CN103772285B - A kind of recovery method of Analgin finished mother liquid - Google Patents
A kind of recovery method of Analgin finished mother liquid Download PDFInfo
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- CN103772285B CN103772285B CN201310239239.XA CN201310239239A CN103772285B CN 103772285 B CN103772285 B CN 103772285B CN 201310239239 A CN201310239239 A CN 201310239239A CN 103772285 B CN103772285 B CN 103772285B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
- C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
- C07D231/48—Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom
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Abstract
The invention discloses a kind of recovery method of Analgin finished mother liquid.The method comprises the following steps: Analgin finished mother liquid carries out concentrating by (1), decrease temperature crystalline, and carries out solid-liquid separation and obtain a reclaimed materials and secondary recovery mother liquor; (2) the secondary recovery mother liquor that step (1) obtains is concentrated, and the enriched material obtained is mixed with water and extraction agent, separate the organic phase containing organic impurity, by obtain carry out concentrating containing the aqueous phase of Analgin finished product, decrease temperature crystalline, and carry out solid-liquid separation and obtain secondary returning rewinding and three times and reclaim mother liquors, wherein, described extraction agent is one or more in benzene, sherwood oil, hexanaphthene, toluene, o-Xylol, m-xylene, p-Xylol, chloroform and ethyl acetate, is preferably ethyl acetate.The content of the Analgin crude product in the reclaimed materials in the present invention is all more than 80%, and the percent crystallization in massecuite of Analgin finished mother liquid can reach 90-95%.
Description
Technical field
The present invention relates to a kind of recovery method of Analgin finished mother liquid.
Background technology
Analgin (Sulpyrine) is white or slightly yellowish crystallization or crystalline powder, soluble in water.It belongs to pyrazolone antipyretic and analgesic, can be made into injection liquid, has more significant refrigeration function and stronger analgesic activity, and has certain anti-inflammatory anti rheumatism action.Be mainly used in acute high fever clinically, the state of an illness be anxious heavy, again without other efficient solution medicine of a warm nature can when promptly bring down a fever.At present, Analgin has market widely in the whole world, is in great demand.
The preparation method that Analgin is conventional is that pyrazolone produces quinizine oil through firstization reaction, hydrolysis, alkaline purification; quinizine oil produces quinizine oil through nitrosation reaction, reduction reaction, hydrolysis neutralization reaction; aminoantipyrene oil produces formyl amino antipyrine through acylation reaction; novalgin oil is generated again through first, hydrolysis, once neutralization, Two-step neutralization, dehydration; then through condensation reaction; refining crystallization generates the nearly wet product of Analgin, obtains Analgin finished product after dry packing.In the preparation technology of traditional Analgin finished product, the single crystallization rate of Analgin finished product is about 74%, and the Analgin of remaining about 26% enters into centrifuge mother liquor.Therefore, how high efficiente callback, one of the material in Analgin finished product centrifuge mother liquor is utilized to be the key reducing production cost.At present, the traditional method of process Analgin finished mother liquid be by Analgin finished product centrifuge mother liquor through four times concentrated, cooling, crystallization, centrifugal process, reclaim the material (crystal) at every turn obtained step by step.This way complex operation, reclaimed materials quality lower (Luo Waer content in crude product refers to the mass percent of Analgin crude product in reclaimed materials crystal product, and Analgin content in crude product value is higher, and illustrate that the foreign matter content in product is lower, quality product is higher).Wherein, the content of the Analgin crude product in secondary returning rewinding is about 75%, and the content of the Analgin crude product in No. three, four reclaimed materials, below 50%, need be refined further, and in addition, reclaiming mother liquor for five times also needs to carry out cover and continue to react to the useless mother post that methylates.Because in Analgin mother liquor, impurity is many, need strict crystallization control condition.Whole return period reaches more than 10 days, so just causes the significant wastage of the resources such as human and material resources.The recovery process flow process of traditional Analgin finished mother liquid as shown in Figure 1.
Therefore, develop that Analgin content in crude product in a kind of reclaimed materials is higher and recovery method that the is Analgin finished mother liquid that treatment cycle is brief is significant.
Summary of the invention
The above-mentioned defect that the object of the invention is to overcome prior art provides a kind of recovery method of Analgin finished mother liquid.
The invention provides a kind of recovery method of Analgin finished mother liquid, wherein, the method comprises the following steps:
(1) Analgin finished mother liquid is carried out concentrate, decrease temperature crystalline, and carry out solid-liquid separation and obtain a reclaimed materials and secondary recovery mother liquor;
(2) the secondary recovery mother liquor that step (1) obtains is concentrated, and the enriched material obtained is mixed with water and extraction agent, separate the organic phase containing organic impurity, by obtain carry out concentrating containing the aqueous phase of Analgin finished product, decrease temperature crystalline, and carry out solid-liquid separation and obtain secondary returning rewinding and reclaim mother liquors three times;
Wherein, described extraction agent is one or more in benzene, sherwood oil, hexanaphthene, toluene, o-Xylol, m-xylene, p-Xylol, chloroform and ethyl acetate, is preferably ethyl acetate.
The present inventor finds under study for action, in the recovery process of Analgin finished mother liquid, organic impurity and the Analgin finished product different solvabilities in aqueous phase and organic phase can be utilized, the aqueous phase containing Analgin finished product and the organic phase containing organic impurity is separated by extracting, obtain the aqueous phase solution that Analgin finished product concentration is higher, thus realize being effectively separated the organic impurity in Analgin finished mother liquid and Analgin crude product, improve the content of the Analgin crude product in reclaimed materials.
By the recovery method of Analgin finished mother liquid provided by the invention, effectively can remove organic impurity, and can make the content of the Analgin crude product in a reclaimed materials and secondary returning rewinding all more than 80%, and the percent crystallization in massecuite of Analgin finished mother liquid can reach 90-95%.And obtained by the present invention reclaimed materials and secondary returning rewinding can be back to the condensation reaction of Analgin as Analgin crude product (fundatrix), three times recovery mother liquor directly can be back in Analgin finished mother liquid because organic impurity content is low and carry out concentrated and decrease temperature crystalline, need not overlap and be further processed to the post that methylates, shorten treatment cycle.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the production technique figure that the Analgin finished mother liquid of prior art reclaims;
Fig. 2 is the artwork that Analgin finished mother liquid provided by the invention reclaims.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of recovery method of Analgin finished mother liquid, wherein, the method comprises the following steps:
(1) Analgin finished mother liquid is carried out concentrate, decrease temperature crystalline, and carry out solid-liquid separation and obtain a reclaimed materials and secondary recovery mother liquor;
(2) the secondary recovery mother liquor that step (1) obtains is concentrated, and the enriched material obtained is mixed with water and extraction agent, separate the organic phase containing organic impurity, by obtain carry out concentrating containing the aqueous phase of Analgin finished product, decrease temperature crystalline, and carry out solid-liquid separation and obtain secondary returning rewinding and reclaim mother liquors three times;
Wherein, described extraction agent is one or more in benzene, sherwood oil, hexanaphthene, toluene, o-Xylol, m-xylene, p-Xylol, chloroform and ethyl acetate, is preferably ethyl acetate.
In the present invention, described Analgin finished mother liquid refers to the ethanolic soln containing Analgin material of the centrifugal rear generation of first time crystallization, and the concentration of the Analgin finished product in described Analgin finished mother liquid is generally 10-14 % by weight.Organic impurity in Analgin finished mother liquid be generally in 4-novalgin, macromolecular colloid material, pyramidon and two (4-methylamino quinizine) methane one or more.
According to the present invention, the object concentrated Analgin mother liquor in step (1) can be more conducive to follow-up decrease temperature crystalline with remove portion solvent, therefore, usually, in step (1), make the density of the Analgin finished mother liquid after concentrating be 1.15-1.3g/mL to the condition that described Analgin finished mother liquid concentrates, be preferably 1.2-1.26g/mL.But, the present inventor finds, in the process preparing Analgin finished product, owing to containing ethanol residual in preparation process in Analgin finished mother liquid, in order to effect of extracting can be ensured better, eliminate the impact that residual ethanol produces the effect of extracting in step (2) further.On the one hand, concentrated object is beneficial to follow-up decrease temperature crystalline after desolventizing, on the other hand, also preferably to reach the remaining ethanol of removal to the concentrated condition of described Analgin finished mother liquid and ensure the object of the effect of extracting in step (2) further better.Therefore, the concentrated preferably concentrating under reduced pressure described in step (1).Described concentrated condition comprises: concentrated temperature is 45-90 DEG C, and vacuum tightness is 0.04-0.08MPa.Consider and ethanol is removed better not affect the object of the effect of extracting in step (2) to concentrated can the reaching of described Analgin finished mother liquid, under preferable case, described concentrated condition comprises: concentrated temperature is 45-65 DEG C, and vacuum tightness is 0.04-0.06MPa.In the present invention, vacuum tightness=barometric point-absolute pressure.
According to the present invention, described concentrating can be implemented by the usual manner of this area, such as, first can be concentrated by recovery tower, then be concentrated by thickener; Or directly concentrated by thickener.
According to the present invention, in step (1), the condition of described decrease temperature crystalline is not particularly limited, it can be the condition of the decrease temperature crystalline that this area routine adopts, usually, the Analgin finished mother liquid after concentrating can be made to be cooled to 10-30 DEG C, to be preferably cooled to 20-30 DEG C.
According to the present invention, in step (1), the mode of described decrease temperature crystalline is not particularly limited, it can be the decrease temperature crystalline mode of this area routine, as long as the object of decrease temperature crystalline can be realized, consider the percent crystallization in massecuite that can improve Analgin mother liquor further, usually, described decrease temperature crystalline is divided into two stages, the condition of the decrease temperature crystalline of first stage comprises: be cooled to 25-30 DEG C, decrease temperature crystalline time used is 2-4h, the heat-eliminating medium of cooling can be conventional various heat-eliminating mediums, preferably, cooling is implemented by adopting tap water as heat-eliminating medium in the cooling of described first stage, the condition of the decrease temperature crystalline of subordinate phase comprises: be cooled to 10-15 DEG C, and decrease temperature crystalline time used is 1-3h, and preferably, the cooling of described subordinate phase implements cooling by adopting icy salt solution as heat-eliminating medium.It should be noted that, the temperature of described cooling is lower than concentrated temperature.
According to the present invention, in step (1), the method for described solid-liquid separation can be the solid-liquid separating method of various routine known in the field, such as, can be filtering separation and/or centrifugation.Under preferable case, described solid-liquid separation is centrifugation.In the present invention, described centrifugal condition is not particularly limited, as long as magma can be realized to be separated obtains crystal and liquid phase, is separated with secondary recovery mother liquor (liquid phase) by No. time reclaimed materials of in magma (crystal).Usually, described centrifugal condition comprises: centrifugal rotating speed is that 200-1800 turns/min, and the centrifugal time is 30-90min, and under preferable case, described centrifugal condition comprises: centrifugal rotating speed is that 500-1500 turns/min, and the centrifugal time is 30-60min.
According to the present invention, in step (2), that carries out described secondary recovery mother liquor is concentratedly not particularly limited, usually, make the density of described enriched material can be 1.25-1.8g/mL to the condition that described secondary recovery mother liquor concentrates, under preferable case, the density of described enriched material is made to be 1.5-1.8g/mL to the condition that described secondary recovery mother liquor concentrates.
According to the present invention, being not particularly limited in step (2) to the concentrated condition of secondary recovery mother liquor and mode, can be concentrated condition and the mode of this area routine.In the present invention, identical with mode with the concentrated condition in above-mentioned step (1) with way choice to the concentrated condition of secondary recovery mother liquor in step (2), do not repeat them here.
In the present invention, after to secondary recovery mother liquor concentrations, enriched material is mixed with water and extraction agent, to utilize organic impurity to come effectively to be separated with the deliquescent difference in organic phase at aqueous phase with Analgin finished product.In the present invention, mainly utilize organic impurity and the Analgin finished product different solvabilities in aqueous phase and organic phase, the aqueous phase containing Analgin finished product and the organic phase containing organic impurity is separated by extracting, thus obtain the higher aqueous phase solution of Analgin finished product concentration, thus realize being effectively separated the organic impurity in Analgin finished mother liquid and Analgin crude product, improve the content of the Analgin crude product in reclaimed materials.
As long as the present invention can to meet with the selectable range of the volume ratio of described secondary recovery mother liquor described water, described extraction agent, organic impurity is effectively separated with Analgin crude product, usually, the volume ratio of described water, described extraction agent and described secondary recovery mother liquor can be 0.2-1:0.1-0.5:1, under preferable case, the volume ratio of described water, described extraction agent and described secondary recovery mother liquor is 0.2-0.4:0.1-0.2:1.
In the present invention, for the ease of the organic phase containing organic impurity and the aqueous phase containing Analgin are carried out layering effectively, under preferable case, the method that enriched material mixes with water and extraction agent is comprised after first described enriched material being mixed with water and mixing with described extraction agent again.
Generally, after described enriched material mixes with water, the pH value of gained mixture is generally in the scope of 7-10, but in order to obtain the effect better removing organic impurity, under preferable case, after described enriched material mixes with water, the pH value of the mixture of gained is 7.5-8.5.
In the present invention, described extraction agent is one or more in benzene, sherwood oil, hexanaphthene, toluene, o-Xylol, m-xylene, p-Xylol, chloroform and ethyl acetate, is preferably ethyl acetate.Wherein, the boiling range of sherwood oil can be 30-60 DEG C, one or more in 60-90 DEG C and 90-120 DEG C.
In the present invention, described extraction is carried out under normal temperature (25 DEG C).
In the present invention, the volume of described extraction agent refers to the relative density of the quality of described extraction agent divided by described extraction agent.
According to the present invention, in step (2), after being mixed with water and extraction agent by enriched material, separate the organic phase containing organic impurity, by obtain carry out concentrating containing the aqueous phase of Analgin finished product, decrease temperature crystalline, and carry out solid-liquid separation and obtain secondary returning rewinding and reclaim mother liquors three times.
According to the present invention, to the concentrated restriction do not had especially of the aqueous phase containing Analgin finished product obtained, usually, make the density of the aqueous phase after concentrating can be 1.1-1.3g/mL to the condition that described aqueous phase concentrates, under preferable case, the density of the aqueous phase after concentrating is made to be 1.2-1.24g/mL to the condition that described aqueous phase concentrates.
According to the present invention, the condition concentrate the aqueous phase containing Analgin finished product obtained and mode are not particularly limited, and can be concentrated condition and the mode of this area routine.In the present invention, identical with mode with the concentrated condition in above-mentioned step (1) with way choice to the concentrated condition of aqueous phase in step (2), do not repeat them here.
It should be noted that, in the recovery method of Analgin finished mother liquid, in step (2) in the condition concentrated containing the aqueous phase of Analgin finished product obtained and step (1) can be identical or different to the concentrated condition of Analgin finished mother liquid, namely to the temperature concentrated containing the aqueous phase of Analgin finished product obtained with can be identical or different to the concentrated temperature of Analgin finished mother liquid, to the vacuum tightness concentrated containing the aqueous phase of Analgin finished product obtained with can be identical or different to the concentrated vacuum tightness of Analgin finished mother liquid.
According to the present invention, the decrease temperature crystalline process of the aqueous phase after concentrated in step (2) can be the condition of the decrease temperature crystalline that this area routine adopts, described concentrated after condition and the way choice of cooling of aqueous phase can be identical with mode with the condition of the decrease temperature crystalline in step (1) above, do not repeat them here.
It should be noted that, in the recovery method of Analgin finished mother liquid, in step (2), can be identical or different to the condition of the decrease temperature crystalline that the aqueous phase after concentrated carries out in the condition of decrease temperature crystalline and step (1).Namely can be identical or different to the cooling temperature of the decrease temperature crystalline that the aqueous phase after concentrated carries out in the cooling temperature of decrease temperature crystalline process and step (1), can be identical or different to the cooling time used of the decrease temperature crystalline that the aqueous phase after concentrated carries out in cooling time used of decrease temperature crystalline process and step (1).
According to the present invention, step is not particularly limited the method for solid-liquid separation in (2), it can be the method for solid-liquid separation well known in the art, as long as magma can be realized to be separated obtains crystal and liquid phase, the secondary returning rewinding (crystal) namely in magma with reclaim mother liquor (liquid phase) three times and be separated.Under preferable case, the method for described solid-liquid separation is centrifugation, and described centrifugal condition is identical with condition centrifugal described in step (1), does not repeat them here.
According to the present invention, in step (2), the weight loss on drying of described enriched material is not particularly limited, can change in wider scope, usually, the weight loss on drying of described enriched material can be 5-20 % by weight, under preferable case, the weight loss on drying of described enriched material is 5-10 % by weight.
In the present invention, the condition determination of the weight loss on drying of described enriched material is 70 DEG C, the quality dried out after the enriched material obtained after the weight loss on drying of described enriched material refers to secondary recovery mother liquor concentrations is dried to constant weight accounts for the mass percent of the quality of Analgin wet product, for illustration of the degree removing organic impurity.
The quality of the secondary returning rewinding that the present invention obtains be by step (2) add water and organic solvent extracts, make dissolve organic contaminants in organic solvent, make Analgin finished product be dissolved in aqueous phase, Analgin finished product and organic impurity are realized effectively be separated and realize.
In the present invention, the organic impurity content reclaiming mother liquor due to three times that obtain is low, under preferable case, the method also comprises and described three times is reclaimed mother liquors and return in step (1) carry out concentrated and decrease temperature crystalline together with Analgin finished mother liquid, is beneficial to and saves production cost.The described mode returned by described three recovery mother liquors can be the usual manner of this area, does not repeat them here.
In addition, consider the impact on environment, step (1) and step (2) are preferably implemented in confined conditions.Describedly airtightly can carry out step (1) in airtight container and step (2) is implemented.
Below will be described the present invention by embodiment.
The content of Analgin crude product is measured by redox titration method.
The percent crystallization in massecuite calculation formula of Analgin finished mother liquid is as follows:
Embodiment 1
The method that the present embodiment reclaims for illustration of Analgin finished mother liquid provided by the invention.
(1) (density is 0.92g/mL to measure 1000mL Analgin finished mother liquid, the content of Analgin finished product is 11.1 % by weight), in confined conditions, with efficient concentration device (Zhe Bo Machinery Co., Ltd., model is QN-300, identical below) concentrated, controlling concentrated temperature is 45 DEG C, vacuum tightness is 0.04MPa, the density being concentrated into the Analgin finished mother liquid after concentrating is 1.21g/mL, then decrease temperature crystalline is carried out, tap water is first adopted to lower the temperature as heat-eliminating medium, 30 DEG C are cooled to after 2 hours, use icy salt solution again instead to lower the temperature as heat-eliminating medium, 15 DEG C are cooled to after 1h, then carry out centrifugal, centrifugal rotating speed is 1500 turns/min, a reclaimed materials (67g is obtained after centrifugal 30min, the content of Analgin crude product is 88%) and secondary recovery mother liquor,
(2) the secondary recovery mother liquor of above-mentioned 380mL is concentrated, the density being concentrated into the secondary recovery mother liquor after concentrating is 1.62g/mL, controlling concentrated temperature is 45 DEG C, vacuum tightness is 0.04MPa, the weight loss on drying of gained enriched material is 5.3 % by weight, then enriched material is mixed with the water of 120mL, and the pH value measuring gained mixture is 7.5, then in gained mixture, add ethyl acetate 38g and carry out extracting and demixing, the organic phase containing organic impurity of gained is separated, the aqueous phase containing Analgin finished product of gained is concentrated, controlling concentrated temperature is 65 DEG C, vacuum tightness is 0.05MPa, the density being concentrated into the aqueous phase after concentrating is after 1.23g/mL, carry out decrease temperature crystalline again, first lower the temperature as heat-eliminating medium with tap water, 30 DEG C are cooled to after 2 hours, use icy salt solution again instead to lower the temperature as heat-eliminating medium, 15 DEG C are cooled to after 1h, then carry out centrifugal, centrifugal rotating speed is 1500 turns/min, secondary returning rewinding (40g is obtained after centrifugal 30min, the content of Analgin crude product is 85%) and reclaim mother liquor three times, three recovery mother liquors are returned in step (1) carry out concentrated and decrease temperature crystalline together with Analgin finished mother liquid.Through calculating, the content of Analgin crude product is 86.9%, and the percent crystallization in massecuite of Analgin finished mother liquid is 91%.
Comparative example 1
The recovery of Analgin finished mother liquid is carried out according to the method for embodiment 1, difference is, in step (2), do not add water and ethyl acetate, directly the secondary recovery mother liquor that step (1) obtains is carried out concentrating, decrease temperature crystalline and centrifugally operated obtain secondary returning rewinding (content of Analgin crude product is 76%) and reclaim mother liquors three times.Through calculating, the content of Analgin crude product is 79%, and the percent crystallization in massecuite of Analgin finished mother liquid is 81.6%.
Embodiment 2
The method that the present embodiment reclaims for illustration of Analgin finished mother liquid provided by the invention.
(1) (density is 0.92g/mL to measure 1000mL Analgin finished mother liquid, the content of Analgin finished product is 11 % by weight), in confined conditions, concentrate with efficient concentration device, controlling concentrated temperature is 60 DEG C, vacuum tightness is 0.06MPa, the density being concentrated into the Analgin finished mother liquid after concentrating is 1.25g/mL, then lower the temperature, tap water is first adopted to lower the temperature as heat-eliminating medium, 28 DEG C are cooled to after 3 hours, use icy salt solution again instead to lower the temperature as heat-eliminating medium, 12 DEG C are cooled to after 2h, then carry out centrifugal, centrifugal rotating speed is 1000 turns/min, a reclaimed materials (75g is obtained after centrifugal 40min, the content of Analgin crude product is 85%) and secondary recovery mother liquor,
(2) the secondary recovery mother liquor of above-mentioned 360mL is concentrated, the density being concentrated into the secondary recovery mother liquor after concentrating is 1.80g/mL, controlling concentrated temperature is 60 DEG C, vacuum tightness is 0.06MPa, the weight loss on drying of gained enriched material is 7.1 % by weight, then mix in enriched material with the water of 120mL, and the pH value measuring gained mixture is 8.5, then in gained mixture, add ethyl acetate 50g and carry out extracting and demixing, the organic phase containing organic impurity of gained is separated, the aqueous phase containing Analgin of gained is concentrated, controlling concentrated temperature is 60 DEG C, vacuum tightness is 0.06MPa, the density being concentrated into the aqueous phase after concentrating is after 1.22g/mL, lower the temperature again, first lower the temperature as heat-eliminating medium with tap water, 28 DEG C are cooled to after 3 hours, use icy salt solution again instead to lower the temperature as heat-eliminating medium, 12 DEG C are cooled to after 2h, then carry out centrifugal, centrifugal rotating speed is 1000 turns/min, secondary returning rewinding (36g is obtained after centrifugal 40min, the content of Analgin crude product is 83%) and reclaim mother liquor three times, three times are reclaimed in the Analgin finished mother liquid that mother liquor returns in step (1) and carry out concentrated and decrease temperature crystalline together.Through calculating, the content of Analgin crude product is 84.4%, and the percent crystallization in massecuite of Analgin finished mother liquid is 92.5%.
Embodiment 3
The method that the present embodiment reclaims for illustration of Analgin finished mother liquid provided by the invention.
(1) (density is 0.92g/mL to measure 1000mL Analgin finished mother liquid, the content of Analgin finished product is 10.8 % by weight), in confined conditions, concentrate with efficient concentration device, control concentrated temperature 50 C, vacuum tightness is 0.05MPa, the density being concentrated into the Analgin finished mother liquid after concentrating is 1.24g/mL, then lower the temperature, tap water is first adopted to lower the temperature as heat-eliminating medium, 26 DEG C are cooled to after 3 hours, use icy salt solution again instead to lower the temperature as heat-eliminating medium, 10 DEG C are cooled to after 1h, then carry out centrifugal, centrifugal rotating speed is 800 turns/min, a reclaimed materials (70g is obtained after centrifugal 55min, the content of Analgin crude product is 86.2%) and secondary recovery mother liquor,
(2) the secondary recovery mother liquor of above-mentioned 350mL is concentrated, the density being concentrated into the secondary recovery mother liquor after concentrating is 1.75g/mL, controlling concentrated temperature is 50 DEG C, vacuum tightness is 0.05MPa, the weight loss on drying of gained enriched material is 8.5 % by weight, then enriched material is mixed with the water of 120mL, and the pH value measuring gained mixture is 8, then in gained mixture, add ethyl acetate 30g and carry out extracting and demixing, the organic phase containing organic impurity of gained is separated, aqueous phase gained being contained Analgin finished product concentrates, controlling concentrated temperature is 50 DEG C, vacuum tightness is 0.06MPa, the density being concentrated into the aqueous phase after concentrating is after 1.21g/mL, lower the temperature again, first lower the temperature as heat-eliminating medium with tap water, 30 DEG C are cooled to after 2 hours, use icy salt solution again instead to lower the temperature as heat-eliminating medium, 15 DEG C are cooled to after 1h, then carry out centrifugal, centrifugal rotating speed is 800 turns/min, secondary returning rewinding (40g is obtained after centrifugal 55min, the content of Analgin crude product is 83.8%) and reclaim mother liquor three times, three recovery mother liquors are returned in step (1) carry out concentrated and decrease temperature crystalline together with Analgin finished mother liquid.Through calculating, the content of Analgin crude product is 85.3%, and Analgin finished mother liquid finished product percent crystallization in massecuite is 94.5%.
Embodiment 4
The method that the present embodiment reclaims for illustration of Analgin finished mother liquid provided by the invention.
Carry out the recovery of Analgin finished mother liquid according to the method for embodiment 1, difference is, the o-Xylol adding same volume number in step (2) replaces ethyl acetate as extraction agent.Through calculating, the content of Analgin crude product is 81%, and the percent crystallization in massecuite of Analgin finished mother liquid is 90.5%.
Embodiment 5
Carry out the recovery of Analgin finished mother liquid according to the method for embodiment 1, difference is, the hexanaphthene adding same volume number in step (2) replaces ethyl acetate as extraction agent.Through calculating, the content of Analgin crude product is 82.1%, and the percent crystallization in massecuite of Analgin finished mother liquid is 90.7%.
Embodiment 6
Carry out the recovery of Analgin finished mother liquid according to the method for embodiment 1, difference is, the chloroform adding same volume number in step (2) replaces ethyl acetate as extraction agent.Through calculating, the content of Analgin crude product is 81.3%, and the percent crystallization in massecuite of Analgin finished mother liquid is 90.2%.
Embodiment 7
Carry out the recovery of Analgin finished mother liquid according to the method for embodiment 1, difference is, in step (2), the enriched material obtained is mixed with water and ethyl acetate simultaneously, through calculating, the content of Analgin crude product is 82.7%, and the percent crystallization in massecuite of Analgin finished mother liquid is 90.8%.
Embodiment 8
The recovery of Analgin finished mother liquid is carried out according to the method for embodiment 1, difference is, be temperature in the concentrated condition of step (1) be 45 DEG C, pressure is 0.1MPa, obtains a reclaimed materials (content of Analgin crude product is 84%) and secondary recovery mother liquor; The secondary returning rewinding (content of Analgin crude product is 81%) obtained through step (2) and reclaim mother liquors three times, through calculating, the content of Analgin crude product is 82.3%, and the percent crystallization in massecuite of Analgin finished mother liquid is 90.2%.
As can be seen from the data of embodiment 1-7, the content of the Analgin crude product in the reclaimed materials obtained by the recovery method of Analgin finished mother liquid provided by the invention is all more than 80%, and the percent crystallization in massecuite of Analgin finished mother liquid can reach 90%-95%.By comparing of embodiment 8 and embodiment 1, known, can in removal step (1) ethanol prerequisite under, recovering effect is better.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a recovery method for Analgin finished mother liquid, is characterized in that, the method comprises the following steps:
(1) Analgin finished mother liquid is carried out concentrate, decrease temperature crystalline, and carry out solid-liquid separation and obtain a reclaimed materials and secondary recovery mother liquor;
(2) the secondary recovery mother liquor that step (1) obtains is concentrated, and the enriched material obtained is mixed with water and extraction agent, separate the organic phase containing organic impurity, by obtain carry out concentrating containing the aqueous phase of Analgin finished product, decrease temperature crystalline, and carry out solid-liquid separation and obtain secondary returning rewinding and reclaim mother liquors three times;
Wherein, described extraction agent is one or more in benzene, sherwood oil, hexanaphthene, toluene, o-Xylol, m-xylene, p-Xylol, chloroform and ethyl acetate, and the volume ratio of described water, described extraction agent and described secondary recovery mother liquor is 0.2-1:0.1-0.5:1.
2. method according to claim 1, wherein, described extraction agent is ethyl acetate.
3. method according to claim 1, wherein, in step (1), makes the density of the Analgin finished mother liquid after concentrating be 1.15-1.3g/mL to the condition that described Analgin finished mother liquid concentrates.
4. method according to claim 1, wherein, in step (2), makes the density of described enriched material be 1.25-1.8g/mL to the condition that described secondary recovery mother liquor concentrates.
5. method according to claim 1, wherein, in step (2), makes the density of the aqueous phase after concentrating be 1.1-1.3g/mL to the condition that described aqueous phase concentrates.
6. method according to claim 1, wherein, in step (2), comprises the method that enriched material mixes with water and extraction agent first being mixed with water by described enriched material and mixes with described extraction agent.
7. according to the method in claim 1-6 described in any one, wherein, in step (1) and step (2), described concentrated condition comprises: concentrated temperature is 45-90 DEG C, and vacuum tightness is 0.04-0.08MPa.
8. method according to claim 1, wherein, in step (1) and step (2), the Tc of described decrease temperature crystalline is 10-30 DEG C.
9. method according to claim 1, wherein, in step (2), the weight loss on drying of described enriched material is 5-20 % by weight.
10. method according to claim 1, wherein, the method also comprises and described three times is reclaimed mother liquors and return in step (1) carry out concentrated and decrease temperature crystalline together with Analgin finished mother liquid.
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| CN102584706A (en) * | 2011-12-23 | 2012-07-18 | 山东新华制药股份有限公司 | Recovery process of analginum finished product centrifugal mother liquid |
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| CN102584706A (en) * | 2011-12-23 | 2012-07-18 | 山东新华制药股份有限公司 | Recovery process of analginum finished product centrifugal mother liquid |
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