CN210736624U - Production system for recycling taurine mother liquor completely - Google Patents
Production system for recycling taurine mother liquor completely Download PDFInfo
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Abstract
The utility model discloses a production system of full recovery processing taurine mother liquor for ethylene oxide method taurine production technology handles taurine last mother liquor, reduces the filtration resistance of last mother liquor through preprocessing device, preprocessing device is including reaction unit and/or enrichment facility, cooling crystallization device, the first filter equipment that connects gradually. Therefore, more impurities in the taurine mother liquor can be removed, the problem of impurity separation is solved, the time for impurity removal and recovery is greatly shortened, the pure taurine mother liquor is obtained by further removing salt through activated carbon decoloration and impurity removal and ammonia introduction, and the recovery of the mother liquor is realized to improve the product yield.
Description
Technical Field
The utility model relates to a production method in the process of chemically synthesizing taurine, in particular to a method and a production system for removing impurities and recycling mother liquor generated in the process of producing taurine by an ethylene oxide method.
Background
Taurine, chemical name 2-aminoethanesulfonic acid, is the most abundant sulfur-containing free amino acid in the cells of the body. The chemical synthesis process route of taurine mainly comprises an ethylene oxide method and an ethanolamine method. The preparation method of the ethylene oxide comprises the following three steps:
(1) ethylene oxide is taken as a starting material, and the addition reaction of the ethylene oxide and sodium bisulfite is carried out to obtain sodium isethionate;
the main reaction is as follows:
CH2CH2O+NaHSO3→HOCH2CH2SO3Na
HOCH2CH2SO3Na+NH3→H2NCH2CH2SO3Na+H2O
2H2NCH2CH2SO3Na+H2SO4→2H2NCH2CH2SO3H+Na2SO4
addition side reaction:
CH2CH2O+H2O→HOCH2CH2OH
(2) ammonolyzing the hydroxyethyl sodium sulfonate to obtain sodium taurate;
ammonolysis side reaction:
2HOCH2CH2SO3Na+NH3→HN(CH2CH2SO3Na)2+2H2O
3HOCH2CH2SO3Na+NH3→N(CH2CH2SO3Na)3+3H2O
(3) acidifying to obtain taurine, such as hydrochloric acid, preferably sulfuric acid, and neutralizing to obtain taurine and inorganic salt.
The addition and synthesis reactions inevitably produce by-products including ethylene glycol and polymers of ethylene glycol. The ammonolysis reaction is a reversible reaction, about more than 20% of sodium isethionate can enter the next procedure along with a production system, mother liquor obtained by separation is obtained after the ammonolysis reaction finished solution is neutralized by sulfuric acid, and the last mother liquor is obtained by 1-3 times of concentration, separation and extraction. The impurities in the last mother liquor mainly comprise taurine, sodium isethionate, sodium sulfate, iminodiacetic acid sodium sulfonate, glycol, polyethylene glycol, trace metal ions and other components, and belong to high-pollution discharge. When the mother liquor adopted by the existing production method is circularly used, the problem of accumulation and increase of byproducts can be caused, and when the byproducts reach a threshold value, the problem can be solved only by a method of discharging part of the mother liquor, so that waste and pollution are caused.
Chinese patents CN101508657, CN10158658, CN10158659 and CN101486669 describe a process for neutralizing sodium taurate using sulfuric acid, thereby obtaining taurine and sodium sulfate. After cooling, the crystal suspension is filtered to obtain crude taurine easily. However, the spent mother liquor still contains taurine, sulfates and other organic impurities.
Regarding the utilization of the mother liquor, in the research on the taurine ammonolysis reaction process (author: Liu Fu Min and Ji Li Min) in No. 5 of Shandong chemical engineering, volume 44 in 2015, the process of the taurine reaction and other organic impurities such as ethylene glycol and polyethylene glycol existing in the reaction are described in detail, and the influence of mother liquor application on the yield is also analyzed. The higher the mother liquor content in the reaction system, the higher the product yield. The amount of the mother liquor in the actual production process cannot be increased without limit, a large amount of byproducts are increased in the reaction system along with the increase of the content of the mother liquor, and the output of the last mother liquor in the production process can only meet 9.0 percent (v/v) of the set amount. Comprehensively considers the production comprehensive cost and the yield quality, and is most suitable for selecting the mother liquor with the content of 6.3-8.3% (v/v). Therefore, the removal of impurities in the mother liquor is a precondition for realizing the increase of the mother liquor, otherwise, the increase of the application amount can lead to more byproducts in the production and more unstable production.
Chinese patent CN107056659A describes a method for neutralizing sodium taurate by ion exchange to obtain taurine, and recycling the mother liquor to further improve the yield. The process route mainly avoids the generation of sulfate, recycles sodium atoms in the sulfate, greatly saves raw materials such as sulfuric acid, sodium hydroxide and the like, and the extracted mother liquor is used as the raw material to return to the ammonolysis reaction. However, the process does not avoid the generation of side reactions such as addition, synthesis and the like, and the mother liquor still needs to be subjected to impurity removal treatment.
Regarding the impurity removal treatment of the mother liquor, chinese patent CN105732440 discloses a method for producing taurine by fully recovering the mother liquor, which mainly removes impurities through 2-stage neutralization to obtain a crude product of taurine, and the mother liquor is further subjected to pressure filtration and catalysis to remove sodium sulfate and then is recycled to a synthesis process. Wherein the removal effect of the ethylene glycol and other organic polymers in the waste water is limited through 2-stage neutralization and impurity removal.
In summary, although the existing taurine preparation process is relatively mature, there are still many disadvantages in separation and purification of taurine and recycling of mother liquor, especially, the viscosity of organic impurities in the mother liquor of the end liquor generated by the system for producing taurine is high, and separation of organic impurities in large-scale production is a problem which is difficult to solve, and an effective solution is urgently sought.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a preliminary treatment process and system of taurine last mother liquor can effectively reduce the viscosity of the last mother liquor, gets rid of partial impurity simultaneously, increases substantially recovery processing efficiency.
Further, the utility model provides an adopt above-mentioned pretreatment methods's edulcoration recovery method and system to realize the full recycle of mother liquor.
Through a large number of researches and experiments, the inventor unexpectedly discovers a method for removing impurities and recycling taurine mother liquor, and adds a pretreatment process to the mother liquor in the process for preparing taurine by using the existing ethylene oxide method, so that the viscosity of the last mother liquor is reduced, and then the subsequent decolorization and impurity removal treatment is carried out, and the taurine mother liquor can be efficiently and completely recycled.
A method for fully recycling taurine mother liquor is used for a taurine production process by an ethylene oxide method, and the method for processing the final mother liquor of taurine comprises the following steps:
(1) sequentially adding alkali and acid into the final taurine mother liquor to generate salt in the solution, or directly adding salt into the final taurine mother liquor, wherein the generated salt and the added salt are used for reducing the filtration resistance;
(2) concentrating and crystallizing the material collected in the step (1);
(3) filtering to obtain the transparent final mother liquor of taurine.
Preferably, the reaction temperature of the step (1) is 50-95 ℃, the pH value after adding acid is 7.0-10.5, the reaction temperature is preferably 50-75 ℃, and the pH value is 8.5-10.0.
Preferably, the amount of the alkali added in the step (1) is 5 to 50 percent of the volume of the taurine last mother liquor, and the best amount is 15 to 35 percent.
Further, the alkali in the step (1) is: any one or a mixture of any two or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and the like; the acid can be sulfuric acid, hydrochloric acid, organic acid, etc., or salt formed by reacting the above alkali with the above acid can be added, such as sodium hydroxide and sulfuric acid to form sodium sulfate, potassium hydroxide and sulfuric acid to form potassium sulfate, etc., wherein the concentration is 1m3The amount of the substance added with the salt in the last mother liquor volume is 530mol-5300 mol: preferably, liquid alkali and sulfuric acid are added in sequence, sodium taurate is generated firstly and sodium sulfate is generated secondly according to the chemical acid-base reaction principle, so that the advantage of selection is that no new impurities are added to the production system, and the recovery and application are facilitated.
Preferably, the concentration and evaporation water content of the step (2) is 30-60%, preferably 35-45%, and the concentration multiple is about 1.4-2.5, preferably 1.5-1.8 times, so as to obtain the crystallization solution.
Preferably, the step (2) is performed with temperature reduction and crystallization after concentration.
And (3) further performing activated carbon decoloration and impurity removal treatment on the pretreated final mother liquor, adding activated carbon into the taurine final mother liquor obtained in the step (3) under a cooling condition for decoloration, adding alkali to adjust the pH value to 9.0-10.5, and filtering.
Preferably, the temperature reduction condition means that the temperature of the production system is lower than the temperature of the previous working procedure, and the treatment temperature of the system is controlled to be 15-25 ℃, more preferably 18-22 ℃;
preferably, the outlet feed liquid obtained after the activated carbon decolorization and the alkali addition filtration is treated by introducing ammonia, the mother liquid after impurity removal is obtained by solid-liquid separation, and the mother liquid is completely returned to the ammonolysis process.
And after the activated carbon is decolorized, when ammonia is required to be introduced for treatment, adding liquid ammonia or ammonia gas into the outlet liquid, wherein the mass volume ratio of ammonia is more than 15 g/100 ml, preferably 17-19 g/100 ml, and removing impurities such as salt and the like.
The method skillfully utilizes the reaction, firstly reacts the reaction solution with liquid alkali to enable substances in the solution to exist in a sodium salt form, then the substances are neutralized by sulfuric acid to generate sodium sulfate, and then the sodium sulfate and impurities are separated out through concentration and crystallization, so that the generated sodium sulfate indirectly plays a role in filter aid, the aim of rapid separation is achieved, and the industrial implementation is facilitated.
Based on the inventive concept, the method for removing impurities and recovering mother liquor is applied to the production process of taurine by an ethylene oxide method, and comprises the following steps:
s1, reacting ethylene oxide with a sodium bisulfite solution to obtain sodium isethionate;
s2, mixing the sodium isethionate obtained in the step S1, the treated mother liquor and ammonia water to obtain a reaction solution, absorbing ammonia to a certain concentration, carrying out ammonolysis reaction under the action of a catalyst, and evaporating and concentrating to obtain a sodium taurate solution;
s3, preparing the sodium taurate solution obtained in the step S2 into a solution with a certain concentration, wherein a feed solution of taurine can be obtained by passing through acidic cation exchange resin, and a crude product and a mother solution of taurine are obtained by concentrating and crystallizing; or adding sulfuric acid to pH7.0-8.5 to obtain taurine crystal liquid, and cooling and crystallizing to obtain crude taurine and mother liquor;
s5, adding a certain amount of alkali into the taurine last mother liquor collected in the S4, and uniformly stirring, wherein liquid alkali is preferably selected. Then adding a certain amount of acid to the solution until the pH value is 7.0-10.5, and controlling the reaction temperature to be 50-75 ℃. In particular, the acid is preferably sulfuric acid, and the pH is adjusted to 8.5 to 10, preferably 9.0 to 9.5.
S6, transferring the material collected in the S5 to a concentration system for concentration, and concentrating and evaporating the material to have 30-60% of water, preferably 35-45% of water, and the concentration multiple is about 1.4-2.5, preferably 1.5-1.8 times, so as to obtain a crystallization solution. The water content is preferably 40% -42% evaporated, and the concentration ratio is preferably 1.65-1.72 times.
S7, transferring the material collected in the step S6 to a cooling crystallization kettle, cooling to 65-99 ℃, preferably to 72-78 ℃, and then pumping into a plate frame for filtering to obtain a transparent solution.
S8, cooling the solution collected in the step S7 to 15-25 ℃, preferably 18-22 ℃, adding a certain amount of activated carbon, adding liquid alkali to the pH of 9.0-10.5, preferably cooling to the pH of 9.5-10, and separating by using filtering equipment such as a plate frame, a microporous filter and the like to obtain a mother solution;
s9, introducing liquid ammonia or ammonia gas into the mother liquor collected in the step S8 under the condition of temperature reduction until the mass volume ratio of the ammonia content is more than 15 g/100 ml (15%), preferably 17-19 g/100 ml (17-19%), separating out a large amount of salt and other impurities, filtering by using a blade filter or a sealing plate frame to obtain clear mother liquor, and returning the obtained mother liquor to the step S2 for use in the ammonolysis process.
It should be noted that, the sodium isethionate generated in S1 may be concentrated, crystallized and dried to obtain a corresponding solid, or the mixed liquid obtained from the reaction may be directly mixed with the ammonia water of S2 without treatment after the direct reaction is completed to obtain a corresponding reaction solution, wherein the ammonia concentration in the reaction solution after ammonia absorption is 20-28 wt% (weight percentage).
Specifically, the concentration of the sodium bisulfite solution in S1 is 9-36 wt%, and the mass ratio of sodium bisulfite to ethylene oxide is 1: 0.95-1.
Specifically, the catalyst in S2 is any one or a mixture of any two or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate, and the ammonolysis reaction is carried out at the temperature of 150-290 ℃ and under the pressure of 10-25 MPa. Preferably, the base added in S5 is the same as the catalyst in S2, avoiding the generation of new impurities.
Specifically, when the sodium taurate is treated by selecting the acidic cation exchange resin column in S3, the concentration of the sodium taurate solution is 15-35%, preferably 18-20%. When the sodium taurate is treated with sulfuric acid in S3, the concentration of the sodium taurate solution is 25% -40%, preferably 32% -38%.
And in the S3, the crude taurine needs to be dissolved by adding water, activated carbon and the like, then the solution is decolored, filtered, cooled, crystallized, centrifuged and dried to obtain a finished taurine product, and the centrifuged fine mother liquor can be recycled to the preparation of the sodium taurate solution or the taurine decoloration ingredient.
Specifically, the mother liquor in the S4 is subjected to concentration and crystallization for multiple times, and can be concentrated once or twice, so that a secondary or tertiary crude product can be obtained respectively, and the obtained final mother liquor of the taurine can be a secondary mother liquor or a tertiary mother liquor. When the acid cation exchange resin column is selected from S3 to treat sodium taurate, the preferred final mother liquor of taurine is secondary mother liquor; when the sodium taurate is treated by sulfuric acid in S3, the preferred final mother liquor of taurine is the third mother liquor.
Utilize foretell method, the utility model provides a production system of full recovery processing taurine mother liquor reduces the filtration resistance of last mother liquor through preprocessing device, preprocessing device is including reaction unit and/or enrichment facility, cooling crystallization device, the first filter equipment who connects gradually.
Preferably, the discharge gate of the pretreatment device is connected with an activated carbon decoloration and impurity removal device, the activated carbon decoloration and impurity removal device comprises a decoloration kettle and a second filtering device, the decoloration kettle is provided with a feed inlet for adding activated carbon and alkali, and is provided with a cooling mechanism for reducing the temperature in the kettle.
Preferably, the activated carbon decoloration edulcoration device is including the decoloration cauldron, advance plate frame filter pump, plate frame filter, transfer kettle, advance accurate filter pump, accurate filter and the receiving storage tank that connect gradually.
Preferably, the terminal discharge gate of active carbon decoloration edulcoration device is connected with leading to ammonia desalination device, it includes leading to ammonia reation kettle and airtight filter equipment that are equipped with circulation path to lead to ammonia desalination device.
Preferably, the ammonia introducing reaction kettle is provided with an ammonia inlet, a feed inlet and a discharge outlet, a terminal discharge outlet of the ammonia introducing reaction kettle is connected with the feed inlet of the closed filtering device through a pump, and the pump is provided with a rotary discharge valve for discharging the filtered clear materials.
Preferably, the first filtering device is a plate-and-frame filter.
Preferably, the reaction device and the cooling magma device of the pretreatment device are respectively provided with a cooling mechanism for reducing the temperature in the kettle.
Preferably, the cooling mechanism is a water circulation condensation layer arranged outside, and the condensation layer is provided with a cooling water inlet valve and a cooling water outlet valve.
The utility model discloses with prior art, have following advantage and beneficial effect:
1. the utility model discloses a method and system, add salt in taurine last mother liquor, perhaps add the sour processing with taurine last mother liquor through adding alkali, utilize different temperatures, concentration, PH realizes that impurity is appeared, and the phenomenon that active ingredient does not appear, add or generate salt and the impurity formation bridging that appears, reduce the filtration resistance, the viscosity of mother liquor has also fallen at the bottom simultaneously, the difficult problem of separation impurity has been solved, shorten the time that the edulcoration was retrieved greatly, thereby effectively get rid of more impurity in the taurine mother liquor, further remove salt and obtain pure taurine mother liquor through leading to ammonia processing, the realization is retrieved the mother liquor and is improved the product yield.
2. The utility model discloses the active carbon decoloration edulcoration device that adopts accomplishes under the cooling condition, utilizes impurity such as active carbon absorption a certain amount of ethylene glycol, metal ion and a small amount of organic matter for impurity in the taurine mother liquor is got rid of more thoroughly.
3. The utility model discloses a production system is retrieved in edulcoration adopts optimal design, pertinence utilizes effectual edulcoration device to remove all kinds of impurity that last mother liquor contained, and is high-efficient thorough, easy operation, running cost hang down.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of the last mother liquor pretreatment of an embodiment of the present invention;
FIG. 2 is a flow chart of a process for producing taurine by an ethylene oxide method according to an embodiment of the present invention; according to the taurine resin neutralization process, activated carbon decoloration and impurity removal and ammonia introduction treatment are carried out after pretreatment;
FIG. 3 is a flow chart of a process for producing taurine by an ethylene oxide method according to an embodiment of the present invention; according to the taurine sulfuric acid neutralization process, activated carbon decoloration and impurity removal and ammonia introduction treatment are carried out after pretreatment;
FIG. 4 is a schematic structural view of a mother liquor pretreatment apparatus in an embodiment of the present invention;
FIG. 5 is a schematic structural view of an activated carbon decoloring and decontaminating apparatus according to an embodiment of the present invention;
FIG. 6 is a schematic structural view of an ammonia introducing and desalting device in an embodiment of the present invention.
Detailed Description
The following detailed description of the present invention will be made with reference to the accompanying drawings and specific embodiments, which are provided for illustration only and are not intended to limit the scope of the present invention.
As shown in fig. 1, the utility model provides a method of taurine mother liquor edulcoration and recovery increases a pretreatment process to the last mother liquor processing in the taurine technology is prepared to current ethylene oxide legal system, successively adds alkali and acid, concentration crystallization and filtration to the taurine last mother liquor promptly, falls the viscosity of the last mother liquor earlier, obtains transparent taurine last mother liquor, then carries out processing such as subsequent decoloration edulcoration, can all recycle high-efficiently.
As shown in fig. 2 and 3, the pretreatment process is applied to a process for preparing taurine by an ethylene oxide method.
S1, reacting ethylene oxide with a sodium bisulfite solution to obtain sodium isethionate; in this step, impurities such as ethylene glycol, polyethylene glycol and the like are generated.
S2, mixing the sodium isethionate obtained in the step S1, the impurity-removed mother liquor and ammonia water to obtain a reaction solution, absorbing ammonia to a certain concentration, carrying out ammonolysis reaction under the action of a catalyst, carrying out flash evaporation treatment after the reaction is finished to discharge redundant ammonia gas from the reaction solution to be recycled as a raw material of the ammonolysis reaction, and carrying out evaporation concentration to obtain a sodium taurate solution; the ethylene glycol by-product in the sodium isethionate solution produced in step S1 is converted to organic impurities such as polyether alcohols. Because the ammonolysis reaction is a reversible reaction, the aim of improving the conversion rate of raw materials can be fulfilled according to the existence of the sodium ditallow and the sodium trithione in the chemical equilibrium theory. The mother liquor after impurity removal treatment is recycled, so that the aims of increasing the reuse of the liquor and reducing side reactions can be fulfilled, and the aims of further stabilizing the production and improving the yield are fulfilled.
S3, preparing the sodium taurate solution obtained in the step S2 into a solution with a certain concentration, passing the solution through an acidic cation exchange resin column to obtain a taurine feed solution, concentrating and crystallizing the taurine feed solution to obtain a taurine crude product and a mother solution, and separating the taurine crude product and the mother solution at the temperature of about 25 ℃; or adopting a sulfuric acid neutralization process, adding sulfuric acid until the pH value is 7.0-8.5 to obtain a taurine crystallization liquid, cooling and crystallizing to obtain a taurine crude product and a mother liquid, and separating at about 32-35 ℃.
And S4, concentrating and crystallizing the mother liquor collected in the S3 for multiple times, separating and extracting taurine through equipment such as a plate frame and the like, and concentrating the final mother liquor of the taurine.
S5, adding a certain amount of caustic soda liquid into the taurine last mother liquor collected in the step S4, wherein the adding amount is 5-50% of the volume of the last mother liquor, and uniformly stirring. Then adding a certain amount of sulfuric acid to the solution until the pH value is 7.0-10.5, controlling the reaction temperature to be 50-95 ℃, firstly allowing the substances in the solution to exist in the form of sodium salt, and then adding sulfuric acid to generate sodium sulfate.
S6, transferring the material collected in the step S5 to a concentration system for concentration, concentrating and evaporating 30-60% of water, wherein the concentration multiple is about 1.4-2.5 times, and controlling the concentration multiple and the concentration temperature to obtain the best crystallization effect and separate out impurities and sodium sulfate.
S7, the material that S6 collected changes to cooling crystallization kettle, the control temperature of 65-99 ℃ is cooled down, because the sodium sulfate solubility can rise along with the temperature reduction, and the solubility of taurine can rise along with the temperature rise, guarantee that impurity and sodium sulfate reach certain proportion, and taurine can not separate out, high temperature also makes solution viscosity lower in addition, because of there being a certain amount of sodium sulfate crystal solid in the impurity, form and filter the bridge, be favorable to the impurity separation, squeeze into the sheet frame again and filter and can realize quick separation.
S8, cooling the solution collected in the step S7 to 15-25 ℃, adding a certain amount of activated carbon, adding liquid alkali to the pH value of 9.0-10.5, and separating by using filtering equipment such as a plate frame and a microporous filter to obtain a mother solution;
s9, introducing liquid ammonia into the taurine-containing mother liquor collected in the step S8 and subjected to thorough impurity removal under the condition of temperature reduction until the ammonia content is more than 15%, precipitating a large amount of sulfate and other impurities, filtering the obtained product by using a blade filter or a closed plate frame to obtain clear mother liquor, and returning the obtained mother liquor to the ammonolysis process for use (the step S2). The filtration device described above needs to meet environmental requirements and must be closed to prevent ammonia leakage.
In order to explain the technical effects of the present invention, the following examples are given. The starting materials used in the following examples are commercially available products unless otherwise specified, the methods used are conventional methods unless otherwise specified, and the material contents are mass volume percentages unless otherwise specified.
Example 1
This example shows that the final mother liquor of taurine is subjected to alkali-acid addition treatment and activated carbon decolorization and impurity removal treatment:
(1) and taurine last mother liquor: taking 1500mL of taurine mother liquor, wherein the mass volume percentage is 10% (calculated by taurine, 10g of taurine is contained in 100mL of solution), adding 375mL of liquid alkali with the concentration of 32%, stirring uniformly, adding 100mL of concentrated sulfuric acid with the concentration of 98%, and controlling the reaction temperature at 50-75 ℃.
(2) Concentrating the solution to 1185ml, performing suction filtration on the concentrated solution at 75 ℃, wherein the suction filtration lasts for 15min (minutes), and filtering to obtain 975ml of filtrate to obtain 510g of solid, wherein the solid is dry, and the detected water content is 15%.
(3) Adding 46ml of 32% liquid caustic soda into the filtrate, cooling to 18-22 ℃, adding 1g of activated carbon, stirring for a certain time, and performing suction filtration to obtain 970ml of mother liquor. The main components are taurine and sodium isethionate, the detected taurine content is 15.2 percent, and the detected sodium isethionate content is 18.2 percent, compared with the final mother liquor of the taurine before treatment, the contents of the taurine and the sodium isethionate are both obviously improved, and the contents of impurities such as ethylene glycol, Fe and the like are obviously reduced.
The detection data are as follows:
| item | Taurine last mother liquor (before treatment) | Taurine last mother liquor (after treatment) |
| |
6％ | 0.5％ |
| Fe | 10ppm | ＜1ppm |
| Taurine content | 10％ | 15.2％ |
| Sodium isethionate content | 12％ | 18.2％ |
| Appearance of the product | Yellow colour | Light yellow |
Example 2
This example shows the control treatment experiment of the final taurine mother liquor:
(1) and taurine last mother liquor: taking 1500mL of taurine mother liquor, wherein the mass volume percentage of the taurine mother liquor is 10% (calculated by taurine, 10g of taurine is contained in 100mL of solution), concentrating the solution to 1185mL, carrying out suction filtration on the concentrated solution at 75 ℃, wherein when the suction filtration time is 3 hours, the solid obtained by suction filtration is thinner, more viscous, more in water content and 30% (mass percentage) in water content, and compared with example 1, the suction filtration effect is poor, the power of suction filtration equipment is required to be higher, the energy consumption is high, and the efficiency is low.
(2) And taurine last mother liquor: taking 1500mL of taurine mother liquor, wherein the mass volume percentage of the taurine mother liquor is 10% (calculated by taurine, 10g of taurine is contained in 100mL of solution), concentrating the solution to 1185mL, separating the concentrated solution at 75 ℃, adopting a centrifugal machine for separation, centrifuging for 15 minutes, and centrifuging to obtain a dilute solid, viscous solid and more water, wherein the water content is 28% (mass percentage), which is mainly limited by the high viscosity of the concentrated solution and the poor separation effect.
Example 3
The last mother liquor treated in example 1 was treated with ammonia and recycled.
And (3) introducing ammonia for recovering mother liquor: the mother liquor collected in example 1 was passed through liquid ammonia to a content of 15% -20%, and filtered to obtain a clear solution.
Preparing sodium taurate: in the presence of sodium hydroxide as a catalyst, carrying out ammonolysis reaction on a sodium isethionate solution (produced by enterprises), a mother solution subjected to ammonia treatment and ammonia gas at the temperature of 280 ℃ plus ammonia and the pressure of 10-15MPa for 1 hour, and after the reaction is finished, carrying out flash evaporation to remove the ammonia gas to obtain a solution, namely the sodium taurate solution.
The treated mother liquor is detected to be basically free of sulfate.
Example 4
The mother liquor of the last time before the treatment in example 1 was subjected to ammonia introduction treatment as it is, and then recovered and used in step S7.
And (3) introducing ammonia for recovering mother liquor: the raw material (i.e. the last mother liquor before treatment) in example 1 was charged with ammonia to a content of 15% -20%, and filtered to obtain a clear solution.
Preparing sodium taurate: in the presence of sodium hydroxide as a catalyst, carrying out ammonolysis reaction on a sodium isethionate solution (produced by enterprises), a mother solution subjected to ammonia treatment and ammonia gas at the temperature of 280 ℃ plus ammonia and the pressure of 10-15MPa for 1 hour, and after the reaction is finished, carrying out flash evaporation to remove the ammonia gas to obtain a solution, namely the sodium taurate solution.
Example 5
Selecting two groups of examples and corresponding reference examples, and displaying ammonolysis reaction conditions and subsequent extraction of crude taurine content under various mother liquor recycling conditions;
all the following examples are 1.5 mol of hydroxyethyl sodium sulfonate, sodium taurate solution is prepared according to the methods of the examples 3 and 4, the obtained sodium taurate solution is treated by cation exchange resin to obtain tauric acid solution, the tauric acid solution is concentrated and then cooled and crystallized to obtain crude taurine, and the taurine content is detected.
The yield was calculated according to the following formula:
wherein the ammonolysis yield is divided by the mass of pure taurine (mass of sodium isethionate divided by 148 × 125) × 100%
By comparing experiment 3 with experiment 4 in example 5, the ammonolysis reaction yield is increased by increasing the mother liquor after treatment, meanwhile, the crude product content is not influenced, and the mother liquor after treatment is relatively less in impurities.
Through the comparison of experiment 1 and experiment 3 in example 5, experiment 2 and experiment 4 compare, and the mother liquor cover quantity before and after the processing is under the same condition (the pure quantity is the same), the ammonolysis reaction yield is obviously increased, and crude product content is obviously promoted simultaneously, fully shows that the impurity of the mother liquor is thoroughly reduced after the processing, so that the side reaction under the ammonolysis reaction condition is greatly reduced, and the product quality is greatly improved.
By comprehensively comparing experiments 1, 2, 3 and 4 in example 5, the effective content of the treated mother liquor is greatly increased, the yield is increased, the crude product content is obviously increased, and the use amount of the treated mother liquor can be obviously increased (when the purity is equivalent).
Example 6
This example shows that the final mother liquor of taurine is subjected to salting and activated carbon decolorization and impurity removal:
(1) and taurine last mother liquor: taking 1500mL of taurine mother liquor, wherein the mass volume percentage is 10% (calculated by taurine, 10g of taurine is contained in 100mL of solution), adding Na into the taurine mother liquor2SO4127.8g (i.e. 0.9mol) of salt is stirred uniformly, and the temperature is controlled between 50 and 75 ℃.
(2) Concentrating the solution to 1185ml, performing suction filtration on the concentrated solution at 75 ℃ for 15 minutes, and filtering to obtain 1050ml filtrate to obtain 210g of solid, wherein the solid is dry, and the detected water content is 23%.
(3) Adding 50ml of 32% liquid caustic soda into the filtrate, cooling to 18-22 ℃, adding 1g of activated carbon, stirring for a certain time, and performing suction filtration to obtain 1046ml of mother liquor. The main components are taurine and sodium isethionate, the detected taurine content is 13.8 percent, and the detected sodium isethionate content is 16.5 percent, compared with the final mother liquor of the taurine before treatment, the contents of the taurine and the sodium isethionate are both obviously improved, and the contents of impurities such as ethylene glycol, Fe and the like are obviously reduced.
The detection data are as follows:
| item | Taurine last mother liquor (before treatment) | Taurine last mother liquor (after treatment) |
| |
6％ | 0.8％ |
| Fe | 10ppm | ＜1ppm |
| Taurine content | 10％ | 13.8％ |
| Sodium isethionate content | 12％ | 16.5％ |
| Appearance of the product | Yellow colour | Light yellow |
Example 7
This example shows that the final mother liquor of taurine is subjected to salting and activated carbon decolorization and impurity removal treatment:
(1) and taurine last mother liquor: taking 1500mL of taurine mother liquor, wherein the mass volume percentage is 10% (calculated by taurine, 10g of taurine is contained in 100mL of solution), adding Na into the taurine mother liquor2SO4568g (i.e. 4mol) of salt are stirred uniformly, and the temperature is controlled at 50-75 ℃.
(2) Concentrating the solution to 1185ml, performing suction filtration on the concentrated solution at 75 ℃ for 15 minutes, and filtering to obtain 985ml filtrate to obtain 774g of solid, wherein the solid is dry, and the detected water content is 15%.
(3) Adding 47ml of 32% liquid caustic soda into the filtrate, cooling to 18-22 ℃, adding 1g of activated carbon, stirring for a certain time, and performing suction filtration to obtain 980ml of mother liquor. The main components are taurine and sodium isethionate, the detected taurine content is 14.8 percent, and the detected sodium isethionate content is 17.8 percent, compared with the final mother liquor of taurine before treatment, the contents of taurine and sodium isethionate are both obviously improved, and the contents of impurities such as ethylene glycol, Fe and the like are obviously reduced.
The detection data are as follows:
| item | Taurine last mother liquor (before treatment) | Taurine last mother liquor (after treatment) |
| |
6％ | 0.6％ |
| Fe | 10ppm | ＜1ppm |
| Taurine content | 10％ | 14.8％ |
| Sodium isethionate content | 12％ | 17.8％ |
| Appearance of the product | Yellow colour | Light yellow |
The process equipment of the present invention will be described in detail with reference to the accompanying drawings.
As shown in fig. 4, the utility model provides a preprocessing device that taurine mother liquor edulcoration was retrieved uses the edulcoration recovery method shown in fig. 1, it adds sour cauldron 1 including the alkali that connects gradually, concentrated cauldron 2, concentrated ejection of compact crystal thick liquid jar 3, plate frame filter 4 and transfer cauldron 34 are connected, connect power equipment such as necessary pump between each equipment, concentrated cauldron 2 is connected with heat exchanger 39, add alkali and all be equipped with cooling mechanism on sour cauldron 1 and the concentrated ejection of compact crystal thick liquid jar 3 for reduce the temperature of the interior material of cauldron. Wherein, the alkali and acid adding kettle 1, the concentrated discharged crystal slurry tank 3 and the transfer kettle 34 are all normal pressure equipment.
Wherein, a feed inlet 9 of the alkali and acid adding kettle 1 is connected with a discharge outlet of the taurine last mother liquor obtained in the previous process. A mother liquor feeding port 9, an exhaust port 10 and a stirring mechanism 11 are arranged above the alkali and acid adding kettle 1, and a discharging valve 14 is arranged below the alkali and acid adding kettle; a water circulation condensation layer is arranged outside the alkali-adding and acid-adding kettle 1 and used for reducing the temperature in the alkali-adding and acid-adding kettle 1, the condensation layer is provided with a cooling water inlet valve 12 and a cooling water outlet valve 13, raw material pumps 5 and 6 are arranged between the concentration kettle 2 and the alkali-adding and acid-adding kettle 1, and the raw material pump 5 is provided with a feeding valve 15 and a discharging valve 16; the raw material pump 6 is provided with a feed valve 17 and a discharge valve 18, wherein the discharge valve 16 and the feed valve 17 are both connected with a heat exchanger 39. An exhaust valve 19 (the valve is normally open) is arranged above the concentration kettle 2, the lower part of the concentration kettle is connected with a raw material pump 7, the raw material pump 7 is provided with a feeding valve 20 and a discharging valve 21, the feeding valve 21 is connected with a feeding hole 24 of the concentrated discharging crystal slurry tank 3, a mother liquid feeding hole 24, an exhaust hole 25 and a stirring mechanism 26 are arranged above the concentrated discharging crystal slurry tank 3, and a discharging valve 27 is arranged below the concentrated discharging crystal slurry tank 3; concentrated ejection of compact crystal thick liquid jar 3's outside is equipped with the hydrologic cycle condensate layer, a temperature for reducing in the cauldron, this intermediate layer is equipped with cooling water inlet valve 22 and cooling water outlet valve 23, connect plate frame filter pump 8 through advancing plate frame filter pump feed valve 28, plate frame filter pump 8 is equipped with discharge valve 29 and backflow valve 31, the access & exit of plate frame filter 4 is equipped with feed valve 30 and discharge valve 32 respectively, it links to each other with transfer cauldron 34 to pass through transfer cauldron feed valve 33, transfer cauldron 34's top is equipped with feed inlet 35, gas vent 36 and rabbling mechanism 37, bottom discharge valve 38 links to each other with follow-up equipment. Besides the above-mentioned pipeline valves, the device is also provided with valves and connecting parts necessary for some production equipment, which are common technical means in the field and are not described herein.
In FIG. 5, a preferred subsequent impurity removal device is shown, namely, the material from the transfer pot 34 enters an activated carbon decoloring and impurity removal device. Namely, the final mother liquor of taurine obtained by pretreatment in the previous step is decolorized and decontaminated by active carbon. Specifically, the activated carbon decoloring and impurity removing device comprises a decoloring kettle 44, a plate-and-frame filter pump 52, a plate-and-frame filter 56, a transfer kettle 60, a precise filter pump 66, a precise filter 70 and a receiving storage tank 76 which are connected in sequence. The fine filter 70 has a finer filter pore size than the plate and frame filter 56, and can filter out small particle impurities. Wherein, the decoloring kettle 44, the transfer kettle 60 and the receiving storage tank 76 are all normal pressure equipment.
A water circulation condensation layer is arranged outside the decoloring kettle 44 and is used for reducing the temperature in the decoloring kettle 44, the interlayer is provided with a cooling water inlet valve 45 and a cooling water outlet valve 46, the decoloring kettle 44 is provided with a stirring mechanism 49, a mother liquid feeding port 47 and an exhaust port 48 are arranged above the decoloring kettle 44, a discharge valve 50 is arranged at the bottom of the decoloring kettle, the interlayer is connected with a plate frame filter pump 52 through a plate frame filter pump feeding valve 51, the plate frame filter pump 52 is provided with a discharge valve 53 and a return valve 54, a feeding valve 55 and a discharge valve 57 are respectively arranged at the inlet and the outlet of the plate frame filter 56 and are connected with a transfer kettle 60 through a transfer kettle feeding valve 58, a feeding port 61, an exhaust port 62 and a stirring mechanism 63 are arranged above the transfer kettle 60, a bottom discharge valve 64 is connected with a precision filter pump feeding valve 65, the outlet end of the precision filter pump 66 is connected with a discharge valve 67, the precision filter 70 is provided with a cleaning water inlet valve 71, a cleaning water outlet valve 72 and an exhaust valve 74, a discharge valve 75 of the precision filter is connected with an inlet of a receiving storage tank 76, the receiving storage tank 76 is provided with an exhaust port 77, and a discharge valve 78 of the receiving storage tank is connected with subsequent equipment. Valves and connecting parts necessary for other production equipment are all common technical means in the field, and are not described herein in detail. And a liquid feeding port is preferably arranged on the decoloring kettle and is used for adding liquid alkali and liquid acid.
After the device is added, the filtration efficiency and the processing capacity can be improved through two-stage filtration. The operation method comprises the following steps: activated carbon is added from a mother liquor feeding port 47 and can also be added from other openings, and is not limited here, a discharge valve 50 of a plate-frame filtering and decoloring kettle is closed, materials are added into a decoloring kettle 44 through the feeding port 47 of the decoloring kettle, a cooling water outlet valve 46 and a cooling water inlet valve 45 are opened, cooling water is introduced for cooling, a stirring mechanism 49 of the decoloring kettle is started simultaneously, and the cooling water inlet valve 45 and the cooling water outlet valve 46 are closed after the temperature is reduced to a specified temperature. The decolorization kettle discharge valve 50, the plate-frame filter pump feed valve 51, the plate-frame feed valve 55, the plate-frame discharge valve 57 and the transfer kettle feed valve 58 are opened, the transfer kettle discharge valve 64 is closed, the plate-frame filter pump 52 is started, the plate-frame filter pump return valve 54 is used for adjusting the plate-frame feed pressure, the activated carbon and the materials enter the plate-frame filter 56 together, the activated carbon is blocked in the filter 56, and the plate frame is opened to discharge the activated carbon with adsorbed impurities. After the materials in the transfer kettle 60 reach a certain volume, the transfer kettle discharge valve 64, the feed valve 65 of the feed precision filter pump, the feed return valve 68 of the feed precision filter pump, the feed valve 73 of the precision filter pump, the exhaust valve 74 of the precision filter and the discharge valve 75 of the precision filter are opened, the feed precision filter pump 66 is started, the discharge valve 67 of the feed precision filter pump is opened, after the discharge of the exhaust valve 74 of the precision filter pump, the exhaust valve 74 of the precision filter is closed, and the feed pressure of the precision filter 70 is adjusted through the feed return valve 68 of the feed precision filter pump. The material collected by the receiving storage tank 76 is sent to the subsequent working section for processing.
As shown in figure 6, the utility model optimizes the process and the equipment in the above embodiment, and the activated carbon decoloration and impurity removal device and the ammonia introducing desalting device of the impurity removal and recovery system are composed. The ammonia-introducing desalting device comprises an ammonia-introducing reaction kettle 82, a pump 91 and a leaf filter 96 which are connected in sequence, and the leaf filter 96 can also be replaced by a closed plate-and-frame filter. An ammonia absorber 99, an ammonia inlet valve 84, a feeding valve 83, a clear liquid return kettle valve 87 and an emptying valve 88 are arranged above the ammonia introducing reaction kettle 82, a safety valve 86 and a safety valve front control valve 85 are arranged, a discharging valve 89 is arranged at the bottom of the ammonia introducing reaction kettle, the discharging valve 89 is connected with a pump feeding valve 90, a pump discharging valve 92 and a rotary discharging valve 93 are respectively arranged at the other end of the pump 91, the outlet direction of the pump discharging valve 92 is connected with the ammonia absorber 99 through a vane inlet machine backflow valve 94, and is connected with a vane filter 96 through a vane machine feeding valve 95, an overflow valve 98 and a discharging valve 97 are arranged on the vane filter, and the discharging valve 97 is connected with the clear liquid return kettle valve 87. Also, the device is provided with valves and connecting parts necessary for production equipment, which are common technical means in the field and are not described herein.
The ammonia-introducing desalting device can remove salt and impurities in the mother liquor, and is simple in operation process. The operation method comprises the following steps: opening a front control valve 85 of the safety valve, opening an emptying valve 88, opening a feeding valve 83, adding the mother liquor into the ammonia introducing reaction kettle 82, and closing the feeding valve 83 after feeding. Opening a bottom discharge valve 89, a pump feeding valve 90 and a blade feeding machine reflux valve 94, starting a pump 91, opening a pump feeding valve 92, opening an ammonia feeding valve 84 after stabilization, closing an emptying valve 88, stopping absorption when the ammonia content is absorbed to be more than 15% (mass-volume ratio, 15 g/100 ml), and closing an ammonia feeding valve 75; the overflow valve 98 of the leaf machine, the clear liquid return valve 87 and the feeding valve 95 of the leaf machine are opened, after the leaf filter 96 is full, the discharging valve 97 of the leaf machine is opened, and the overflow valve 98 of the leaf machine is closed. The circulation process is repeated, the material state in the ammonia reaction kettle 96 is sampled and observed until the filtration is clear. After the filtration is clear, the material transferring valve 93 can be opened to transfer the material to the ammonolysis reaction process.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical scheme described in the previous embodiments can be modified, or the preparation reaction conditions can be replaced, or part of technical features can be replaced equivalently; such modifications and substitutions do not depart from the spirit and scope of the present invention in its corresponding aspects.
Claims (9)
1. The utility model provides a production system of taurine mother liquor is handled entirely to recovery processing for handle taurine last time mother liquor in ethylene oxide method taurine production technology, its characterized in that reduces the filtration resistance of last time mother liquor through preprocessing device, preprocessing device is including reaction unit and/or enrichment facility, cooling crystallization device, the first filter equipment who connects gradually.
2. The production system of claim 1, wherein the discharge port of the pretreatment device is connected with an activated carbon decoloring and impurity removing device, the activated carbon decoloring and impurity removing device comprises a decoloring kettle and a second filtering device, the decoloring kettle is provided with feed ports for adding activated carbon and alkali, and is provided with a cooling mechanism for reducing the temperature in the kettle.
3. The production system of claim 2, wherein a discharge port of the activated carbon decoloring and impurity removing device is connected with an ammonia introducing desalting device, and the ammonia introducing desalting device comprises an ammonia introducing reaction kettle provided with a circulation passage and a closed filtering device.
4. The production system of claim 3, wherein the activated carbon decolorizing and impurity removing device comprises a decolorizing kettle, a plate-and-frame filter pump, a plate-and-frame filter, a transfer kettle, a precise filter pump, a precise filter and a receiving storage tank which are connected in sequence.
5. The production system of claim 3, wherein a terminal discharge port of the activated carbon decoloring and impurity removing device is connected with an ammonia introducing desalting device, and the ammonia introducing desalting device comprises an ammonia introducing reaction kettle provided with a circulation passage and a closed filtering device.
6. The production system of claim 5, wherein the ammonia introducing reaction kettle is provided with an ammonia inlet, a feed inlet and a discharge outlet, the terminal discharge outlet of the ammonia introducing reaction kettle is connected with the feed inlet of the closed filtering device through a pump, and the pump is provided with a rotary discharge valve for discharging filtered clear materials.
7. The production system of claim 6, wherein the first filter device is a plate and frame filter.
8. The production system according to any one of claims 1 to 7, wherein the reaction vessel and the temperature-reducing crystallization device of the pretreatment apparatus are each provided with a temperature-reducing mechanism for reducing the temperature in the vessel.
9. The production system of claim 8, wherein the cooling mechanism is an externally disposed water circulation condensation layer provided with a cooling water inlet valve and a cooling water outlet valve.
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| CN201921737662.1U CN210736624U (en) | 2019-10-16 | 2019-10-16 | Production system for recycling taurine mother liquor completely |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315657A (en) * | 2021-12-24 | 2022-04-12 | 潜江永安药业股份有限公司 | Method for recycling taurine mother liquor |
| CN114590826A (en) * | 2022-04-18 | 2022-06-07 | 四川兴晟锂业有限责任公司 | Treatment process and equipment for potassium-rich mother liquor of lithium hydroxide production system |
| US20220324793A1 (en) * | 2021-03-25 | 2022-10-13 | Hubei Grand Life Science And Technology Co., Ltd. | System and method for efficiently preparing taurine |
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2019
- 2019-10-16 CN CN201921737662.1U patent/CN210736624U/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220324793A1 (en) * | 2021-03-25 | 2022-10-13 | Hubei Grand Life Science And Technology Co., Ltd. | System and method for efficiently preparing taurine |
| US11840502B2 (en) * | 2021-03-25 | 2023-12-12 | Hubei Grand Life Science And Technology Co., Ltd. | System and method for efficiently preparing taurine |
| CN114315657A (en) * | 2021-12-24 | 2022-04-12 | 潜江永安药业股份有限公司 | Method for recycling taurine mother liquor |
| CN114315657B (en) * | 2021-12-24 | 2023-09-29 | 潜江永安药业股份有限公司 | Method for recycling taurine mother liquor |
| CN114590826A (en) * | 2022-04-18 | 2022-06-07 | 四川兴晟锂业有限责任公司 | Treatment process and equipment for potassium-rich mother liquor of lithium hydroxide production system |
| CN114590826B (en) * | 2022-04-18 | 2023-07-18 | 四川兴晟锂业有限责任公司 | Treatment process and equipment for potassium-rich mother liquor of lithium hydroxide production system |
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