before raw material enters reactor reaction, remove and melt and vaporescence produces
Raw isophthalodinitrile self condense product.
The present invention selects specific cocoanut active charcoal, owing to the service life of activated carbon and the pore volume of activated carbon are relevant,
The pore volume of activated carbon is the biggest, and service life is the longest；But pore volume is crossed conference and is caused catalytic mechanical hydraulic performance decline, finally
Affect the use of activated carbon.Accordingly, it would be desirable under the normal service condition ensureing activated carbon, select pore volume to try one's best big
Activated carbon.During fluidized-bed reaction, activated carbon is in suspended state, between activated carbon and activated carbon and chamber wall
Between can collide, so the preferred pore diameter of fluid-bed process existsThe pore volume of scope is 0.57～0.65ml/g
Activated carbon, and the preferred pore diameter of fixed bed process existsThe pore volume of scope is the activity of 0.6～0.77ml/g
Charcoal.
Additionally, in catalytic process, it is considered that: macropore (pore diameter is more than 50nm) plays the effect of transport；
Mesopore (pore diameter is 2～50nm) also can be the passage leading to micropore with adsorbed gas simultaneously；Micropore (hole
Diameter be less than 2nm) determine catalyst performance；And it is a diameter of in the catalytic process mesopore of isophthalodinitrile
Hole in chlorination catalytic process, contribute maximum.Therefore fluid bed is the most a diameter ofHole account for 70～80%
Activated carbon；Fixed bed is the most a diameter ofHole account for the activated carbon of 65～70%.
The granularity of the cocoanut active charcoal selected in the present invention is 6～30 mesh.The maximum fluidization velocity of fluid bed, critical flow
Speed, the time of staying all relevant with the particle diameter of catalyst；Particle diameter is excessive, easily causes reactant and reacts in fluid bed and do not fill
Point, and particle diameter is too small, activated carbon is the most easy to wear, causes catalyst to reduce service life.Therefore fluid bed
The granularity of the cocoanut active charcoal used is preferably 10～30 mesh；And the granularity of the cocoanut active charcoal that fixed bed uses is preferably
6～10 mesh.
The present invention adds rare earth Lewis acid in activated carbon: Ytterbium trichloride, and tradition Lewis acid iron chloride, chlorination
One or both in zinc.Tradition Lewis acid needs to be excessively used as catalyst, and easy in inactivation, and rare earth element
There is the highest coordination ability, it is possible to accept electronics generation complexing, there is electronics and the chemical property of uniqueness, because of
This, rare earth Lewis acid as catalyst than traditional Lewis acid more advantage.Ytterbium element electronic configuration formula is
[Xe]4f146S2, easily lose the electronics in two 6s subgrades and 4f subgrade electronically form the most stable valency of positive trivalent
State, in chlorination catalytic process, Yb provides unoccupied orbital for halogen so that it is become strong electrophilic reagent and isophthalodinitrile shape
Become complex, finally give HCl and termil.But rare earth Lewis acid is expensive, use in a large number
Cause production cost to raise, therefore use in activated carbon, add rare earth Lewis acid and the side of tradition Lewis acid simultaneously
Method, obtains selectivity, catalysis activity and the most comparatively ideal catalyst of stability.Only add tradition Lewis acid, live
In property charcoal, the content of metal chloride needs to reach more than 20%；And add rare earth Lewis acid and tradition Lewis simultaneously
Acid, muriatic content only needs 0.1～0.5% just can reach identical catalytic effect, substantially reduces metal chloride
Usage amount, had both reduced production cost, had saved again resource.According to the activated carbon adsorption dynamics adsorption kinetics to metal chloride,
In the modifying process of cocoanut active charcoal, the time that activated carbon impregnates in metal chloride solutions is more than 24 hours,
It is preferably 30～48h.
The present invention by being passed through nitrogen concentration of chlorine during diluting reaction, be possible not only to make reaction temperature by
300 DEG C are reduced to 240～250 DEG C, and can effectively control local superchlorination and form Perchlorobenzene, therefore control isophthalic diformazan
Nitrile is 1:6～9 with the mol ratio of nitrogen, preferably 1:7～9；Control to lead to fixed bed and the ratio of fluid bed chlorine simultaneously,
Isophthalodinitrile superchlorination in fluid bed can be avoided, thus improve the yield of raw material, reduce Perchlorobenzene in product and contain
Amount, it is to avoid product the most refined, makes cost be substantially reduced, therefore controls fixed bed and the ratio of fluid bed chlorine
For: 1:2.5～5, preferably 1:3～4.
The reacted tail gas of the present invention is successively with water, FeCl2、Ca(OH)2Absorb, it is achieved tail gas zero-emission, and with
Useless control useless, turn waste into wealth, detailed process is shown in CN201220380340.8.
By the above-mentioned activated carbon modified and optimization of production technology, the content of Perchlorobenzene is made to be reduced to below 10ppm,
Improve conversion ratio >=96% of isophthalodinitrile, improve purity >=99% of termil product and produce
Rate >=93%, reaches more than 600h the service life of activated carbon, is simultaneously achieved hexachlorobenzene content less than 10ppm's
The large-scale production of Bravo.
Detailed description of the invention
Embodiment 1～5 (activation of catalyst)
Embodiment 1 (being not added with rare earth Lewis acid Ytterbium trichloride)
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 1, the coconut palm that fluid bed uses
The granularity of shell activated carbon is 10～14 mesh, and pore diameter existsThe pore volume of scope is 0.6ml/g, the most a diameter ofThe ratio of hole be 70.4%；The granularity of the cocoanut active charcoal that fixed bed uses is preferably 6～8 mesh, hole
Gap diameter existsThe pore volume of scope is preferably 0.62ml/g, the most a diameter ofThe ratio of hole excellent
Elect 67.5% as.Above-mentioned cocoanut active charcoal is impregnated into Cl-Solubility be (chlorination in 5mol/L metal chloride solutions
Ferrum FeCl3Concentration be 1mol/L, zinc chloride ZnCl2Concentration be 1mol/L), be heated to 80 DEG C, impregnate 30h
After, leach activated carbon, (activated carbon that fluid bed and fixed bed are selected is designated as respectively to obtain modified activated carbon after drying
Activated carbon A1, activated carbon A2)；Elementary analysis test result: metal chloride in activated carbon A1, activated carbon A2
Content be 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 coconut palm that fluid bed uses
The granularity of shell activated carbon is 10～14 mesh, and pore diameter existsThe pore volume of scope is 0.6ml/g, the most a diameter ofThe ratio of hole be 70.4%；The granularity of the cocoanut active charcoal that fixed bed uses is preferably 6～8 mesh, hole
Gap diameter existsThe pore volume of scope is preferably 0.62ml/g, the most a diameter ofThe ratio of hole excellent
Elect 67.5% as.Above-mentioned cocoanut active charcoal is impregnated into Cl-Solubility be (chlorine in 0.06mol/L metal chloride solutions
Change ytterbium YbCl3Concentration be 20mmol/L), be heated to 80 DEG C, after dipping 30h, leach activated carbon, dried
To modified activated carbon (activated carbon that fluid bed and fixed bed are selected is designated as activated carbon B1, activated carbon B2 respectively)；Unit
Element analyzes test result: in activated carbon A1, activated carbon 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 coconut palm that fluid bed uses
The granularity of shell activated carbon is 10～14 mesh, and pore diameter existsThe pore volume of scope is 0.6ml/g, the most a diameter ofThe ratio of hole be 70.4%；The granularity of the cocoanut active charcoal that fixed bed uses is preferably 6～8 mesh, hole
Gap diameter existsThe pore volume of scope is preferably 0.62ml/g, the most a diameter ofThe ratio of hole excellent
Elect 67.5% as.Above-mentioned cocoanut active charcoal is impregnated into Cl-Solubility be (its in 0.15mol/L metal chloride solutions
Middle Ytterbium trichloride YbCl3Concentration be 1.92mmol/L, iron chloride FeCl3Concentration be 28.85mmol/L, zinc chloride
ZnCl2Concentration be 28.85mmol/L), be heated to 80 DEG C, dipping 30h after, leach activated carbon, obtain after drying
Modified activated carbon (activated carbon that fluid bed and fixed bed are selected is designated as activated carbon C1, activated carbon C2 respectively)；Element
Analyze test result: in activated carbon C1, activated carbon C2, the content of metal chloride is 0.32%, 0.29%；Chlorination
The addition of ytterbium is in cocoanut active charcoal the 1.6% of metal chloride total addition level, 1.5%.
Embodiment 4
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 4, the coconut palm that fluid bed uses
The granularity of shell activated carbon is 10～14 mesh, and pore diameter existsThe pore volume of scope is 0.6ml/g, the most a diameter ofThe ratio of hole be 70.4%；The granularity of the cocoanut active charcoal that fixed bed uses is preferably 6～8 mesh, hole
Gap diameter existsThe pore volume of scope is preferably 0.62ml/g, the most a diameter ofThe ratio of hole excellent
Elect 67.5% as.Above-mentioned cocoanut active charcoal is impregnated into Cl-Solubility be (its in 0.18mol/L metal chloride solutions
Middle Ytterbium trichloride YbCl3Concentration be 1.75mmol/L, iron chloride FeCl3Concentration be 34.95mmol/L, zinc chloride
ZnCl2Concentration be 34.95mmol/L), be heated to 80 DEG C, dipping 30h after, leach activated carbon, obtain after drying
Modified activated carbon (activated carbon that fluid bed and fixed bed are selected is designated as activated carbon D1, activated carbon D2 respectively)；Unit
Element analyzes test result: in activated carbon D1, activated carbon D2, the content of metal chloride is 0.28%, 0.26%；Chlorine
The addition changing ytterbium is in cocoanut active charcoal the 1.2% of metal chloride total addition level, 1.3%..
Embodiment 5
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 5, the coconut palm that fluid bed uses
The granularity of shell activated carbon is 14～18 mesh, and pore diameter existsThe pore volume of scope is 0.63ml/g, wherein diameter
ForThe ratio of hole be 73.5%；The granularity of the cocoanut active charcoal that fixed bed uses is preferably 8～10 mesh,
Pore diameter existsThe pore volume of scope is preferably 0.68ml/g, the most a diameter ofThe ratio of hole
It is preferably 68.3%.Above-mentioned cocoanut active charcoal is impregnated into Cl-Solubility be (its in 0.15mol/L metal chloride solutions
Middle Ytterbium trichloride YbCl3Concentration be 2.83mmol/L, iron chloride FeCl3Concentration be 28.3mmol/L, zinc chloride
ZnCl2Concentration be 28.3mmol/L), be heated to 80 DEG C, dipping 36h after, leach activated carbon, obtain after drying
Modified activated carbon (activated carbon that fluid bed and fixed bed are selected is designated as activated carbon E1, activated carbon E2 respectively)；Element
Analyze test result: in activated carbon E1, activated carbon E2, the content of metal chloride is 0.35%, 0.33%；Chlorination
The addition of ytterbium is in cocoanut active charcoal the 1.5% of metal chloride total addition level, 1.6%..
Embodiment 6
The cocoanut active charcoal (purchased from Jiangxi Chemical Co., Ltd. everyday) selected in embodiment 6, the coconut palm that fluid bed uses
The granularity of shell activated carbon is 14～18 mesh, and pore diameter existsThe pore volume of scope is 0.63ml/g, wherein diameter
ForThe ratio of hole be 73.5%；The granularity of the cocoanut active charcoal that fixed bed uses is preferably 8～10 mesh,
Pore diameter existsThe pore volume of scope is preferably 0.68ml/g, the most a diameter ofThe ratio of hole
It is preferably 68.3%.Above-mentioned cocoanut active charcoal is impregnated into Cl-Solubility be (its in 0.18mol/L metal chloride solutions
Middle Ytterbium trichloride YbCl3Concentration be 1.75mmol/L, iron chloride FeCl3Concentration be 34.95mmol/L, zinc chloride
ZnCl2Concentration be 34.95mmol/L), be heated to 80 DEG C, dipping 36h after, leach activated carbon, obtain after drying
Modified activated carbon (activated carbon that fluid bed and fixed bed are selected is designated as activated carbon F1, activated carbon FE2 respectively)；Unit
Element analyzes test result: in activated carbon F1, activated carbon F2, the content of metal chloride is 0.31%, 0.28%, chlorination
The addition of ytterbium is in cocoanut active charcoal the 1.3% of metal chloride total addition level, 1.4%.
Embodiment 7～14 (isophthalodinitrile catalytic chlorination technological process)
Embodiment 7
Adding 1000kg activated carbon A1 in fluid bed, add 1200kg activated carbon A2 in fixed bed, inspection is anti-
Answer device and the air-tightness of whole system pipeline, it is ensured that after air tight, be passed through nitrogen and heat liter high-temperature to 120 DEG C,
Keep 120 DEG C of 1h, then heat to 250 DEG C, be passed through chlorine activated carbon, start to be passed through chlorine, until two
Reactor each point temperature stabilization, in tail gas, inspection does not measures HCl, and activation terminates, and soak time is generally 3 hours；Urge
After agent activation terminates, with feeder, raw material isophthalodinitrile is put in melting device, at 170～190 DEG C,
Raw material is melted in melting device；Then the isophthalodinitrile of molten state feeds from the upper charge door of carburator, at the bottom of carburator
Portion is furnished with expansion chamber, and temperature is 220～240 DEG C；Nitrogen enters carburator from lower charging aperture, by the raw material of vaporization from upper
Side takes carburator out of；Wherein isophthalodinitrile is 1:6 with the mol ratio of nitrogen.
The amount of required for reaction chlorine is divided into two parts, and the chlorine by 2/3 mixes with the isophthalodinitrile gas containing nitrogen
Closing, enter fluidized-bed reaction, the temperature of fluid bed is 250～280 DEG C, is mixed into remaining 1/3 chlorine the most again
Entering in fixed bed and react, the temperature of fixed bed is 280～300 DEG C；Wherein enter fixed bed and the ratio of fluid bed chlorine
For: 1:3, isophthalodinitrile is 1:7 (i.e. 1.75 times of theoretical value) with the mol ratio of total chlorine.Reacted gas
Body obtains the crystal powder of termil after cooling；The tail gas producing reaction is successively with water, FeCl2、
Ca(OH)2Absorb.Interpretation of result: the conversion ratio of isophthalodinitrile is 94.3%, termil product pure
Degree is 98.5% and productivity is 92.2%, and hexachlorobenzene content is 34ppm, reaches 241h the service life of activated carbon.
Embodiment 8
Implementation process in embodiment 8, with reference to embodiment 7, adds 1000kg activated carbon B1 in fluid bed, solid
Fixed bed adds 1200kg activated carbon B2.Interpretation of result: the conversion ratio of isophthalodinitrile is 96.8%, tetrachloro isophthalic
The purity of dimethoxy nitrile product is 99.3%, productivity is 93.7%, and hexachlorobenzene content is 8ppm, the service life of activated carbon
Reach 634h.
Embodiment 9
Implementation process in embodiment 9, with reference to embodiment 7, adds 1000kg activated carbon C1 in fluid bed, solid
Fixed bed adds 1200kg activated carbon C2；Isophthalodinitrile is 1:8 with the mol ratio of nitrogen, enters fixed bed and stream
The ratio changing bed chlorine is: 1:3.5, and isophthalodinitrile is 1:8 (i.e. the 2 of theoretical value with the mol ratio of total chlorine
Times)；Fluid bed, the temperature of fixed bed are 240～250 DEG C.Interpretation of result: the conversion ratio of isophthalodinitrile is 96.5%,
The purity of termil product is 99.1%, productivity is 93.4%, and hexachlorobenzene content is 9ppm, activated carbon
Service life reaches 610h.Additionally, use above-mentioned D1, D2；E1、E2；F1、F2；Respectively substitute C1 and
C2, obtained product purity is all more than 99%, and the productivity of product is all more than 93%, and the content of Perchlorobenzene
The most all at below 10ppm.
Embodiment 10 (being not equipped with expansion chamber bottom carburator)
Implementation process in embodiment 10, with reference to embodiment 9, is not equipped with expansion chamber bottom carburator.Interpretation of result:
The conversion ratio of benzene dicarbonitrile is 92.1%, and the purity of termil product is 98.2%, productivity is 91.5%,
The service life of activated carbon reaches 258h.
Embodiment 11 (chlorine is all passed through fluid bed)
Implementation process in embodiment 11 is with reference to embodiment 9, and chlorine is with certain flow velocity and the isophthalic diformazan containing nitrogen
Nitrile gas mixes, and enters fluidized-bed reaction, and isophthalodinitrile is 1:8 (i.e. the 2 of theoretical value with the mol ratio of chlorine
Times)；Fluidized-bed temperature is 280～300 DEG C.Interpretation of result: the conversion ratio of isophthalodinitrile is 95.5%, tetrachloro isophthalic
The purity of dimethoxy nitrile product is 98.6%, productivity is 93.5%, and hexachlorobenzene content is 21ppm, the use longevity of activated carbon
Life reaches 597h.
Embodiment 12
Implementation process in embodiment 12, with reference to embodiment 9, adds 1000kg activated carbon D1 in fluid bed, solid
Fixed bed adds 1200kg activated carbon D2.Interpretation of result: the conversion ratio of isophthalodinitrile is 94%, tetrachloro isophthalic two
The purity of formonitrile HCN product is 98.5%, productivity is 93.2%, and hexachlorobenzene content is 7ppm, reaches the service life of activated carbon
To 568h.
Embodiment 13
Implementation process in embodiment 13, with reference to embodiment 9, adds 1000kg activated carbon E1 in fluid bed, solid
Fixed bed adds 1200kg activated carbon E2；Isophthalodinitrile is 1:9 with the mol ratio of nitrogen, enters fixed bed and stream
The ratio changing bed chlorine is: 1:3.5, and isophthalodinitrile is 1:8 (i.e. the 2 of theoretical value with the mol ratio of total chlorine
Times).Interpretation of result: the conversion ratio of isophthalodinitrile is 96.5%, the purity of termil product is 99.4%,
Productivity is 93.6%, and hexachlorobenzene content is 8ppm, reaches 640h the service life of activated carbon.
Embodiment 14
Implementation process in embodiment 14, with reference to embodiment 9, adds 1000kg activated carbon F1 in fluid bed, solid
Fixed bed adds 1200kg activated carbon F2；The ratio entering fixed bed and fluid bed chlorine is: 1:5, isophthalic diformazan
Nitrile is 1:10 (i.e. 2.5 times of theoretical value) with the mol ratio of total chlorine.Interpretation of result: the conversion of isophthalodinitrile
Rate is 94.7%, and the purity of termil product is 98.9%, and productivity is 92.8%, and hexachlorobenzene content is
13ppm, reaches 570h the service life of activated carbon.
By embodiment interpretation of result, use modified activated carbon gas phase catalysis produce termil have with
Lower advantage: one is reduction of the content of Perchlorobenzene；Two is to efficiently solve catalyst easily to bond, and hole is susceptible to plugging asks
Topic；Three is to improve catalyst service life and selectivity of catalyst；Four is the conversion ratio that improve isophthalodinitrile,
Improve the purity of product.
A kind of method preparing the hexachlorobenzene content Bravo less than 10ppm of the present invention has passed through concrete example
Being described, those skilled in the art can use for reference present invention, and the link such as suitable feed change, process conditions is come
Realizing other purpose corresponding, it is correlated with and changes all without departing from present disclosure, all similar replacements and change
Will become apparent to those skilled in the art that and be considered as being included within the scope of the present invention.
Claims (9)
1. the method preparing the hexachlorobenzene content Bravo less than 10ppm, it is characterised in that described method bag
Include following steps:
Step one, the activation of catalyst: be filled in fluid bed and fixed bed by modification cocoanut active charcoal, protect at nitrogen
Protect down, be warming up to 120 DEG C and cocoanut active charcoal carried out except water processes；After 1h, it is warming up to 250 DEG C, is passed through chlorine
Activation cocoanut active charcoal, without hydrogen chloride gas to tail gas；
Described modified cocoanut active charcoal is containing rare earth Lewis acid Ytterbium trichloride and traditional Lewis muriatic coconut husk of acid
Activated carbon, described traditional Lewis acid chloride is iron chloride and/or zinc chloride；Described rare earth Lewis acid Ytterbium trichloride
With traditional 0.1～0.5 weight % that the Lewis muriatic total addition level of acid is cocoanut active charcoal total amount, rare earth Lewis
Acid Ytterbium trichloride is 1:30～100 with traditional Lewis muriatic mol ratio of acid；
Step 2, the pretreatment of isophthalodinitrile: raw material isophthalodinitrile is put in melting device with feeder,
Raw material is melted at 170～190 DEG C in melting device；Isophthalodinitrile after Rong Rong enters carburator, from carburator
Upper charge door feeds, and carburettor temperature is 220～240 DEG C, and bottom is furnished with expansion chamber；Nitrogen enters vapour from lower charging aperture
Change device, take the raw material of vaporization out of carburator from top；Wherein isophthalodinitrile is 1:6～9 with the mol ratio of nitrogen；
Step 3, chlorination: the amount of required for reaction chlorine is divided into two parts, in the chlorine of 2/3 and step 2, contains nitrogen
The isophthalodinitrile gas mixing of gas, enters in fluid bed, and the temperature of fluid bed is 250～300 DEG C；In fluid bed
Complete the first step reaction gas be mixed into remaining 1/3 chlorine again fixed bed carry out supplement reaction, fixed bed
Temperature is 280～320 DEG C；Isophthalodinitrile is 1:7～10 with the mol ratio of chlorine；
Step 4, post processing: reacted gas obtains the crystal powder of termil after cooling；To instead
The tail gas that should produce is successively with water, FeCl2、Ca(OH)2Absorb.
Method the most according to claim 1, it is characterised in that the grain of the cocoanut active charcoal in described step one
Degree is 6～30 mesh, and specific surface area is not less than 800m2/ g, pore diameter existsThe pore volume of scope is not less than
0.53ml/g, the most a diameter ofThe ratio of hole not less than 65%.
Method the most according to claim 1, it is characterised in that the preparation of the cocoanut active charcoal of described step one
It is: configuration rare earth Lewis acid Ytterbium trichloride and traditional Lewis acid chloride solution, is heated to 80 DEG C, is subsequently adding coconut palm
Shell activated carbon, after dipping 1-3h, leaches activated carbon, obtains the cocoanut active charcoal being modified after drying；Wherein impregnate molten
Cl in liquid-Solubility more than 0.1mol/L；Dip time is more than 24h.
Method the most according to claim 1, it is characterised in that the coconut husk that in described step one, fluid bed uses
The granularity of activated carbon is 10～30 mesh, and pore diameter existsThe pore volume of scope is 0.57～0.65ml/g；The most straight
Footpath isThe ratio of hole be 70～80%.
5. want the method described in 4 according to right, it is characterised in that the coconut husk that in described step one, fixed bed uses is lived
The granularity of property charcoal is preferably 6～10 mesh, and pore diameter existsThe pore volume of scope is 0.6～0.77ml/g, Qi Zhongzhi
Footpath isThe ratio of hole be 65～70%.
Method the most according to claim 1, it is characterised in that described step one middle rare earth Lewis acid chlorination
Ytterbium and 0.25～0.4 weight % that traditional Lewis muriatic total addition level of acid is cocoanut active charcoal total amount.
Method the most according to claim 1, it is characterised in that described step one middle rare earth Lewis acid chlorination
Ytterbium is 1:30～60 with traditional Lewis muriatic mol ratio of acid.
Method the most according to claim 1, it is characterised in that in described step 2, isophthalodinitrile and nitrogen
The mol ratio of gas is 1:7～9.
9. according to method according to claim 1, it is characterised in that in described step 3, isophthalodinitrile
It is 1:8～9 with the mol ratio of chlorine.
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| CN107511155B (en) * | 2016-06-15 | 2020-05-12 | 江苏新河农用化工有限公司 | Catalyst for preparing chlorothalonil and preparation method and application thereof |
| CN107537171A (en) * | 2016-06-28 | 2018-01-05 | 江苏新河农用化工有限公司 | A kind of isophthalodinitrile evaporator |
| CN107056650A (en) * | 2016-10-20 | 2017-08-18 | 江苏维尤纳特精细化工有限公司 | The preparation of high-purity Bravo |
| CN107597091B (en) * | 2017-09-25 | 2019-07-19 | 江苏苏利精细化工股份有限公司 | A kind of production method of high-purity Perchlorobenzonitrile |
| CN107935885A (en) * | 2017-11-30 | 2018-04-20 | 江苏维尤纳特精细化工有限公司 | The preparation method of tetrachloro-p-phenylene's dimethoxy nitrile of low content hexachloro-benzene |
| CN108329235B (en) * | 2018-03-02 | 2020-10-02 | 天津赛普泰克科技有限公司 | Process for producing high-purity chlorothalonil |
| CN111285783B (en) * | 2018-12-06 | 2023-04-18 | 江苏新河农用化工有限公司 | Refining and purifying system and method for high-content chlorothalonil |
| CN109293529B (en) * | 2018-12-06 | 2023-11-24 | 江苏新河农用化工有限公司 | Purifying device and method for producing chlorothalonil with content of hexachlorobenzene not more than 10ppm |
| CN109369454B (en) * | 2018-12-06 | 2023-11-24 | 江苏新河农用化工有限公司 | Continuous rectification and purification system and method for unqualified chlorothalonil |
| CN109265365B (en) * | 2018-12-06 | 2021-11-19 | 江苏新河农用化工有限公司 | Continuous rectification and purification process for high-content chlorothalonil |
| CN111285784B (en) * | 2018-12-06 | 2023-04-18 | 江苏新河农用化工有限公司 | Unqualified chlorothalonil purification system and method |
| CN109438284B (en) * | 2018-12-06 | 2021-12-07 | 江苏新河农用化工有限公司 | Continuous rectification purification process for low-content chlorothalonil |
| CN110845366B (en) * | 2019-12-03 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method and preparation system of chlorothalonil |
| CN112939812B (en) * | 2021-02-07 | 2022-05-03 | 江苏新河农用化工有限公司 | Chlorothalonil production process |
| CN114315640B (en) * | 2021-11-05 | 2023-06-23 | 上海安谱实验科技股份有限公司 | Stable isotope labeled chlorothalonil and synthesis method thereof |
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