CN106518744B - Cupric sulfate centrifuge mother liquor method for crystallising - Google Patents
Cupric sulfate centrifuge mother liquor method for crystallising Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/02—Thiosulfates
Abstract
The invention discloses a kind of Cupric sulfate centrifuge mother liquor method for crystallising, it includes：Stabilizer is added into Cupric sulfate centrifuge mother liquor, crystalline mother solution is obtained with insulation reaction after liquid caustic soda regulation pH value, thickening, centrifugation desalination；Crystalline mother solution is cooled to less than 30 DEG C under agitation, hydrochloric acid, which is added portionwise, finally makes the pH value of mother liquor to 5.3~5.7 and insulation reaction, continue to be cooled to and be incubated 4~10 hours at 0 DEG C, the temperature of mother liquor is set to be maintained at 5~8 DEG C before discharging, separation of solid and liquid after discharging, the liquid alkali isolated adjusts pH value and obtains dimehypo to 6.8~7.2, and the solid isolated obtains Cupric sulfate after drying.Each influence factor of the present invention in Cupric sulfate crystallization process, has formulated a kind of compound crystallization mode, Cupric sulfate flour extraction can be made to reach 45%, Determination of Shachongdan is maintained at more than 95%, and this method has more preferably prospects for commercial application.
Description
Technical field
The invention belongs to field of pesticide production, and in particular to utilization of the method for crystallising in pesticide producing.
Background technology
Cupric sulfate, dimehypo are nereistoxin bionic pesticides, 150 various agricultural insects can be prevented and treated, particularly to rice borer
Worm has special efficacy, prevents and treats the govern-house-variety of snout moth's larva always in China's Rice Production for many years.
China is the country that nereistoxin and similar bionic pesticide production yields is maximum in the world, the nereistoxin that the Ministry of Agriculture issues
Nearly more than 500 parts of the registration card of bionic pesticide.Wherein issue 284 parts of the registration card of Cupric sulfate active compound and preparation (containing compound product).
For the purposes of Cupric sulfate centrifuge mother liquor, domestic enterprise uses collect Cupric sulfate centrifuge mother liquor for many years always, its
In contain about 22% or so Cupric sulfate and isomers Cupric sulfate, first plus alkali lye regulation pH value, Cupric sulfate is converted into dimehypo,
Add water and be directly modulated into 18% dimehypo water solution, sell.
18% dimehypo water solution derives from Cupric sulfate centrifuge mother liquor, therefore more sodium chloride is contained in the inside, while also contains
There is substantial amounts of chemical impurity, the Con trolling index of the dimehypo water solution sodium chloride of national Specification 18% is：≤ 12.0%.The product
Largely used for a long time in farmland, certain pollution can be caused to environment.Therefore, 18% dimehypo water solution is classified as by country
" high pollution, high environmental risk " catalogue item, will be eliminated.
ZL200810122525.3 is disclosed Cupric sulfate centrifuge mother liquor by being concentrated by evaporation, and desalination removal of impurities, is prepared height and is contained
The method for measuring Cupric sulfate and dimehypo, the high content Cupric sulfate obtained by this method can be not only used for agricultural and control worm, can be used for again
The synthesis of high-end product cartap；Obtained high content dimehypo mother's medicine, can prepare 29% dimehypo water solution, make therein miscellaneous
Matter-sodium chloride content substantially reduces, and is advantageous to environmental protection.Therefore the implementation of patent is to extending nereistoxin and similar bionic pesticide
Service life, lifting China's pesticide industry whole competitiveness is played an important role.The patent is during industrialization, according to killing
The single added value of worm is higher than dimehypo, and Cupric sulfate is solid matter in addition, and dimehypo is liquid substance, Cupric sulfate and desinsection two-phase
Than substantial amounts of resource can be saved in packaging, storage, transport etc., therefore need to put forth effort to kill in Cupric sulfate centrifuge mother liquor is improved
Made an effort on the single flour extraction of worm.
The flour extraction of Cupric sulfate is improved using different modes now with different document reports, such as uses high-efficiency evaporator
Carry out dehydration by evaporation, to improve flour extraction；Have and add effective stabilizer, reduce active ingredient degraded, to improve flour extraction, but all do not have
There is the research to Cupric sulfate crystallization mode, to improve the method for flour extraction.
The content of the invention
The purpose of the present invention is on the basis of existing technology, there is provided a kind of Cupric sulfate centrifuge mother liquor method for crystallising.
The purpose of the present invention can be reached by following measures：
A kind of Cupric sulfate centrifuge mother liquor method for crystallising, it comprises the following steps：
(A) stabilizer is added into Cupric sulfate centrifuge mother liquor, adjusts pH value to 6.8~7.2 with liquid caustic soda, be warming up to 40~60
DEG C insulation reaction, evaporator vacuum system is opened, it is when relative degree of vacuum reaches below -0.09Mpa, the centrifugation after insulation is female
Liquid imports in evaporator and thickening is carried out at 50~60 DEG C, is obtained to carrying out centrifuging desalination to obtained concentrate after dehydration
Crystalline mother solution；
(B) crystalline mother solution is cooled to less than 30 DEG C under agitation, and Part I hydrochloric acid is slowly added at 20~30 DEG C simultaneously
Insulation reaction 4~10 hours, then it is cooled to 10~20 DEG C and is slowly added to Part II hydrochloric acid simultaneously insulation reaction 4~10 hours,
Being cooled to 0~10 DEG C again and being slowly added to Part III hydrochloric acid finally makes the pH value of mother liquor to 5.3~5.7 and insulation reaction 4~10
Hour, continue to be cooled to being incubated 4~10 hours at 0 DEG C, the temperature of mother liquor is maintained at -5~-8 DEG C before discharging, solid-liquid after discharging
Separation, the liquid alkali regulation pH value isolated to 6.8~7.2 obtain dimehypo, and the solid isolated is killed after drying
Worm is single.
After Cupric sulfate centrifuge mother liquor in the present invention refers to that Cupric sulfate thiosulfuric acidization isolates a Cupric sulfate after reacting
Caused mother liquor；Its mass content is 15%~30%, preferably 20%~30%, further preferred 24%.
Stabilizer in the present invention is selected from butylated hydroxy anisole, dibutyl hydroxy toluene, propylgallate, the tert-butyl group
One or more in hydroquinones, tetrahydrofuran, sodium hydrogensulfite, potassium bisulfite, are preferably selected from TBHQ
Or the one or more in sodium hydrogensulfite.
In the present invention quality dosage of stabilizer for Cupric sulfate centrifuge mother liquor quality 0.2~0.8 ‰, preferably 0.3~
0.7 ‰, further preferred 0.4~0.6 ‰.
In step (A), the mass content of liquid caustic soda is 25%~35%, preferably 30%, the insulation reaction temperature in step (A)
Degree is preferably 45~50 DEG C, and the insulation reaction time is 0.5~1 hour.After dehydration concentration the content of Cupric sulfate be maintained at 55%~
Between 65%.Sodium hydroxide may be selected in alkali in the present invention, and sodium hydrate aqueous solution may be selected in liquid caustic soda.
In step (B), Part I hydrochloric acid is the 55~64%, preferably 60% of hydrochloric acid total amount, and Part II hydrochloric acid is
The 25~34% of hydrochloric acid total amount, preferably 30%, the hydrochloric acid total amount are the total of Part I, Part II and Part III hydrochloric acid
Amount, Part III hydrochloric acid preferably makes the pH value of mother liquor, and to 5.4~5.6, most preferred pH value is 5.5.
In step (B), insulation reaction 5~8 hours after addition Part I hydrochloric acid, add Part II hydrochloric acid and be simultaneously incubated
Reaction 5~8 hours, Part III hydrochloric acid is added after 0~10 DEG C of insulation reaction 5~8 hours, is cooled to insulation reaction 5 at 0 DEG C
~8 hours.
In step (B), for crystalline mother solution from cooling down until all being carried out under agitation before discharging, stir speed (S.S.) is 20~100
Rev/min, preferable stir speed (S.S.) is 40~80 revs/min.
In step (B), the mass concentration of the hydrochloric acid is more than 20%, and preferably more than 25%.
Cupric sulfate centrifuge mother liquor obtains main positive structure body, isomery in crystalline mother solution after alkali tune, concentration and evaporation desalination
Body and sodium chloride：
1st, positive structure body
2nd, isomers
The Cupric sulfate of needs is only after wherein positive structure body acidifying, because the mother liquor system is complicated, during acidizing crystal
Interaction, the flour extraction to Cupric sulfate and content all have a great impact in a different manner.Inventor has found, in desinsection
In single recovery preparation process, temperature when adding hydrochloric acid and mixing speed and the concentration of hydrochloric acid in step, crystallization process
All there is certain influence on the flour extraction of Cupric sulfate, and the application is by the appropriate each step of adjustment in whole process, especially
It is to be interacted by steps such as substep cooling acid adding, fractional crystallization and stirrings, the Cupric sulfate of more than 95% content can be obtained,
So that the flour extraction of Cupric sulfate brings up to 45% or so by original 40% or so.
A kind of existing crystallization desinsection single operation is as follows：Stabilizer will be added in Cupric sulfate centrifuge mother liquor, use 30% liquid
Alkali adjusts pH value to 6.8~7.2, is warming up to 45~50 DEG C, is then incubated 0.5~1 hour, opens evaporator vacuum system, treat
When vacuum reaches more than -0.08Mpa, open steam and be pumped into centrifuge mother liquor and carry out thickening, during control temperature as 50~60
DEG C, the concentrate of collection carries out centrifugation desalination, the centrifugate after the desalination of collection, obtains crystalline mother solution, adds salt acid for adjusting pH
Value is to 5.5 or so, when kettle temperature is down to -5~-8 DEG C, is incubated 10~24 hours, discharging centrifugation, and filtrate adds adjusting PH with base value to be 7 or so,
Dimehypo is obtained, is Cupric sulfate after filter cake drying.Temperature during adjustment addition hydrochloric acid, mixing speed and hydrochloric acid are dense respectively
Degree, to evaluate influence of each factor to Cupric sulfate：
1st, during acid adding temperature influence
Dimehypo is all very sensitive to temperature and pH value, and easy chain rupture is decomposed, so as to influence the flour extraction of Cupric sulfate and kill
The single content of worm, and temperature is too low, sticking of mother liquid spends the parcel for greatly, causing crystal salt, so influenceing the content of Cupric sulfate.
2nd, the influence of mixing speed
| Test sequence number | Mixing speed (rev/min) | Cupric sulfate flour extraction (%) | Determination of Shachongdan (%) |
| 1 | 20 | 40.2 | 94.8 |
| 2 | 40 | 40.1 | 95.1 |
| 3 | 60 | 40.2 | 95.3 |
| 4 | 80 | 39.8 | 95.2 |
| 5 | 100 | 39.4 | 95.5 |
Mixing speed is too fast, and the content of Cupric sulfate is beneficial to, but has an impact to flour extraction, and mixing speed is too low, right
The content of Cupric sulfate also has an impact.
3rd, the influence of concentration of hydrochloric acid
| Test sequence number | Concentration of hydrochloric acid (%) | Cupric sulfate flour extraction (%) | Determination of Shachongdan (%) |
| 1 | 10 | 37.2 | 95.4 |
| 2 | 15 | 38.3 | 95.2 |
| 3 | 20 | 39.8 | 95.3 |
| 4 | 25 | 40.0 | 95.2 |
| 5 | 30 | 40.3 | 95.1 |
Concentration of hydrochloric acid influences less on Determination of Shachongdan, but has certain influence on flour extraction, the mainly big dissolving of water
Part Cupric sulfate.
And each influence factor of the present invention in Cupric sulfate crystallization process, a kind of compound crystallization mode has been formulated, can
So that Cupric sulfate flour extraction reaches 45%, Determination of Shachongdan is maintained at more than 95%, before this method has more preferably commercial Application
Scape.
Embodiment
Embodiment 1
500 gram of 24% Cupric sulfate centrifuge mother liquor, 0.12 gram of TBHQ are added in 1000ml reaction bulbs
(TBHQ) pH value and 0.12 gram of sodium hydrogensulfite, is adjusted to 7.1 using 30% liquid caustic soda, is first warming up to 45~50 DEG C, is then incubated
0.5 hour, open vacuum system, when vacuum reach below -0.09Mpa, distillation dehydration, during control temperature as 50~60
DEG C, deviate from 345.1 grams of water, carry out filtering 39.4 grams of desalination after the concentrate cooling of collection, the filtrate after the desalination of collection is to tying
Brilliant bottle, stirring is opened, be kept stirring for speed as 60 revs/min, be cooled to 30 DEG C, at 20~30 DEG C, start to be slowly added to 30%
When the 60% of hydrochloric acid total amount, 5 hours are incubated at 20~30 DEG C, then being down to 10~20 DEG C, the 30% of 30% hydrochloric acid total amount is added,
When being incubated 5 hours at 10~20 DEG C, then being down to 0~10 DEG C, remaining 30% hydrochloric acid is added, regulation pH value is to 5.5,0~10
When being incubated 5 hours at DEG C, then being down to -5~-8 DEG C, 8 hours are incubated, discharging filters, and filtrate adds adjusting PH with base value to be 7.0, obtains desinsection
Double 164.15 grams of female medicines, analysis content are 38.78%；Filter cake is Cupric sulfate, obtains 57.16 grams of Cupric sulfate after drying, analysis contains
Measure as 95.1%, yield 98.35%, Cupric sulfate flour extraction 45.3%.Embodiment 2
500 gram of 24% Cupric sulfate centrifuge mother liquor, 0.2 gram of TBHQ (TBHQ) are added in 1000ml reaction bulbs
With 0.2 gram of sodium hydrogensulfites, using 30% liquid caustic soda regulation pH value to 6.9,45~50 DEG C are first warming up to, is then incubated 0.5 hour,
Open vacuum system, when vacuum reach below -0.09Mpa, distillation dehydration, during control temperature as 50~60 DEG C, abjection water
342.3 grams, carry out filtering 38.1 grams of desalination after the cooling of the concentrate of collection, the filtrate after the desalination of collection is opened and stirred to bottle is crystallized
Mix, be kept stirring for speed as 60 revs/min, be cooled to 30 DEG C, at 20~30 DEG C, start to be slowly added to 30% hydrochloric acid total amount
60%, when being incubated 5 hours at 20~30 DEG C, then being down to 10~20 DEG C, the 30% of 30% hydrochloric acid total amount is added, at 10~20 DEG C
Lower insulation 5 hours, then when being down to 0~10 DEG C, remaining 30% hydrochloric acid is added, it is small to be incubated 5 to 5.6 at 0~10 DEG C for regulation pH value
When, then when being down to -5~-8 DEG C, 8 hours are incubated, discharging filters, and filtrate adds adjusting PH with base value to be 6.9, obtains dimehypo mother medicine 164.57
Gram, analysis content is 38.92%；Filter cake is Cupric sulfate, 56.81 grams of Cupric sulfate is obtained after drying, analysis content is as
95.1%, yield 98.4%, Cupric sulfate flour extraction 45.02%.
Embodiment 3
500 gram of 24% Cupric sulfate centrifuge mother liquor, 0.12 gram of TBHQ are added in 1000ml reaction bulbs
(TBHQ) pH value and 0.2 gram of sodium hydrogensulfite, is adjusted to 7.2 using 30% liquid caustic soda, is first warming up to 45~50 DEG C, is then incubated
0.5 hour, open vacuum system, when vacuum reach below -0.09Mpa, distillation dehydration, during control temperature as 50~60
DEG C, deviate from 346.8 grams of water, carry out filtering 39.9 grams of desalination after the concentrate cooling of collection, the filtrate after the desalination of collection is to tying
Brilliant bottle, stirring is opened, be kept stirring for speed as 60 revs/min, be cooled to 30 DEG C, at 20~30 DEG C, start to be slowly added to 30%
When the 60% of hydrochloric acid total amount, 5 hours are incubated at 20~30 DEG C, then being down to 10~20 DEG C, the 30% of 30% hydrochloric acid total amount is added,
When being incubated 5 hours at 10~20 DEG C, then being down to 0~10 DEG C, remaining 30% hydrochloric acid is added, regulation pH value is to 5.7,0~10
When being incubated 5 hours at DEG C, then being down to -5~-8 DEG C, 8 hours are incubated, discharging filters, and filtrate adds adjusting PH with base value to be 7.0, obtains desinsection
Double 163.01 grams of female medicines, analysis content are 39.17%；Filter cake is Cupric sulfate, obtains 56.96 grams of Cupric sulfate after drying, analysis contains
Measure as 95.3%, yield 98.45%, Cupric sulfate flour extraction 45.2%.
Comparative example 1
500 gram of 24% Cupric sulfate centrifuge mother liquor, 0.12 gram of TBHQ are added in 1000ml reaction bulbs
(TBHQ) pH value and 0.12 gram of sodium hydrogensulfite, is adjusted to 7.1 using 30% liquid caustic soda, is first warming up to 45~50 DEG C, is then incubated
0.5 hour, open vacuum system, when vacuum reach below -0.09Mpa, distillation dehydration, during control temperature as 50~60
DEG C, deviate from 347.5 grams of water, carry out filtering 38.4 grams of desalination after the concentrate cooling of collection, the filtrate after the desalination of collection is to tying
Brilliant bottle, 30 DEG C are cooled to, start to be slowly added to 30% salt acid for adjusting pH value to 5.5, when being down to -5~-8 DEG C, be incubated 24 hours,
Discharging filters, and filtrate adds adjusting PH with base value to be 7.0, obtains 172.65 grams of dimehypo mother medicine, and analysis content is 40.5%；Filter cake is desinsection
It is single, 50.51 grams of Cupric sulfate is obtained after drying, analysis content is 95.5%, yield 98.47%, Cupric sulfate flour extraction 40.2%.
Comparative example 2
500 gram of 24% Cupric sulfate centrifuge mother liquor, 0.12 gram of TBHQ are added in 1000ml reaction bulbs
(TBHQ) pH value and 0.2 gram of sodium hydrogensulfite, is adjusted to 7.1 using 30% liquid caustic soda, is first warming up to 45~50 DEG C, is then incubated
0.5 hour, open vacuum system, when vacuum reach below -0.09Mpa, distillation dehydration, during control temperature as 50~60
DEG C, deviate from 350.1 grams of water, carry out filtering 39.4 grams of desalination after the concentrate cooling of collection, the filtrate after the desalination of collection is to tying
Brilliant bottle, stirring is opened, be kept stirring for speed as 60 revs/min, be cooled to 30 DEG C, started to be slowly added to 30% hydrochloric acid, adjust pH value
To 5.5, when being incubated 5 hours at 20~30 DEG C, then being down to -5~-8 DEG C, 24 hours are incubated, discharging filters, and filtrate adds adjusting PH with base
It is worth for 6.9, obtains 166.47 grams of dimehypo mother medicine, analysis content is 40.7%；Filter cake is Cupric sulfate, and Cupric sulfate is obtained after drying
53.32 grams, analysis content is as 95.2%, yield 98.76%, Cupric sulfate flour extraction 42.3%.
Claims (11)
1. a kind of Cupric sulfate centrifuge mother liquor method for crystallising, it is characterised in that it comprises the following steps：
(A) stabilizer is added into Cupric sulfate centrifuge mother liquor, adjusts pH value to 6.8~7.2 with liquid caustic soda, be warming up to 40~60 DEG C of guarantors
Temperature reaction, opens evaporator vacuum system, when relative degree of vacuum reaches below -0.09Mpa, the centrifuge mother liquor after insulation is led
Enter and carry out thickening in evaporator at 50~60 DEG C, crystallized to carrying out centrifuging desalination to obtained concentrate after dehydration
Mother liquor；
(B) crystalline mother solution is cooled to less than 30 DEG C under agitation, and Part I hydrochloric acid is slowly added at 20~30 DEG C and is incubated
Reaction 4~10 hours, then it is cooled to 10~20 DEG C and is slowly added to Part II hydrochloric acid simultaneously insulation reaction 4~10 hours, then drop
Temperature is slowly added to Part III hydrochloric acid to 0~10 DEG C finally makes the pH value of mother liquor to 5.3~5.7 and insulation reaction 4~10 hours,
Continue to be cooled to and be incubated 4~10 hours at 0 DEG C, the temperature of mother liquor is maintained at -5~-8 DEG C before discharging, separation of solid and liquid after discharging,
The liquid alkali isolated adjusts pH value and obtains dimehypo to 6.8~7.2, and the solid isolated obtains Cupric sulfate after drying.
2. according to the method for claim 1, it is characterised in that the Cupric sulfate centrifuge mother liquor refers to Cupric sulfate thiosulfuric acid
Caused mother liquor after a Cupric sulfate is isolated after changing reaction；Its Cupric sulfate mass content is 15%~30%.
3. according to the method for claim 1, it is characterised in that the stabilizer is selected from butylated hydroxy anisole, dibutyl hydroxyl
One kind or more in base toluene, propylgallate, TBHQ, tetrahydrofuran, sodium hydrogensulfite, potassium bisulfite
Kind；The quality dosage of stabilizer is 0.2~the 0.8 ‰ of Cupric sulfate centrifuge mother liquor quality.
4. according to the method for claim 3, it is characterised in that the stabilizer is selected from TBHQ or sulfurous acid
One or more in hydrogen sodium.
5. according to the method for claim 1, it is characterised in that the mass content of the liquid caustic soda is 25%~35%, in step
(A) insulation reaction temperature is 45~50 DEG C in.
6. according to the method for claim 1, it is characterised in that in step (B), Part I hydrochloric acid is hydrochloric acid total amount
55~64%, Part II hydrochloric acid is the 25~34% of hydrochloric acid total amount, and the hydrochloric acid total amount is Part I, Part II and the
The total amount of three parts hydrochloric acid, Part III hydrochloric acid make the pH value of mother liquor to 5.4~5.6.
7. according to the method for claim 6, it is characterised in that in step (B), Part I hydrochloric acid is hydrochloric acid total amount
60%, Part II hydrochloric acid is the 30% of hydrochloric acid total amount, and the hydrochloric acid total amount is Part I, Part II and Part III salt
The total amount of acid, Part III hydrochloric acid make the pH value of mother liquor to 5.5.
8. according to the method for claim 1, it is characterised in that in step (B), be incubated instead after adding Part I hydrochloric acid
Answer 5~8 hours, add Part II hydrochloric acid simultaneously insulation reaction 5~8 hours, add Part III hydrochloric acid after 0~10 DEG C of insulation
Reaction 5~8 hours, is cooled to insulation reaction 5~8 hours at 0 DEG C.
9. according to the method for claim 1, it is characterised in that in step (B), crystalline mother solution is from before cooling down until discharging
All carry out under agitation, stir speed (S.S.) is 20~100 revs/min.
10. according to the method for claim 1, it is characterised in that in step (B), the mass concentration of the hydrochloric acid is 20%
More than.
11. the method according to claim 9 or 10, it is characterised in that in step (B), stir speed (S.S.) be 40~80 turns/
Minute, the mass concentration of the hydrochloric acid is more than 25%.
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| CN1063310C (en) * | 1996-03-02 | 2001-03-21 | 陈节生 | Agricultural chemical having fertilizer function and its prodn. method |
| CN101293862B (en) * | 2008-06-23 | 2010-12-15 | 江苏天容集团股份有限公司 | Method for preparing high content monosultap and dimehypo with monosultap anticentripetal mother solution |
| CN104447458B (en) * | 2014-12-11 | 2016-10-05 | 湖南国发精细化工科技有限公司 | The process for purification of Cupric sulfate in Cupric sulfate synthesis technique |
| CN105503680B (en) * | 2015-12-29 | 2017-09-19 | 江苏天容集团股份有限公司 | The method for improving Cupric sulfate centrifuge mother liquor flour extraction |
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