CN104324704B - A kind of removing method of vikane - Google Patents
A kind of removing method of vikane Download PDFInfo
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- CN104324704B CN104324704B CN201410477152.0A CN201410477152A CN104324704B CN 104324704 B CN104324704 B CN 104324704B CN 201410477152 A CN201410477152 A CN 201410477152A CN 104324704 B CN104324704 B CN 104324704B
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/34—Specific shapes
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Abstract
The removing method of a kind of vikane, it comprises the following steps: 1). preparation nitration St DVB porous microsphere；2). utilize nitration St DVB porous microsphere that vikane is adsorbed；Described nitration St DVB porous microsphere preparation method is as follows: by sodium chloride and poly-vinyl alcohol solution mix homogeneously, preparation polymerization aqueous phase；Monomer styrene, divinylbenzene, initiator B PO, porogen toluene and normal heptane are mixed, stirs, preparation polymerization organic facies；After aqueous phase and organic facies being uniformly dispersed by the volume ratio mixing of 5:1, being transferred in reactor by mixture, mixing speed is set as 400rpm；Oil bath is used to be to slowly warm up to 70 DEG C (4 DEG C/h), after forming liquid pearl, constant temperature 2h, then heat to 90 DEG C (10 DEG C/h), ripening 8h, prepare St DVB polymer microballoon；Above-mentioned St DVB polymer microballoon nitration again.
Description
Technical field
The present invention relates to the removing method of a kind of vikane.
Background technology
Owing to bromomethane has the chemical property damaged the ozone layer, so expressly providing in the Montreal Protocol (Montreal protocol) of signing in 1987 and forbidding bromomethane utilization of pesticides, and because sulfuryl fluoride fumigating synergistic agent takes effect in terms of eliminating the insect of agricultural and building very much, become a kind of fumigating insecticide being widely adopted in the whole world after being prohibited from using for bromomethane insecticide.Because bromomethane has the chemical property damaged the ozone layer, so expressly providing in the Montreal Protocol (Montreal protocol) of signing in 1987 and forbidding bromomethane utilization of pesticides, a kind of fumigating insecticide being widely adopted in the whole world after vikane becomes and is prohibited from using for bromomethane insecticide afterwards.
But scientist finds through research now, and vikane is a kind of potent greenhouse gases in fact.It is reported, it is 4800 times of one kilogram of carbon dioxide that one kilogram of vikane is discharged in air the effect to global warming.Although only existing minimal amount of vikane, about 1.5 part per trillions in air now, in the most each million air molecules, only 1.5 is vikane, but it is increasing with the speed of annual 5%.Additionally, vikane is also a kind of convulsant, although vikane is lower than other fumigant to the toxicity of higher mammal, but it still has strong toxic action to human body, it is therefore desirable to obtain a kind of effective ways removing vikane.
Summary of the invention
The technical problem to be solved is to provide the removing method of a kind of vikane for above-mentioned present situation so that it is can remove vikane efficiently, easily.
The present invention solves the technical scheme that above-mentioned technical problem used:
The removing method of a kind of vikane, it comprises the following steps: 1). preparation nitration St-DVB porous microsphere；
2). utilize nitration St-DVB porous microsphere that vikane is adsorbed；
Described nitration St-DVB porous microsphere preparation method is as follows:
By sodium chloride and poly-vinyl alcohol solution mix homogeneously, preparation polymerization aqueous phase；
Monomer styrene, divinylbenzene, initiator B PO, porogen toluene and normal heptane are mixed, stirs, preparation polymerization organic facies；
After aqueous phase and organic facies being uniformly dispersed by the volume ratio mixing of 5:1, being transferred in reactor by mixture, mixing speed is set as 400rpm；Oil bath is used to be to slowly warm up to 70 DEG C (4 DEG C/h), after forming liquid pearl, constant temperature 2h, then heat to 90 DEG C (10 DEG C/h), ripening 8h, prepare St-DVB polymer microballoon；
Above-mentioned St-DVB polymer microballoon nitration the most by the following method:
Above-mentioned styrene diethylene benzene copoly mer (ST-DVB) Archon makes St-DVB polymer Archon the most swelling by methylene chloride at less than 20 DEG C, 100ml low temperature nitration mixture (V nitric acid: V sulphuric acid=1:2) it is slowly added into after adding a small amount of carbamide, open stirring, rise to about 30 DEG C to temperature；It is slowly added dropwise nitration mixture with constant pressure dropping funnel under stirring, controls bottle interior reaction temperature below 50 DEG C；After dropping, being heated to 65 DEG C-70 DEG C with oil bath, backflow limit, limit stirring reaction 3 hours, the oxynitride available hydrogen sodium hydroxide solution of effusion absorbs；It is cooled to room temperature, reactant is carefully poured in frozen water, sucking filtration, be washed with deionized water to neutrality, dried available nitration St-DVB polymer microballoon.
Compared with prior art, it is an advantage of the current invention that: with polydivinylbenezene (PDVB) resin as structural resin, by pore former mould plate technique, it is carried out high microporous modified, secondly by surface chemical modification method, resin phenyl ring is grafted vikane is had adsorbing nitro molecular radical, thus prepare adsorptivity height micro-porous resin, reach high-selectivity adsorption low concentration vikane.
Detailed description of the invention
The invention will be further described for following example.
One, the preparation of cross-linked styrene-divinylbenzene porous microsphere
The purification of 1 reagent.
Cinnamic purification step: 1) in 100ml separatory funnel, add 50ml styrene monomer, wash secondary by the NaOH solution (5%) of 15ml and separate；2) with distilled water wash styrene to neutral, isolated styrene monomer is placed in conical flask, adds anhydrous magnesium sulfate to liquid-transparent；3) dried monomer carries out decompression distillation, collects 59 DEG C-60 DEG C, and the fraction of 53.3kPa is standby.
The purge process of divinylbenzene is identical with styrene.
Initiator B PO with chloroform as solvent, methanol make precipitant, use recrystallization method to carry out polishing purification.
The preparation of 2 polymerization aqueous phases.By sodium chloride and poly-vinyl alcohol solution mix homogeneously, preparation polymerization aqueous phase.
The selection degree of polymerization is 1700+/-50, alcoholysis degree be alcoholysis type polyvinyl alcohol (PVA) of 88% as dispersant because the PVA water solublity of 88% is best.Take 12.5g PVA resin and the most slowly put in the dissolution kettle equipped with 500ml deionized water, simultaneously with the speed of 100rpm stir (the slowest, easily sink to the bottom caking；Too fast, easily it be involved in air, cause too much bubble) after about 30 minutes, it is to slowly warm up to 60 DEG C and maintains certain time, until PVA is completely dissolved.
The preparation of 3 polymerization organic faciess.By design quantity, monomer styrene, divinylbenzene, initiator B PO, porogen toluene and normal heptane are mixed, stir, preparation polymerization organic facies.
4 polymerizations.After aqueous phase and organic facies being uniformly dispersed by the volume ratio mixing of 5:1, being transferred in reactor by mixture, mixing speed is set as 400rpm；Oil bath is used to be to slowly warm up to 70 DEG C by 4 DEG C/h, after forming liquid pearl, constant temperature 2h, then it is warming up to 90 DEG C by 10 DEG C/h, ripening 8h, reaction terminates.
5 post processings.After reaction terminates, by products therefrom sucking filtration, the most respectively with distilled water, ethanol equal solvent washing multipass, to remove the soluble impurities such as unreacted monomer and stabilizer.In Soxhlet extractor, extract 8h-24h with acetone, to remove porogen and organic impurities, form loose structure, again with methanol and distilled water wash, the loose structure of the most fixing microsphere；Microsphere vacuum drying 24h after purification, obtains white porosity St-DVB polymer microballoon.
Two, the nitration of cross-linked styrene-divinylbenzene porous microsphere
Specifically comprise the following steps that
Weigh 60g styrene diethylene benzene copoly mer (ST-DVB) Archon, move in low temperature beaker and make St-DVB polymer Archon the most swelling by methylene chloride.Suction strainer, removes solvent, is transferred in the four-hole boiling flask of 1000ml after adding a small amount of carbamide；Being slowly added into 100ml low temperature nitration mixture (V nitric acid: V sulphuric acid=1:2), open stirring, now in bottle, temperature rises to about 30 DEG C；Open condensed water, be under agitation slowly added dropwise 200ml nitration mixture with constant pressure dropping funnel, control bottle interior reaction temperature below 50 DEG C.After dropping, being heated to 65 DEG C-70 DEG C with oil bath, backflow limit, limit stirring reaction 3 hours, the oxynitride available hydrogen sodium hydroxide solution of effusion absorbs.Remove oil bath, be cooled to room temperature, reactant is carefully poured in frozen water, sucking filtration, be washed with deionized water to neutrality, dried available flavous nitration St-DVB polymer microballoon.
Use ASAP 2010 type specific surface area measuring instrument the specific surface area of above-mentioned nitration St-DVB polymer microsphere sample is measured, BET specific surface area be 291.6m2/g, Langmuir specific surface area be 407.5 m2/g.
At 0 DEG C of above-mentioned nitration St-DVB porous microsphere sample, the adsorbance to vikane is: 19.8301 mL, are 17.5372mL at 10 DEG C, are 10.8650mL at 25 DEG C, and therefore, at a temperature of generally using, absorbability is high.
Said method pre-cools nitration mixture and St-DVB polymer, St-DVB polymer is disposably joined in reactor, and the nitration mixture adding 1/3 consumption is mixed with, the nitration mixture of other 2/3 consumption is under agitation slowly dripped by Dropping funnel, is then warmed up to reaction temperature and carries out nitrification；Use nitric acid: sulphuric acid is 1:2, few by acid amount, and the nitro St-DVB fluoropolymer resin degree of nitration obtained is homogeneous, and this method advantage is obvious.
It is demonstrated experimentally that by said method, first prepare nitration St-DVB porous microsphere, then adsorb fumigant vikane under room temperature, normal pressure, be a kind of good method eliminating vikane.
Claims (1)
1. the removing method of a vikane, it is characterised in that: it comprises the following steps:
1). preparation nitration St-DVB porous microsphere；
2). utilize nitration St-DVB porous microsphere that vikane is adsorbed；
Described nitration St-DVB porous microsphere preparation method is as follows: by sodium chloride and poly-vinyl alcohol solution mix homogeneously, preparation polymerization aqueous phase；Monomer styrene, divinylbenzene, initiator B PO, porogen toluene and normal heptane are mixed, stirs, preparation polymerization organic facies；After aqueous phase and organic facies being uniformly dispersed by the volume ratio mixing of 5:1, being transferred in reactor by mixture, mixing speed is set as 400rpm；Oil bath is used to be to slowly warm up to 70 DEG C by 4 DEG C/h speed, after forming liquid pearl, constant temperature 2h, then it is warming up to 90 DEG C by 10 DEG C/h speed, ripening 8h, prepare St-DVB polymer microballoon；
Above-mentioned St-DVB polymer microballoon nitration the most by the following method: above-mentioned St--DVB polymer microballoon makes St-DVB polymer microballoon the most swelling by methylene chloride at less than 20 DEG C, being slowly added into 100ml low temperature nitration mixture after adding a small amount of carbamide, wherein nitration mixture is by VNitric acid:VSulphuric acidMix for 1:2, open stirring, rise to 30 DEG C to temperature；It is slowly added dropwise nitration mixture with constant pressure dropping funnel under stirring, controls bottle interior reaction temperature below 50 DEG C；After dropping, being heated to 65 DEG C-70 DEG C with oil bath, backflow limit, limit stirring reaction 3 hours, the oxynitride sodium hydroxide solution of effusion absorbs；It is cooled to room temperature, reactant is carefully poured in frozen water, sucking filtration, be washed with deionized water to neutrality, dried available nitration St-DVB porous microsphere.
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| CN1240477C (en) * | 2004-01-15 | 2006-02-08 | 沧州市冀中化工厂 | Thermostable strong acid cation resin catalyst and its preparing method |
| CN100404125C (en) * | 2006-07-28 | 2008-07-23 | 肇庆学院 | Kernel-containing boracic acid group absorptive and its preparing method |
| WO2008064525A1 (en) * | 2006-12-01 | 2008-06-05 | Institute Of Process Engineering Chinese Academy Of Sciences | A super macroporous polymeric microsphere and preparation process thereof |
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Address after: 315000 Block A, Qingyi Road, Ningbo High-tech Zone, Zhejiang Province Patentee after: Ningbo Institute of Inspection and Quarantine Science Technology Address before: 315010 No. 9 Mayuan Road, Haishu District, Ningbo City, Zhejiang Province Patentee before: Ningbo Institute of Inspection and Quarantine Science Technology |