CN110523368A - A kind of preparation method, suction chlorine agent and its application of suction chlorine agent - Google Patents
A kind of preparation method, suction chlorine agent and its application of suction chlorine agent Download PDFInfo
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- CN110523368A CN110523368A CN201910794891.5A CN201910794891A CN110523368A CN 110523368 A CN110523368 A CN 110523368A CN 201910794891 A CN201910794891 A CN 201910794891A CN 110523368 A CN110523368 A CN 110523368A
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/80—Phosgene
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/26—Halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2025—Chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The present invention relates to a kind of preparation methods for inhaling chlorine agent, it include: 1) using alumina ball as carrier, the inorganic salts of zinc are reacted in a solvent with 2-methylimidazole, are formed ZIF-8 crystal film in alumina ceramics ball surface, are obtained spherical ZIF-8/ alumina ceramics ball particle；2) the spherical ZIF-8/ alumina ceramics ball particle for obtaining step 1) impregnates in the inorganic salts ammonia spirit of copper, then by separating, washing, drying, roast, obtains suction chlorine agent of the invention.Pass through physical absorption, the method for chemisorption, raw material phosgene is refined using chlorine agent is inhaled, to which the chlorine in phosgene to be reduced within 500ppm, refined phosgene is used for the production of isocyanates, certain improvement result can be brought to the color appearance of isocyanates crude product.
Description
Technical field
The present invention relates to a kind of preparation method for inhaling chlorine agent, inhale chlorine agent and its application.
Background technique
Phosgene is mainly used in the fields such as the intermediate of organic synthesis, pesticide, drug, dyestuff and other heavy chemicals.Light
Gas and amine carry out reaction can be with synthesizing isocyanate, such as toluene di-isocyanate(TDI) (TDI), 4,4 '-diphenylmethane diisocyanates
Ester (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) etc..Currently, isocyanates is main
It is prepared using phosgenation, after corresponding amine such as diphenylmethanediamiand and polymethylene polyphenyl polyamine are mixed with atent solvent
It carries out being sufficiently mixed carry out phosgenation reaction with phosgene again, obtains photochemical reaction liquid, photochemical reaction liquid passes through phosgene removing, solvent
Isocyanates crude product is obtained after removing.Chlorine in phosgene will lead to reaction and produce a large amount of chloro by-products and acids, so that different
Containing a large amount of acid point, hydrolysis chlorine in cyanate crude product, its appearance color is caused to be affected.
CN102092713A discloses a kind of method for producing phosgene by chlorine and reaction of carbon monoxide, chlorine and excess
After carbon monoxide mixes in a mixer, into shell and tube reactor, reaction generates phosgene under activated-carbon catalyst effect, then
Through protecting reactor, it is ensured that chlorine reaction is complete.
CN102060295 discloses a kind of production technology of high-purity phosgene, and operating procedure includes: rich in phosgene and to contain
The mixed gas of the complete excess carbon monoxide of unreacted and other impurity enters at least one rectifying column, and rectifying tower top has fractional condensation
Device, liquid phase provide reflux, most of hydrogen chloride are allowed to be discharged by rectifying tower top with carbon monoxide, while rectifying column bottom obtains high-purity
Phosgene.
CN108212132A discloses a kind of preparation method of chlorine purification agent, and the chlorine purification agent is by following parts by weight
Several raw materials are made: 5-12 parts of sodium chlorite, 12-25 parts of citric acid, 5-12 parts of potassium permanganate, 10-15 parts of bodied ferric sulfate, secondary
It is 12-32 parts of calcium chlorate, 12-20 parts of active silica, 5-12 parts of fungicide, 12-20 parts of sustained release agent, 20-30 parts of activator, high
4-12 parts of molecular flocculant and 20-50 parts of deionized water.
CN101804298A discloses a kind of preparation method of chlorine arresting agent, use supporting medium for calcium hydroxide or
Sodium thiosulfate, carrier are 5A molecular sieve, 13X molecular sieve, silica gel or diatomite, and this method is first to dry and remove supporting medium
Moisture is sieved to obtain granularity≤100 mesh powders with the quasi- sub-sieve of 100 targets after crushing；By the carrier of 80~100 mesh 500
DEG C calcination activation 2h obtains activated carrier, then by mass fraction be 10~40% supporting medium and mass fraction be 60~90%
Activated carrier ground and mixed it is uniform, the sample after grinding is then roasted into 3-8h at 450 DEG C~500 DEG C, finally merging is dry
It is cooled to room temperature in dry device, obtains chlorine arresting agent.
Detect in phosgene whether contain chlorine using the active carbon protection reactor for being filled with active carbon in the prior art, and
So that carbon monoxide is further reacted with chlorine；Using rectifying column separation chlorine, phosgene energy consumption is higher and separation is incomplete；It improves
The molar excess rate of CO can reduce the chlorine content in phosgene, but can improve CO separating energy consumption, and CO is fixed gas, can be increased
Add security risk；Using aqueous suction chlorine agent meeting so that containing moisture in phosgene, the production for being applied to isocyanates to phosgene is produced
It is raw to influence；It is unfavorable in industry the removing of chlorine in phosgene using powdered suction chlorine agent, may cause entrainment in phosgene and inhale chlorine
Agent.
Therefore it needs to invent a kind of safely and effectively method to reduce the chlorine content in phosgene, improves isocyanate products
Color.
Summary of the invention
It is an object of the present invention to provide one kind for absorbing the skill of chlorine in chlorine and/or hydrogen chloride, especially absorption phosgene
Art refines raw material phosgene using chlorine agent is inhaled, by physical absorption, the method for chemisorption so that containing in raw material phosgene
Some chlorine is adsorbed by suction chlorine agent, so that the chlorine in phosgene is reduced within 500ppm, refined phosgene is used for different
The production of cyanate, to the crude product L of isocyanates*There is the improvement of 2-4.
In order to reach the goals above, the present invention adopts the following technical scheme:
The first aspect of the invention provides a kind of preparation method for inhaling chlorine agent, and preparation method includes the following steps:
1) using alumina ball as carrier, the inorganic salts of zinc are reacted in a solvent with 2-methylimidazole, in aluminium oxide
Porcelain ball surface forms ZIF-8 crystal film, obtains spherical ZIF-8/ alumina ceramics ball particle；
2) the spherical ZIF-8/ alumina ceramics ball particle for obtaining step 1) soaks in the inorganic salts ammonia spirit of copper
Stain obtains suction chlorine agent of the invention then by separating, washing, drying, roast.
In the preparation method for inhaling chlorine agent, suction chlorine agent carrier is alumina ball, and surface is smooth, particle diameter
It is preferred that between 3-10mm, more preferable 5-8mm；Its average pore size preferably between 100-300nm, more preferable 150-200nm it
Between.Alumina ball in the particle size range can guarantee that suction chlorine agent bed pressure drop is lower, and with the aluminium oxide with the aperture
Porcelain ball is as carrier, and in inhaling chlorine agent preparation process, alumina ceramics ball surface can be evenly distributed on by inhaling chlorine agent component, provides preferably
Suction chlorine effect.
Preferably, in step 1), the inorganic salts, 2-methylimidazole, solvent of zinc are configured to reaction solution, by reaction solution
It is mixed with alumina ball；The volume ratio of reaction solution and alumina ball is between 10-20.
In the preparation method for inhaling chlorine agent, the inorganic salts of the step 1) zinc are in zinc acetate, zinc chloride, zinc nitrate
One or more, preferably one of zinc acetate, zinc nitrate or a variety of；
Solvent is selected from the ammonium hydroxide methanol mixed solution of volume fraction 5-10%, methanol, in N,N-dimethylformamide (DMF)
One or more, preferably one of 5-10% ammonium hydroxide methanol mixed solution, methanol or a variety of；Wherein 5-10% ammonium hydroxide methanol
Solution is that 20-25wt% concentrated ammonia liquor and methanol are prepared according to volume ratio.
In the preparation method for inhaling chlorine agent, in step 1), the inorganic salts of zinc, 2-methylimidazole, solvent molar ratio be
1:2-10:100-300, preferably 1:4-8:150-250.When the ammonium hydroxide methanol mixing that solvent used is volume fraction 5-10% is molten
When liquid, the mole of solvent is in terms of the sum of mole of ammonia, water and methanol in ammonium hydroxide methanol mixed solution.
In the preparation method for inhaling chlorine agent, in step 1), the preparation of ZIF-8 crystal film is reacted by pre-added pure
Change ZIF-8 crystal seed to cause: in the reaction solution of inorganic salts, 2-methylimidazole, the solvent composition of prepared zinc, 0.1- is added
The purifying ZIF-8 crystal seed of 0.5wt% (on the basis of the quality of reaction solution) is used as reaction solution after evenly mixing, is added closed
In reaction kettle, then crystallization 1-3 hours at 80-120 DEG C.
In the preparation method for inhaling chlorine agent, in step 1), the ZIF-8 crystal of alumina ball carrier surface is prepared
Film surface is fine and close, without obvious hole.
In the preparation method for inhaling chlorine agent, in step 1), the aluminium oxide for the surface crystal film containing ZIF-8 being prepared
Porcelain ball is preferred first to impregnate 12-24h in methyl alcohol, to wash away remaining unreacted reactant, is then dried in vacuo 12- at 40-60 DEG C
48h。
In the preparation method for inhaling chlorine agent, in step 2), the inorganic salts of the copper are selected from copper nitrate, copper chloride, alkali formula
One of copper carbonate, copper sulphate are a variety of, preferably copper nitrate and/or basic copper carbonate；The inorganic salts ammonia spirit of copper it is dense
Degree is 0.005-0.015mol/L, and wherein the concentration of ammonium hydroxide is 20-25wt%.
In the preparation method for inhaling chlorine agent, in step 2), the inorganic salts ammonia spirit dosage of copper is porcelain ball particle volume
2-4 times.The ammonia spirit dipping temperature of inorganic salts of the spherical ZIF-8/ alumina ceramics ball particle in copper is 30-70 DEG C, preferably
40-60℃；Dip time is 1-4h, preferably 2-3h.
In the preparation method for inhaling chlorine agent, in step 2), by spherical ZIF-8/ alumina ceramics ball particle in the inorganic of copper
It is impregnated in salt ammonia spirit, the inorganic salts that can draw copper enter in ZIF-8 crystal duct, subsequent after drying, roasting, In
ZIF-8 crystal load contains copper activity component.
In the preparation method for inhaling chlorine agent, in step 2), the drying is dry 12- under 40-60 DEG C of environment of vacuum
48h, preferably 24-36h.
In the preparation method for inhaling chlorine agent, in step 2), described be roasted under nitrogen atmosphere is roasted, N2Atmosphere roasting temperature
Degree be 300-800 DEG C, preferably 500-600 DEG C, calcining time 1-4h, preferably 2-3h.
The second aspect of the invention is related to the suction chlorine agent prepared by the above method.
The third aspect of the invention, provides the suction chlorine agent in absorbing hydrogen chloride and/or chlorine, in particular for
Absorb the application in terms of the chlorine in phosgene, comprising:
Phosgene crude product is sent into the reactor equipped with suction chlorine agent and is refined, the phosgene of low chlorine content after being refined
Product；The phosgene crude product can be the phosgene of arbitrary prior art preparation, in the phosgene crude product, usually contain 1000-
The chlorine of 3000ppm.
Phosgene crude product enters chlorine in the reactor absorption phosgene equipped with the agent of this suction chlorine, and the flow velocity of phosgene crude product is 100-
300BV/h, preferably 150-250BV/h.
Phosgene gas after absorption is cooled to -20 DEG C to -30 DEG C by heat exchanger, removes carbon monoxide and fixed gas, obtains
To high-purity phosgene product.The phosgene product and amine of low chlorine content are subjected to phosgenation reaction in atent solvent, obtain light
Change reaction solution, photochemical reaction liquid obtains the isocyanates crude product of color perfecting after removing using phosgene removing, atent solvent.
The beneficial effects of the present invention are:
Suction chlorine agent provided by the invention has the characteristics that simple production process, treating capacity are big, can be safely and fast by light
Chlorine in gas is reduced within 500ppm.Chlorine agent will be inhaled through the present invention treated phosgene is used for isocyanates preparation, it can be with
By the L of isocyanates crude product*Improve 2-4.
Specific embodiment
With embodiment, the present invention will be further described below, but the present invention is not limited except as.
The L of isocyanates crude product*Measuring method it is as follows: according to GB/T 6324.6-2014 method measure isocyanates
The X of crude product, Y, Z value (tristimulus values), then referring to L in CN105717108A*Calculation method, according to X, Y, Z value is calculated
To L*Value.
Chlorine content in phosgene is measured using following methods:
(1) testing principle:
Cl2+2KI→2KCl+I2
I2+2Na2S2O3→2NaI+Na2S4O6
(2) detection process:
Enough KI solution is configured, is connected after the freezing of phosgene sampling bottle with glass funnel, KI solution is added in glass funnel,
Opening intermediate connecting valve allows KI solution to fully absorb the chlorine in phosgene, then with ready Na2S2O3Standard solution drop
It is fixed, until KI solution is become colorless by aubergine.
(3) calculation method of the chlorine in phosgene
Wherein, Cl is the content of chlorine in phosgene, mg/L；
V1For the Na of titration consumption2S2O3The volume of standard solution, ml；
V2For the volume of gas sample bottle, L；
C is Na2S2O3The actual concentrations of standard solution, mol/L.
Embodiment raw material sources:
Conventional chemical reagent used uses commercial reagent；
Alumina ball: it buys from Zhong Tian Co., Ltd, Pingxiang Jiangxi, industrial goods；
Phosgene crude product: isocyanate plant production in the magnificent industry park in Ningbo ten thousand, industrial goods；
Polyamines: isocyanate plant production in the magnificent industry park in Ningbo ten thousand, industrial goods；
ZIF-8 crystal seed is synthesized from laboratory, and synthetic method is as follows:
Zinc nitrate, 2-methylimidazole, methanol that molar ratio is 1:8:300 are configured to reaction solution, stirred at room temperature
1h is mixed, obtained crystal seed suspension is washed through 10000rpm centrifugation 10min, methanol, after repeating above-mentioned centrifuge washing operation 3 times,
60 DEG C of oven dryings are placed in constant weight.
In following embodiment, the ammonium hydroxide used is the ammonium hydroxide of mass concentration 25%.
Embodiment 1
(1) zinc nitrate, 2-methylimidazole, methanol that molar ratio is 1:4:300 are configured to reaction solution, stirred to clear
Clearly.It chooses in the reaction kettle of the alumina ball addition polytetrafluoroethyllining lining of diameter 8mm, average pore size 100nm and is used as carrier,
Alumina ceramics sphere volume and reaction solution volume ratio are 1:20.Reaction solution is slowly added into aforesaid reaction vessel, and to reaction
0.10%wt ZIF-8 crystal seed is added in kettle, 100 DEG C is maintained after then sealing reaction kettle crystallization 2 hours, naturally cools to room
Temperature takes out the balloon borne body of kettle internal oxidition aluminium porcelain, is placed in methanol and impregnates 24 hours, then take out the vacuum drying at 40 DEG C.
(2) alumina ball that there is ZIF-8 crystal film on surface is placed in the nitric acid for the 0.005mol/L that volume ratio is 1:2
In the ammonia spirit of copper (i.e. the ammonia spirit volume of copper nitrate is 2 times of alumina ball), maintains 50 DEG C to impregnate 2 hours, remove
Maceration extract is removed, is washed, the dry 12h under 40 DEG C of environment of vacuum, in N2500 DEG C are maintained under atmosphere to roast 2 hours, obtain inhaling chlorine agent
A。
Embodiment 2
(1) zinc chloride, 2-methylimidazole, DMF that molar ratio is 1:8:300 are configured to reaction solution, stirred to clarify.
Choose diameter 4mm, the alumina ball of average pore size 300nm is added in the reaction kettle of polytetrafluoroethyllining lining and is used as carrier, oxygen
Change aluminium porcelain sphere volume and reaction solution volume ratio is 1:10.Reaction solution is slowly added into aforesaid reaction vessel, and to reaction kettle
Middle addition 0.10%wt ZIF-8 crystal seed maintains 100 DEG C crystallization 2 hours after then sealing reaction kettle, cooled to room temperature,
The balloon borne body of kettle internal oxidition aluminium porcelain is taken out, is placed in methanol and impregnates 24 hours, then take out the vacuum drying at 40 DEG C.
(2) alumina ball that there is ZIF-8 crystal film on surface is placed in the chlorination for the 0.015mol/L that volume ratio is 1:4
It in the ammonia spirit of copper, maintains 30 DEG C to impregnate 4 hours, removes maceration extract, washing, the dry 48h under 40 DEG C of environment of vacuum, in N2
300 DEG C are maintained under atmosphere to roast 4 hours, obtain inhaling chlorine agent B.
Embodiment 3
(1) zinc acetate, 2-methylimidazole, methanol that molar ratio is 1:4:200 are configured to reaction solution, stirred to clear
Clearly.It chooses in the reaction kettle of the alumina ball addition polytetrafluoroethyllining lining of diameter 6mm, average pore size 100nm and is used as carrier,
Alumina ceramics sphere volume and reaction solution volume ratio are 1:15.Reaction solution is slowly added into aforesaid reaction vessel, and to reaction
0.10%wt ZIF-8 crystal seed is added in kettle, 100 DEG C is maintained after then sealing reaction kettle crystallization 2 hours, naturally cools to room
Temperature takes out the balloon borne body of kettle internal oxidition aluminium porcelain, is placed in methanol and impregnates 24 hours, then take out the vacuum drying at 40 DEG C.
(2) alumina ball that there is ZIF-8 crystal film on surface is placed in the alkali formula for the 0.01mol/L that volume ratio is 1:3
It in the ammonia spirit of copper carbonate, maintaining 70 DEG C to impregnate 1 hour, removes maceration extract, washing is dried for 24 hours under 40 DEG C of environment of vacuum,
In N2300 DEG C are maintained under atmosphere to roast 4 hours, obtain inhaling chlorine agent C.
Embodiment 4
(1) it is configured to zinc acetate, 2-methylimidazole, 5% ammonium hydroxide methanol solution that molar ratio is 1:6:200 to react molten
Liquid stirs to clarify.Choose the reaction kettle of the alumina ball addition polytetrafluoroethyllining lining of diameter 6mm, average pore size 200nm
Middle to be used as carrier, alumina ceramics sphere volume and reaction solution volume ratio are 1:15.Reaction solution is slowly added into aforesaid reaction vessel
It is interior, and 0.10%wt ZIF-8 crystal seed is added into reaction kettle, 100 DEG C are maintained after then sealing reaction kettle crystallization 2 hours, from
It is so cooled to room temperature, takes out the balloon borne body of kettle internal oxidition aluminium porcelain, be placed in methanol and impregnate 24 hours, then take out the vacuum at 40 DEG C
Drying.
(2) alumina ball that there is ZIF-8 crystal film on surface is placed in the nitric acid for the 0.01mol/L that volume ratio is 1:3
It in the ammonia spirit of copper, maintains 50 DEG C to impregnate 4 hours, removes maceration extract, washing, the dry 36h under 50 DEG C of environment of vacuum, in N2
500 DEG C are maintained under atmosphere to roast 3 hours, obtain inhaling chlorine agent D.
Embodiment 5
Present case uses the suction chlorine agent A in embodiment 1.
Phosgene crude product (wherein chlorine content 1137ppm) enters chlorine in the reactor absorption phosgene equipped with the agent of this suction chlorine,
Flow velocity is 150BV/h.Phosgene gas after inhaling chlorine agent absorption is water-cooled to -20 DEG C by ethylene glycol, removes carbon monoxide
And fixed gas, obtain high-purity phosgene product.
High-purity phosgene product is used to produce polymeric MDI with reference to embodiment 3 in CN101302174, phosgene product and more
Amine carries out phosgenation reaction in atent solvent, obtains photochemical reaction liquid, photochemical reaction liquid is using phosgene removing, atent solvent
The polymeric MDI crude product of color perfecting is obtained after removing.
Chlorine content and the L* of polymeric MDI crude product are shown in Table 1 in high-purity phosgene.
Embodiment 6
Present case uses the suction chlorine agent B in embodiment 2.
Phosgene crude product (wherein chlorine content 1137ppm) enters chlorine in the reactor absorption phosgene equipped with the agent of this suction chlorine,
Flow velocity is 250BV/h.Phosgene gas after inhaling chlorine agent absorption is water-cooled to -20 DEG C by ethylene glycol, removes carbon monoxide
And fixed gas, obtain high-purity phosgene product.
Using method same as Example 5, which is used to produce polymeric MDI, phosgene product and more
Amine carries out phosgenation reaction in atent solvent, obtains photochemical reaction liquid, photochemical reaction liquid is using phosgene removing, atent solvent
The polymeric MDI crude product of color perfecting is obtained after removing.
Chlorine content and the L* of polymeric MDI crude product are shown in Table 1 in high-purity phosgene.
Embodiment 7
Present case uses the suction chlorine agent C in embodiment 3.
Phosgene crude product (wherein chlorine content 1137ppm) enters chlorine in the reactor absorption phosgene equipped with the agent of this suction chlorine,
Flow velocity is 150BV/h.Phosgene gas after inhaling chlorine agent absorption is water-cooled to -20 DEG C by ethylene glycol, removes carbon monoxide
And fixed gas, obtain high-purity phosgene product.
Using method same as Example 5, which is used to produce polymeric MDI, phosgene product and more
Amine carries out phosgenation reaction in atent solvent, obtains photochemical reaction liquid, photochemical reaction liquid is using phosgene removing, atent solvent
The polymeric MDI crude product of color perfecting is obtained after removing.
Chlorine content and the L* of polymeric MDI crude product are shown in Table 1 in high-purity phosgene.
Embodiment 8
Present case uses the suction chlorine agent D in embodiment 4.
Phosgene crude product (wherein chlorine content 1137ppm) enters chlorine in the reactor absorption phosgene equipped with the agent of this suction chlorine,
Flow velocity is 250BV/h.Phosgene gas after inhaling chlorine agent absorption is water-cooled to -20 DEG C by ethylene glycol, removes carbon monoxide
And fixed gas, obtain high-purity phosgene product.
Using method same as Example 5, which is used to produce polymeric MDI, phosgene product and more
Amine carries out phosgenation reaction in atent solvent, obtains photochemical reaction liquid, photochemical reaction liquid is using phosgene removing, atent solvent
The polymeric MDI crude product of color perfecting is obtained after removing.
Chlorine content and the L* of polymeric MDI crude product are shown in Table 1 in high-purity phosgene.
Comparative example 1
Without using suction chlorine agent in present case.
Phosgene raw gas (wherein chlorine content is 1137ppm) is water-cooled to -20 DEG C by ethylene glycol, removes an oxidation
Carbon and fixed gas obtain high-purity phosgene product.
Using method same as Example 5, which is used to produce polymeric MDI, phosgene product and amine exist
Phosgenation reaction is carried out in atent solvent, obtains photochemical reaction liquid, and photochemical reaction liquid is removed using phosgene removing, atent solvent
After obtain polymeric MDI crude product.
Chlorine content and the L* of polymeric MDI crude product are shown in Table 1 in high-purity phosgene.
Table 1
As can be seen from the above table, inhaling chlorine agent has good effect for the content for reducing chlorine in phosgene.And by the height
Pure phosgene product has some improvement to the color of crude product for producing isocyanate products.
Claims (10)
1. a kind of preparation method for inhaling chlorine agent, which comprises the following steps:
1) using alumina ball as carrier, the inorganic salts of zinc are reacted in a solvent with 2-methylimidazole, in alumina ball
Surface forms ZIF-8 crystal film, obtains spherical ZIF-8/ alumina ceramics ball particle；
2) the spherical ZIF-8/ alumina ceramics ball particle for obtaining step 1) impregnates in the inorganic salt solution of copper, then leads to
Separation, washing, drying, roasting are crossed, suction chlorine agent of the invention is obtained.
2. it is described in claim 1 inhale chlorine agent preparation method, which is characterized in that in step 1), the alumina ball it is straight
Diameter is 3-10mm, preferably 5-8mm；Its average pore size is 100-300nm, preferably 150-200nm.
3. the preparation method of any of claims 1 or 2 for inhaling chlorine agent, which is characterized in that in step 1), the inorganic salts of the zinc are selected
From one of zinc acetate, zinc chloride, zinc nitrate or a variety of, preferably one of zinc acetate, zinc nitrate or a variety of；
The solvent be selected from 5-10v% ammonium hydroxide methanol mixed solution, methanol, DMF, preferably 5-10v% ammonium hydroxide methanol mixed solution,
Methanol；
The inorganic salts of zinc, 2-methylimidazole, solvent molar ratio be 1:2-10:100-300, preferably 1:4-8:150-250；With/
Or:
The volume ratio of reaction solution and alumina ball that the inorganic salts and 2-methylimidazole and solvent of zinc are formed is 10-20.
4. the described in any item preparation methods for inhaling chlorine agent of claim 1-3, which is characterized in that in step 1), ZIF-8 crystal is thin
The preparation reaction of film is caused by pre-added purifying ZIF-8 crystal seed: in configured zinc inorganic salts, 2-methylimidazole, solvent
In the reaction solution of composition, the purifying ZIF-8 crystal seed of reaction solution quality 0.1-0.5%wt is added, after evenly mixing as anti-
Liquid is answered, is added in closed reactor, crystallization 1-3 hours at 80-120 DEG C.
5. the described in any item preparation methods for inhaling chlorine agent of claim 1-4, which is characterized in that in step 1), be prepared
The alumina ball of surface crystal film containing ZIF-8 impregnates 12-24h in methyl alcohol, to wash away remaining unreacted reactant, then exists
12-48h is dried in vacuo at 40-60 DEG C.
6. the preparation method described in claim 1 for inhaling chlorine agent, which is characterized in that in step 2), the inorganic salts of the copper are selected from
One of copper nitrate, copper chloride, basic copper carbonate, copper sulphate are a variety of, preferably copper nitrate and/or basic copper carbonate；Copper
Inorganic salt solution is the inorganic salts ammonia spirit of copper, concentration 0.005-0.015mol/L.
7. the preparation method described in any one of claims 1-6 for inhaling chlorine agent, which is characterized in that in step 2), the inorganic salts of copper
Solution usage is 2-4 times of porcelain ball particle volume；Porcelain ball particle dipping temperature in the inorganic salt solution of copper is 30-70 DEG C, excellent
Select 40-60 DEG C；Dip time is 1-4h, preferably 2-3h.
8. the described in any item preparation methods for inhaling chlorine agent of claim 1-7, which is characterized in that in step 2), the drying
For 12-48h, preferably 24-36h dry under 40-60 DEG C of environment of vacuum；
Described be roasted under nitrogen atmosphere roasts, N2Atmosphere maturing temperature is 300-800 DEG C, preferably 500-600 DEG C；Calcining time
1-4h, preferably 2-3h.
9. the suction chlorine agent that any one of -8 preparation methods are prepared according to claim 1.
10. the purposes according to claim 9 for inhaling chlorine agent is preferred for absorbing light for absorbing chlorine and/or hydrogen chloride
Chlorine in gas；Preferably, the flow velocity of phosgene is 100-300BV/h, preferably 150-250BV/h.
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