CN1923779A - Method of preparing sodium pentachlorophenate - Google Patents
Method of preparing sodium pentachlorophenate Download PDFInfo
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- CN1923779A CN1923779A CN 200610032271 CN200610032271A CN1923779A CN 1923779 A CN1923779 A CN 1923779A CN 200610032271 CN200610032271 CN 200610032271 CN 200610032271 A CN200610032271 A CN 200610032271A CN 1923779 A CN1923779 A CN 1923779A
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Abstract
The invention discloses a manufacturing method of sodium pentachlorophenate, which comprises the following steps: (1) adding phenol in the chlorinated autoclave; aerating chlorine gas catalyzed by aluminium to produce penchlorol; (2) putting alkaline in the alkaline tank; loading pentachlorophenol to precede alkalization reaction to obtain sodium pentachlorophenate.
Description
Technical field
The invention belongs to a kind of method of producing sodium pentachlorophenate that relates to.
Background technology
Schistosomicide, rot all are the healthy region epidemic diseases of serious harm numerous people, China has 100,000,000 people to suffer from schistosomicide, there are 4,500 ten thousand people to suffer from rot, had a strong impact on epidemic-stricken area people's healthy and life security, seriously hindered the epidemic-stricken area Economic development, and the intermediate host of schistosomicide is---oncomelania, eliminated oncomelania, also just equal to have eliminated schistosomicide, the intermediate host of rot is---the beans spiral shell, eliminate the beans spiral shell, also just eliminated rot.
Fushou spiral shell is alien species of introducing the seventies, because Fushou spiral shell is gnawed paddy rice in a large number at China's south rice growing area, has caused serious financial loss to the peasant, has been classified as one of alien species of 16 kinds of harm maximums by Environmental Protection in China general bureau.
Schistosomicide, rot are not only popular in China, also are widely current in Southeast Asian countries, and Fushou spiral shell wantonly omits too, and the gesture that all becomes to draw out.
Sodium pentachlorophenate is a kind of weeding, desinsection, sterilant, is one of the choice drug of spiral shell that goes out of generally acknowledging in the world, and China is used for prevention and cure of schistosomiasis in a large number and kills oncomelania and kill Fushou spiral shell, and the whole nation has only Tianjin, Dagu chemical inc one family to produce.Existing technology is three-step approach, i.e. " first and second bodies → trichlorobenzene → Perchlorobenzene → sodium pentachlorophenate " are referring to Fig. 1.The problem that existing explained hereafter exists:
1, the invalid body of raw materials for production is the by product behind the production lindane, has " phenyl-hexachloride " composition in the finished product unavoidably.
2, produce in the trichlorobenzene process and can be emitted in the air by a large amount of toxic and harmfuls of generation, local air is polluted.
When 3, producing Perchlorobenzene and sodium pentachlorophenate waste water is arranged all, 1 ton of sodium pentachlorophenate finished product of every production will discharge the trade effluent of 2.5 tons of difficult degradations in environment.
4, whole production technology all at 280 ℃ of high temperature, is carried out under the 26kg high pressure, and is bigger to production environment danger, very easily produces Dioxins at high-temperature and high-pressure conditions.
Developing a kind of snail killing agent safe, efficient, low toxicity as early as possible is the task of top priority, how to preserve the molluscicidal effect that improves existing sodium pentachlorophenate, cuts down existing explained hereafter influence and four problems of uneasy congruence to environment.It is the main purpose that the developer researches and develops present technique.
Technology contents
The method that the purpose of this invention is to provide a kind of new production sodium pentachlorophenate, this method have the characteristics of safety, efficient, low toxicity, environmental protection.
The inventive method may further comprise the steps:
1, required phenol is added in the chlorination reaction still, in the presence of Al catalysts, feed chlorine and carry out chlorination reaction, after the water collection, get Pentachlorophenol;
2, in the alkalization jar, drop into caustic soda, drop into pentachlorophenol again and carry out getting sodium pentachlorophenate after the quaternization.
Further method is:
In the step 1, described Al catalysts is aluminum chloride or fine aluminium, and the temperature when catalyzer adds chlorination tank is 80-85 ℃, and add-on is the 0.2-1% of phenol; With the chlorine total amount is that benchmark is 1 with phenol: 3.0-3.8, and phenol promptly per ton feeds liquid chlorine 3000Kg-3800Kg, and every still reaction total time is 18-20 hour, and temperature of reaction is 70-195 ℃;
In the step 2, under the temperature of alkalization jar 80-90 ℃, drop into Pentachlorophenol, after feeding intake temperature be controlled at 90-95 ℃, carry out after quaternization 1-2 hour evaporation concentration dewater sodium pentachlorophenate.
Preferred condition is respectively in the described method steps 1:
Phenol is selected oil phenol for use;
The ratio that adds Al catalysts is 1%;
With the chlorine total amount is 1: 3.1;
Every still reaction total time is 20 hours, and is divided into three phases:
Under 70-90 ℃ temperature, reacted 11 hours, use chlorine flow 150Kg/ hour, chlorine dosage is 1: 1.65;
Under 90-160 ℃ temperature, reacted 8 hours, use chlorine flow 170Kg/ hour, chlorine dosage is 1: 1.36;
Under 160-195 ℃ temperature, reacted 1 hour, use chlorine flow 190Kg/ hour, chlorine dosage is 1: 0.19.
Preferred condition is respectively in the described method steps 2:
Pentachlorophenol gradation under 80 ℃ temperature, as three times, each 10 minutes at interval, drop into alkalization jar, after feeding intake temperature is controlled at 90-95 ℃, quaternization under condition of negative pressure, carry out after 2 hours vacuum-evaporation concentrate, dewater sodium pentachlorophenate.
Further method is again:
The tail gas that produces from chlorination tank in the described chlorination reaction can get by-product acid hydrochloric acid after the absorption tower absorbs;
Described Pentachlorophenol is after chlorination reaction, obtains through the water collection.
This production method changes " phenol → Pentachlorophenol → sodium pentachlorophenate " two step method into by the three-step approach " first and second bodies → trichlorobenzene → Perchlorobenzene → sodium pentachlorophenate " of existing technology, and the invalid body raw material of existing technology is replaced by phenol.Chemical equation is as follows:
In fact the process of producing Pentachlorophenol with the phenol chlorination process is exactly the electrophilic substitution reaction on the phenyl ring, electrophilic substitution reaction theory basically identical on its reaction mechanism and rule on orientation and the phenyl ring.Entire reaction course divides two stages to carry out, and under the situation of existing apparatus and ratio of components, the fs needs 10～12 hours approximately; Subordinate phase needs 8～10 hours approximately.
In the fs: because-the inducing and conjugative effect of OH, the cloud density of phenyl ring is increased, make phenyl ring activation, particularly ortho para.Therefore ,-OH is as the ortho para orientating group, and chlorination reaction at first occurs on the ortho para, form the resonance structure of two series, our ortho chloro phenol and para-chlorophenol of intuitively thinking just, along with chlorination reaction further deeply, can generate a series of phenol muriate: 2, the 4-chlorophenesic acid, 2,6-chlorophenesic acid, 2,4, the 6-Trichlorophenol.This process institute energy requirement is lower, finishes than being easier to.Reaction enters subordinate phase, along with increasing of chlorine atom on the phenyl ring, and sterically hindered increase on the one hand, because the passivation of halogen makes the reaction difficulty increase, and speed of response slows down, the activation energy that reacts required is higher on the one hand; On the other hand, because the conjugative effect of the not shared p electron pair on the CL atom and the big л key of phenyl ring, a certain activity is still had at the ortho position of CL atom, but reaction under lewis acidic catalysis, also can be finished in its ortho position of electrophilic reagent attack under lower energy.In entire structure, be exactly the chlorination on 3 and 5.
It more than is the analysis of microscopic theory, on macrokinetics: the phenol chlorination reaction is the gas-liquid phase reaction, phenol and serial muriate thereof all have certain zero pour, gas liquid reaction is carried out smoothly, temperature of reaction should remain on the fusing point of reactant and resultant, according to material characteristic, the fs should be more than 70 ℃, consider the effusion of another product HCL and the viscosity of material, the optimization of stirring power, the temperature in this stage is controlled at 70-90 ℃ and is advisable.Along with the generation of multi-chlorophenol and the increase of content thereof, the viscosity and the fusing point of material constantly rise, and temperature of reaction also should corresponding improve, are elevated to gradually about 180 ℃ from 100 ℃, and temperature of reaction is the best for 10 ℃ to be higher than corresponding resultant fusing point.
Consider environmental protection and safety, the whole process of reaction all can design under atmospheric pressure state carries out, and adopts little negative pressure better, is the refrigerant cooling that circulates with water, and under normal circumstances, this reaction is a safety and stably.
The inventive method adopts " phenol direct chlorination method " to replace traditional " hexachlorobenzene path method ", has effectively controlled impurity and the residue in the product, improved quality product, and " three wastes " that produce in the production process has obtained effective improvement.By following table as can be seen present method compared with prior art have tangible advantage.
The advantage table that present method is compared with existing Technology
| Technology | Raw materials for production | Production stage | Degree of safety | Discharge of wastewater | Exhaust gas emission | Phenyl-hexachloride content | Kill the spiral shell drug effect | Dioxins amount (g/100t) |
| Existing technology | Invalid body | Three-step approach | High Temperature High Pressure | 2.5t | Bigger | More | 10g/m 3 | 3020 |
| Present technique | Oil phenol | Two step method | Middle normal temperature and pressure | Do not have | Do not have | Do not have | 5g/m 3 | 1.25 |
In addition, the inventive method also has following characteristics:
1, discharge of wastewater: adopt when prior art is extracted sodium pentachlorophenate and mix the tube suction method, this method moisture content has just lacked and the medicine in the mother liquor can't be bonded on the filter cloth, thereby water consumption is very big, all second stage employ.Present technique adopts evaporation concentration method, and moisture in the material is become steam earlier, through condenser condenses, makes steam become distilled water, and the distilled water of cleaning participates in recirculated water fully and uses, and not to the environmental emission trade effluent, also can not influence quality product.
2, owing to the oil phenol of having changed cleaning is raw material, can not contain the phenyl-hexachloride composition in the finished product, reduce product toxicity.
3, the product produced of present technique through Guangxi, the disease prevention and control center, Hunan Province does the spiral shell test of pesticide effectiveness extremely, the result shows medication 5g/m
3Soak extremely oncomelania, 24 hours mortality of snails very, than currently available products 10g/m
3Soak oncomelania extremely, death in 48 hours reaches 98 percent, is doubled.
4, this handicraft product in September, 2005 sample presentation do the Dioxins analysis for ecotope research institute of institute of Chinese section, the result shows, the sodium pentachlorophenate of this explained hereafter is torn open and is closed per hundred tons and contain Dioxins 1.25g, the sodium pentachlorophenate that detects existing explained hereafter than (nineteen ninety-fives) such as the Bao Zhicheng of this institute is torn open and is closed per hundred tons to contain the Dioxins amount be 3.02kg, has reduced more than 2400 times.
5, this explained hereafter can not brought the reality of environmental stress to the locality, is admitted by local environmental administration.
Description of drawings
Fig. 1 is the technological process of production figure of existing sodium pentachlorophenate.
Fig. 2 is the technological process of production figure of sodium pentachlorophenate of the present invention.
Embodiment
Embodiment 1:
The inventive method may further comprise the steps:
(1), 1000Kg phenol is added in the chlorination reaction still, in the presence of aluminum chloride, feed chlorine and carry out chlorination reaction, must Pentachlorophenol after the water collection;
(2), in alkalization jar, drop into sheet alkali, drop into again Pentachlorophenol carry out after the quaternization sodium pentachlorophenate.
Embodiment 2:
The inventive method may further comprise the steps:
(1), 1000Kg oil phenol is added in the chlorination reaction still, in chlorination reaction still chuck, feed steam, when making temperature in the kettle be climbed to 80 ℃, ratio in 1% adds fine aluminium as catalyzer, feed chlorine again and carry out chlorination reaction, with the chlorine total amount is 3100Kg, and every still reaction total time is 20 hours, and is divided into three phases:
Under 70-90 ℃ temperature, reacted 11 hours, use chlorine flow 150Kg/ hour, chlorine dosage is 1650Kg;
Under 90-160 ℃ temperature, reacted 8 hours, use chlorine flow 170Kg/ hour, chlorine dosage is 1360Kg;
Under 160-195 ℃ temperature, reacted 1 hour, use chlorine flow 190Kg/ hour, chlorine dosage is 170Kg;
After above-mentioned reaction, get Pentachlorophenol;
(2), in the alkalization jar, drop into sheet alkali, under 80 ℃ temperature, divide three times, each 10 minutes at interval, drop into Pentachlorophenol, after feeding intake temperature is controlled at 90-95 ℃, alkalize after 2 hours, vapor pressure is controlled at about 0.4Mpa, about 90 ℃ of still temperature, vacuum pressure is controlled at-0.02 to-0.03Mpa, carry out evaporation concentration, dewater sodium pentachlorophenate.
Embodiment 3:
The inventive method is:
In the method for described embodiment 2, be 3700Kg with the chlorine total amount, be respectively 1870Kg, 1600Kg, 230Kg at the chlorine dosage of three phases, all the other are identical.
Embodiment 4:
The inventive method is:
In the method for described embodiment 2, the tail gas that produces from chlorination tank gets hydrochloric acid after the absorption tower absorbs, and Pentachlorophenol is after chlorination reaction, obtains through the water collection, and all the other are identical.The technological process of production is referring to Fig. 2.
Claims (10)
1, a kind of method of producing sodium pentachlorophenate is characterized in that may further comprise the steps:
(1), required phenol is added in the chlorination reaction still, in the presence of Al catalysts, feeding that chlorine carries out after the chlorination reaction must Pentachlorophenol;
(2), in alkalization jar, drop into caustic soda, drop into again pentachlorophenol carry out after the quaternization sodium pentachlorophenate.
2, method according to claim 1 is characterized in that:
In the step (1), described Al catalysts is aluminum chloride or fine aluminium, and the temperature when catalyzer adds chlorination tank is 80-85 ℃, and add-on is the 0.2-1% of phenol; With the chlorine total amount is that benchmark is 1 with phenol: 3.0-3.8, and every still reaction total time is 18-20 hour, temperature of reaction is 70-195 ℃.
3, method according to claim 2 is characterized in that:
In the step (2), under the temperature of alkalization jar 80-90 ℃, drop into Pentachlorophenol, after feeding intake temperature be controlled at 90-95 ℃, carry out after quaternization 1-2 hour evaporation concentration dewater sodium pentachlorophenate.
4, method according to claim 3 is characterized in that phenol selects oil phenol for use.
5, method according to claim 3, the ratio that it is characterized in that adding Al catalysts is 1%.
6, method according to claim 3 is characterized in that with the chlorine total amount be 1: 3.1.
7, method according to claim 3 is characterized in that every still reaction total time of chlorination tank is 20 hours, and is divided into three phases:
Under 70-90 ℃ temperature, reacted 11 hours, with 150 kilograms/hour of chlorine flows, chlorine dosage is 1: 1.65;
Under 90-160 ℃ temperature, reacted 8 hours, with 170 kilograms/hour of chlorine flows, chlorine dosage is 1: 1.36;
Under 160-195 ℃ temperature, reacted 1 hour, with 190 kilograms/hour of chlorine flows, chlorine dosage is 1: 0.19.
8, method according to claim 3, it is characterized in that Pentachlorophenol divides three times under 80 ℃ temperature, each 10 minutes at interval, drop into the alkalization jar, after feeding intake temperature is controlled at 90-95 ℃, quaternization under condition of negative pressure, carry out after 2 hours vacuum-evaporation concentrate, dewater sodium pentachlorophenate.
9,, it is characterized in that the tail gas that produces from chlorination tank in the described chlorination reaction gets by-product acid after the absorption tower absorbs according to claim 1 or 3 described methods.
10, method according to claim 9 is characterized in that described Pentachlorophenol is after chlorination reaction, obtains through the water collection.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610032271 CN1923779A (en) | 2006-09-19 | 2006-09-19 | Method of preparing sodium pentachlorophenate |
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| CN 200610032271 CN1923779A (en) | 2006-09-19 | 2006-09-19 | Method of preparing sodium pentachlorophenate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360204A (en) * | 2013-07-11 | 2013-10-23 | 浙江海蓝化工有限公司 | Method for dewatering mixture of hexachlorobenzene and potassium fluoride |
| CN106866399A (en) * | 2017-03-03 | 2017-06-20 | 南通书创药业科技有限公司 | Tetrachloroquinone and preparation method thereof |
| CN109924219A (en) * | 2019-03-22 | 2019-06-25 | 滨州医学院 | A method of control propagation of schistosomiasis in lake regions |
-
2006
- 2006-09-19 CN CN 200610032271 patent/CN1923779A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360204A (en) * | 2013-07-11 | 2013-10-23 | 浙江海蓝化工有限公司 | Method for dewatering mixture of hexachlorobenzene and potassium fluoride |
| CN103360204B (en) * | 2013-07-11 | 2015-09-16 | 浙江海蓝化工集团有限公司 | A kind of method of Perchlorobenzene and the dehydration of Potassium monofluoride mixture |
| CN106866399A (en) * | 2017-03-03 | 2017-06-20 | 南通书创药业科技有限公司 | Tetrachloroquinone and preparation method thereof |
| CN109924219A (en) * | 2019-03-22 | 2019-06-25 | 滨州医学院 | A method of control propagation of schistosomiasis in lake regions |
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