CN107739314B - Glycine mother liquor decoloring method - Google Patents
Glycine mother liquor decoloring method Download PDFInfo
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- CN107739314B CN107739314B CN201711002933.4A CN201711002933A CN107739314B CN 107739314 B CN107739314 B CN 107739314B CN 201711002933 A CN201711002933 A CN 201711002933A CN 107739314 B CN107739314 B CN 107739314B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
Abstract
The invention provides a glycine mother liquor decoloring method, which comprises the following steps: 1) allowing the glycine production mother liquor subjected to cooling crystallization and centrifugation to pass through a fixed bed adsorption column of a styrene-divinylbenzene adsorption material at a flow rate of 1-1.5 BV/h to obtain a decolorized glycine production mother liquor; 2) leaching the fixed bed adsorption column by using 1-2BV of soft water; wherein, the conductivity of the used soft water is less than or equal to 5 micro siemens/cm < 3 >) the residual soft water in the fixed bed adsorption column is drained by using 0.2Mpa net-surfing compressed nitrogen; 4) regenerating the adsorption material in the fixed bed adsorption column by using an organic solvent; 5) and (4) repeating the steps 1) to 4) until all the glycine production mother liquor is decolorized. The method adopts a reproducible styrene-divinylbenzene adsorbing material to realize the decolorization of the glycine production mother liquor. The system has the advantages of simple structure, easy operation, convenient maintenance, safe and reliable operation and good treatment effect, can eliminate secondary pollution, brings considerable economic benefit and reduces the environmental protection pressure of a plant area.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a glycine mother liquor decoloring method.
Background
Glycine is one of the 20 members of the amino acid series, has the simplest structure, is also called aminoacetic acid, is an amino acid which is not necessary for human bodies, has both acidic and basic functional groups in molecules, is a strong electrolyte in aqueous solution, has higher solubility in a strong polar solvent, is basically insoluble in a non-polar solvent, and has higher boiling point and melting point, and can be made to present different molecular forms by adjusting the acidity and the basicity of the aqueous solution. The side bond of glycine is a hydrogen atom. Glycine is not optically isomeric because it has one hydrogen atom in the alpha carbon. Since the side bond of glycine is very small, it can occupy space that other amino acids cannot occupy, for example, as an amino acid in a collagen helix. White crystals or light yellow crystalline powder at normal temperature. Has unique sweet taste, and can alleviate acid and alkaline taste, mask bitter taste of saccharin in food, and enhance sweet taste. If the glycine is taken into a human body in an excessive amount, the glycine cannot be absorbed and utilized by the human body, and the absorption balance of the human body on amino acid is broken to influence the absorption of other amino acid, so that the nutrition imbalance is caused to influence the health. The milk-containing beverage produced by using glycine as a main raw material easily brings adverse effects on the normal growth and development of teenagers and children. Density 1.1607. The melting point is 232-236 ℃ (decomposition). Soluble in water and insoluble in ethanol and diethyl ether. Can react with hydrochloric acid to form hydrochloride. Is present in the muscle of lower animals. Can be prepared by reacting monochloroacetic acid with ammonium hydroxide, or by hydrolyzing gelatin and refining.
In the refining process of glycine, decolorization is the most critical step for ensuring the product to be qualified, and the whiteness of glycine crystals directly depends on the decolorization effect. The decoloration of the traditional active carbon of the common adoption in the decoloration trade of present glycine, the decoloration effect can satisfy the product requirement reluctantly, but because the active carbon is disposable absorption can not the desorption, lead to the high in production cost of enterprise, the active carbon country of adsorbed pigment has been turned into danger useless in addition, the economy and the environmental protection pressure of enterprise have been increased, a big difficult problem that has become the puzzlement enterprise, the enterprise can pass through conventional incineration disposal in early stage, along with the country increases the regulatory dynamics to the flue gas improvement in recent years, the coal fired boiler of enterprise is basically banned entirely, useless active carbon can only be regarded as the useless processing of danger, and workshop workman's operating environment is comparatively poor.
Disclosure of Invention
The invention aims to provide a glycine mother liquor decoloring method, which adopts a reproducible styrene-divinylbenzene adsorbing material to realize the decoloring of glycine production mother liquor, reduces the generation of solid wastes, and is beneficial to environmental protection and the reduction of enterprise production cost.
The invention is realized by the following technical scheme:
a method for decoloring glycine mother liquor comprises the following steps:
1) allowing the glycine production mother liquor subjected to cooling crystallization and centrifugation to pass through a fixed bed adsorption column of a styrene-divinylbenzene adsorption material at a flow rate of 1-1.5 BV/h to obtain a decolorized glycine production mother liquor;
2) draining glycine mother liquor in an adsorption column of the fixed bed by using inert gas, and replacing residual mother liquor by soft water;
3) discharging the mixed feed liquid of the residual soft water and the mother liquid after replacement in the fixed bed adsorption column by using inert gas;
4) regenerating the adsorption material in the fixed bed adsorption column by using an organic solvent;
5) draining the organic solvent in the fixed bed adsorption column by using inert gas, and replacing the residual organic solvent by soft water;
6) and (4) repeating the steps 1) to 5) by using the fixed bed adsorption column after the soft water replacement in the step 5) until all the glycine production mother liquor is decolorized.
Preferably, in the step 1), the volume of the glycine production mother liquor treated by the fixed bed adsorption column is 75-100 BV.
Preferably, the inert gas is nitrogen. Compressed nitrogen was used to drain the fixed bed adsorption column.
Preferably, in step 2), the mother liquor from which the soft water is replaced is used as the raw material dissolved water to prepare the mother liquor.
Preferably, the step 4) specifically comprises the steps of:
4-1) desorbing and regenerating the styrene-divinylbenzene adsorbing material in the fixed bed adsorption column by using an organic solvent;
4-2) using compressed nitrogen to drain residual organic solvent in the fixed bed adsorption column;
4-3) leaching the fixed bed adsorption column by using soft water until the content of the organic solvent in the leaching solution is less than 0.1%.
Preferably, in the step 4-1), the organic solvent is one or more of methanol, ethanol and isopropanol.
Preferably, in the step 4-1), the amount of the organic solvent is 1-2 BV; the desorption flow rate is 0.5-0.75 BV/h.
Preferably, in step 4-1), the desorption solution is collected and the organic solvent is recovered by rectification.
Preferably, the technical indexes of the styrene-divinylbenzene absorbing material are shown in the following table:
compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a glycine mother liquor decoloring method, which selects a macroporous styrene-divinylbenzene adsorbing material which is used for pertinently adsorbing organic pigments in the mother liquor and basically does not adsorb or hardly adsorbs glycine in the glycine mother liquor; the treatment method has the advantages of easy operation, convenient maintenance, safe and reliable operation and good treatment effect, can bring considerable economic benefit to a plant area, and greatly reduces the environmental protection pressure of the plant area.
Furthermore, the conductivity requirement of soft water used for replacing the glycine mother liquor is less than or equal to 5 micro siemens/cm, and the replaced mixed feed liquid can be used as the soft water for producing dissolved materials, so that the material loss is reduced, and the production of production wastewater is avoided.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention aims to provide a glycine mother liquor decoloring method, which replaces the traditional activated carbon decoloring process, reduces the labor intensity, improves the production efficiency of enterprises, reduces the production cost of the enterprises and relieves the environmental protection pressure of plant areas.
A method for decoloring glycine mother liquor, which basically comprises the following steps:
step 1, passing the glycine production mother liquor after cooling crystallization and centrifugation through a fixed bed adsorption column of a styrene-divinylbenzene adsorption material under the condition that the flow rate is 1-1.5 BV/h (BV is the volume of the adsorption material in the fixed bed, namely the bed volume or the column volume), wherein the adsorption material is used for pertinently adsorbing organic pigments in the mother liquor, basically not adsorbing or hardly adsorbing glycine in the mother liquor, and directly pumping the glycine through the column back to the front end for continuous material dissolution.
When the flow rate of the column passing is controlled to be 1-1.5 BV/h, 1BV of adsorbing material can treat 100BV of glycine mother liquor, and the light transmittance of the column passing liquor meets the technical requirements of a plant area; when the flow rate of the column is controlled at 1.5BV/h, 1BV can process 75BV of glycine mother liquor. Therefore, experimental data show that the column flow rate has great influence on the decoloring effect of the glycine mother liquor.
In order to further explore suitable adsorbents, the present invention has been extensively screened and several experiments of adsorbents are presented for illustration.
LS-106, LS-200 and LS-109D are selected, three adsorbing materials are used for carrying out an adsorption decoloration experiment on the glycine production mother liquor, wherein the LS-109D adsorbing material has the best effect, the transmittance of column passing liquid of the other two adsorbing materials and the repeatability of experimental data are obviously lower than those of the LS-109D, and the results are shown in table 1:
table 1: results after treatment of different volumes of mother liquor with adsorbent materials
Experimental data show that the LS-109D adsorbing material has the best decolorizing effect on glycine mother liquor, and the adsorbing performance of the adsorbing material is well recovered after regeneration.
After the adsorbing materials are screened out, the further comparison is carried out through experiments and activated carbon decoloration, and the experimental data are shown in the table 2:
TABLE 2
Based on such criteria, the LS-109D adsorbent material was finally selected.
Step 2, replacing the glycine mother liquor by using soft water on the styrene-divinylbenzene adsorbing material for adsorbing the organic pigment, removing the residual mother liquor in the pore passage of the adsorbing material, and collecting the replacement mother liquor for subsequent burdening;
step 3, draining the residual displacement mother liquor in the fixed bed adsorption column in the step 2 by using compressed nitrogen of 0.2 Mpa;
and 4, desorbing and regenerating the adsorbing material in the fixed bed adsorption column by using 1-2BV of organic solvent, wherein the desorption flow rate is 0.5-0.75 BV/h, collecting the desorption solution, rectifying to recover the organic solvent, and treating the rectified kettle residue after solidification.
The inventor finds in experiments that reducing the desorption flow rate can improve the desorption effect and reduce the use amount of the organic solvent. The whole cost is lowest, and the desorption effect is optimal.
In application, the organic solvent may be selected according to the existing plant and is not limited to one or more of methanol, ethanol and isopropanol.
And 5, draining the residual organic solvent in the adsorption material desorbed in the step 4 by using 0.2Mpa compressed nitrogen, and collecting the discharged desorption solution together and returning to the rectification for recovering the solvent.
And 6, leaching the adsorption material by using soft water at the temperature of 30-40 ℃, removing the residual organic solvent in the pore channel of the adsorption material, washing until the content of the solvent is less than 0.1%, collecting the soft water for cleaning the organic solvent in batches, recycling the soft water for the next time, and determining rectification treatment according to the concentration of the organic solvent, so that the organic solvent can be effectively recovered, and the operation cost is reduced.
The adsorbing material is a post-crosslinked styrene-divinylbenzene adsorbing material with weak polarity, preferably a blue-dark LS-3 adsorbing material;
the organic solvent in step 5 may be methanol, ethanol, isopropanol, etc.
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the characteristics of the glycine mother liquor, a styrene-divinylbenzene adsorption material is selected, organic pigments in the mother liquor are adsorbed in a targeted manner, the glycine in the glycine mother liquor is not adsorbed or hardly adsorbed, the adsorption material after the organic pigments are adsorbed and saturated is leached by 1-2BV of soft water, washing liquid is recovered for subsequent burdening, and the loss of materials is reduced.
2. The glycine mother liquor passes through a lift pump, a pipeline and a fixed bed adsorption column filled with adsorption materials, and the decolorizing effect can meet the requirement. The glycine mother liquor does not need any pretreatment, does not need to add any chemical agent, has short decoloring time, obvious decoloring effect and few and simple used equipment, and the whole set of system can be automatically controlled by a PLC (programmable logic controller), so that the equipment does not need to be shut down and can carry out production operation for 24 hours.
Example 1:
the decolorization method provided by the invention is subjected to process demonstration in circulating mother liquor of industrial grade and food grade amino acid processing plants in certain glycine industry, the plant area used for the experiment produces the circulating mother liquor, the light transmittance of the mother liquor is 58.9%, the light transmittance of the mother liquor is improved by about 5-7% after decolorization by using activated carbon and a comparison experiment is carried out by using the decolorization method provided by the invention, the light transmittance of the mother liquor is improved by 30-35% after the circulating mother liquor is decolorized by using the adsorption decolorization method provided by the invention, the whiteness of crystals is detected after the decolorized mother liquor is cooled and crystallized, the whiteness of the detected crystals is less than 1.2, the product percent of pass is close to 100%, the decolorization effect exceeds the expected effect of the plant area, and a set of 2 tons/hour of industrial equipment is stably operated.
Example 2:
the decoloring method provided by the invention is used for carrying out process demonstration on the circulating mother liquor of a feed-grade glycine processing plant in a certain glycine industry, the plant area used in the experiment produces the circulating mother liquor, the light transmittance of the mother liquor is 22%, the activated carbon basically has no decoloring effect, the mother liquor plant area is subjected to waste, evaporation and biochemical treatment, and the material loss in the production process is serious. Experiments prove that the decolorized mother liquor has the light transmittance of more than 85 percent and can directly enter a mother liquor circulating system, the circulating mother liquor does not need to be subjected to waste evaporation treatment after circulating for a period of time, the material loss of a plant area is greatly reduced, evaporation and biochemical cost is saved, and the environmental protection pressure is reduced while considerable economic benefits are brought to the plant area. The decoloring system and the decoloring method have the advantages of good separation effect, small system floor area, simple operation, reliable operation, convenient maintenance, continuous 24-hour operation and great improvement on production efficiency.
Example 3:
the decolorization method provided by the invention is experimentally demonstrated in the circulating mother liquor of industrial glycine processing plants in certain glycine industry, the test is compared with the decolorization of active carbon currently used in a plant area, the comparison test is carried out on the decolorization effect, the decolorization period, the crystal whiteness and the glycine material loss condition of the circulating mother liquor one by one, the plant area detection data are shown in a table 2, and from the plant area detection data, the decolorization system provided by the invention has the technical advantages of high decolorization efficiency, long operation time, stable decolorization effect, less material loss and the like compared with the active carbon. The decoloring system is small in occupied area, simple to operate, stable and reliable in effect, convenient to maintain, capable of continuously operating for 24 hours and greatly improving the production efficiency.
Claims (3)
1. A method for decoloring glycine mother liquor is characterized by comprising the following steps:
1) allowing the glycine production mother liquor subjected to cooling crystallization and centrifugation to pass through a fixed bed adsorption column of a styrene-divinylbenzene adsorption material at a flow rate of 1-1.5 BV/h to obtain a decolorized glycine production mother liquor;
2) draining glycine mother liquor in an adsorption column of the fixed bed by using inert gas, and replacing residual mother liquor by soft water;
3) discharging the mixed feed liquid of the residual soft water and the mother liquid after replacement in the fixed bed adsorption column by using inert gas;
4) regenerating the adsorption material in the fixed bed adsorption column by using an organic solvent, and specifically comprising the following steps of:
4-1) desorbing and regenerating the styrene-divinylbenzene adsorbing material in the fixed bed adsorption column by using an organic solvent, collecting an analytic solution, rectifying and recovering the organic solvent, wherein the organic solvent is one or more of methanol, ethanol and isopropanol, and the dosage of the organic solvent is 1-2 BV; the desorption flow rate is 0.5-0.75 BV/h;
4-2) exhausting residual organic solvent in the fixed bed adsorption column by using inert gas;
4-3) leaching the fixed bed adsorption column by using soft water until the content of the organic solvent in the leacheate is less than 0.1%;
the technical indexes of the styrene-divinylbenzene absorbing material are shown in the following table:
5) draining the organic solvent in the fixed bed adsorption column by using inert gas, and replacing the residual organic solvent by soft water;
6) and (4) repeating the steps 1) to 5) by using the fixed bed adsorption column after the soft water replacement in the step 5) until all the glycine production mother liquor is decolorized.
2. The method for decoloring glycine mother liquor according to claim 1, wherein in the step 1), the volume of the glycine production mother liquor treated by the fixed bed adsorption column is 75 to 100 BV.
3. The method for decoloring glycine mother liquor according to claim 1, wherein in the step 2), the mother liquor displaced by soft water is used as a raw material dissolved water to be returned to the mother liquor.
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| CN107854864A (en) * | 2017-10-24 | 2018-03-30 | 陕西蓝深特种树脂有限公司 | A kind of phenylglycine produces mother liquor decolorizing process technique |
| CN109761754A (en) * | 2019-01-24 | 2019-05-17 | 西安海润新材料有限公司 | A kind of discoloration method of Xylitol mother liquor |
| CN111995694B (en) * | 2020-08-18 | 2022-07-01 | 云南英格生物技术有限公司 | Method for decoloring and purifying polygonatum kingianum polysaccharide |
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| WO2005097734A1 (en) * | 2004-04-07 | 2005-10-20 | Asahi Kasei Chemicals Corporation | Method of purifying amino acid |
| CN1785990A (en) * | 2005-11-22 | 2006-06-14 | 三达膜科技（厦门）有限公司 | Method of preparing tea polyphenol by resin adsorption method |
| CN101863783A (en) * | 2010-06-22 | 2010-10-20 | 华东理工大学 | Method for separating and purifying gamma-aminobutyric acid (GABA) from glutamine decarboxylase enzymolysis liquid |
| CN103058877A (en) * | 2013-01-15 | 2013-04-24 | 华东理工大学 | Method for separating gamma-aminobutyric acid and glutamic acid by colour spectrum |
| CN103274954A (en) * | 2013-05-22 | 2013-09-04 | 厦门世达膜科技有限公司 | Production process of Gly |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005097734A1 (en) * | 2004-04-07 | 2005-10-20 | Asahi Kasei Chemicals Corporation | Method of purifying amino acid |
| CN1785990A (en) * | 2005-11-22 | 2006-06-14 | 三达膜科技（厦门）有限公司 | Method of preparing tea polyphenol by resin adsorption method |
| CN101863783A (en) * | 2010-06-22 | 2010-10-20 | 华东理工大学 | Method for separating and purifying gamma-aminobutyric acid (GABA) from glutamine decarboxylase enzymolysis liquid |
| CN103058877A (en) * | 2013-01-15 | 2013-04-24 | 华东理工大学 | Method for separating gamma-aminobutyric acid and glutamic acid by colour spectrum |
| CN103274954A (en) * | 2013-05-22 | 2013-09-04 | 厦门世达膜科技有限公司 | Production process of Gly |
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