CN105503579A - Method for recovering succinic acid from succinic acid crystallization mother liquor containing high-concentration inorganic salt through complex extraction - Google Patents
Method for recovering succinic acid from succinic acid crystallization mother liquor containing high-concentration inorganic salt through complex extraction Download PDFInfo
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 365
- 238000000605 extraction Methods 0.000 title claims abstract description 201
- 239000001384 succinic acid Substances 0.000 title claims abstract description 179
- 238000002425 crystallisation Methods 0.000 title claims abstract description 78
- 230000008025 crystallization Effects 0.000 title claims abstract description 78
- 239000012452 mother liquor Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910017053 inorganic salt Inorganic materials 0.000 title claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 15
- 238000000638 solvent extraction Methods 0.000 claims abstract description 15
- 230000000536 complexating effect Effects 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- 238000000855 fermentation Methods 0.000 claims description 9
- 230000004151 fermentation Effects 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- 235000011147 magnesium chloride Nutrition 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 6
- 238000010170 biological method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005862 Whey Substances 0.000 description 1
- 102000007544 Whey Proteins Human genes 0.000 description 1
- 108010046377 Whey Proteins Proteins 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- YYKMWSWVPKLVQY-UHFFFAOYSA-K [Cl-].[Na+].[Cl-].[K+].S(=O)(=O)([O-])O.[K+] Chemical compound [Cl-].[Na+].[Cl-].[K+].S(=O)(=O)([O-])O.[K+] YYKMWSWVPKLVQY-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recovering succinic acid by complexing extraction from succinic acid crystallization mother liquor containing high-concentration inorganic salt, which takes tributyl phosphate as a complexing extraction agent to carry out liquid-liquid extraction with the succinic acid crystallization mother liquor containing high-concentration inorganic salt, and after two phases are separated by layers, the extraction phase is subjected to back extraction with a back extraction agent; and concentrating, decoloring, cooling and crystallizing the succinic acid aqueous solution obtained by back extraction to obtain a succinic acid finished product, and returning the tributyl phosphate subjected to back extraction to an extraction working section to realize recycling. Compared with the prior art, the method has the advantages of simple extraction and back extraction processes, high succinic acid recovery rate, recoverable high-concentration inorganic salt in the raffinate phase and the like, and the separation effect is not influenced by the type and concentration of the salt in the feed liquid.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for recovering succinic acid from succinic acid crystallization mother liquor containing high-concentration inorganic salt through complexation extraction.
Background
Succinic acid (succinic acid) is an important four-carbon dicarboxylic acid platform compound and is used as a raw material in the production of foods, medicines and fine chemicals, and poly (butylene succinate) (PBS) synthesized by taking succinic acid as a precursor belongs to completely biodegradable plastics, and has excellent mechanical properties and heat resistance and is widely concerned. According to statistics, the global yield of the succinic acid is over 2 ten thousand tons at present, the worldwide demand of the succinic acid is expected to reach dozens of ten thousand tons, and the succinic acid has great market potential. Some strict anaerobes and facultative anaerobesThe succinic acid can be synthesized by fermenting with various saccharides (corn, cassava, molasses, waste whey, agricultural straw, etc.), and the microorganism needs to absorb a large amount of greenhouse gas CO in the process2For metabolism of the strains, lmol CO is theoretically consumed per lmol succinic acid produced2The method not only reduces the dependence on fossil resources, but also reduces the emission of greenhouse gases, so that the biological method for preparing the succinic acid becomes a global research hotspot. At present, the work of preparing succinic acid by a domestic and foreign biological method enters a pilot-scale or pilot-scale production stage, but the improvement of the production efficiency and the reduction of the preparation cost are the keys for realizing the large-scale industrial production of the bio-based succinic acid, and the chemical synthesis method can be replaced gradually.
The succinic acid fermentation liquor prepared by the biological method contains various impurities such as cells, residual sugars, proteins, pigments, byproduct organic heteropolyacid, inorganic salts and the like, so the extraction difficulty of the biological succinic acid is far higher than that of the chemical succinic acid, and the separation cost of the biological succinic acid is more than 50% of the total production cost (ApplMicrobiol Biotechnol.2012,95: 841-850.), so that the development of an efficient succinic acid separation technology is important for realizing the industrialization of the biological succinic acid. The succinic acid prepared by the biological method is suitable for biotransformation and synthesis in the environment with the pH value of 6.0-7.2[39]The generated succinic acid is coated with alkaline substance (such as Na)2CO3、NaOH、MgCO3KOH, ammonia, etc.), so that the succinic acid in the fermentation broth exists in the form of salt, and the succinic acid is required to be formed through acidification in separation and extraction and to obtain the product through crystallization. After the crystallization separation, the mother liquid still contains part of succinic acid (20-30 g/L), which is 7-12% of total amount of succinic acid synthesized by microorganisms, and the mother liquid contains high-concentration inorganic salt (about 80-250 g/L), so that the succinic acid in the mother liquid needs to be separated from a large amount of inorganic salt. The electrodialysis method can separate uncharged succinic acid molecules from inorganic salts (US5034105), but the electrodialysis method has high energy consumption and cannot enrich succinic acid molecules. Ion exchange adsorption allows the succinic acid anion to be exchanged onto the resin (CN101348429A), but high concentrations of inorganic anions (e.g., chloride, sulfate) in the crystallization mother liquor are producedGenerates competitive adsorption, and leads the adsorption efficiency of the succinic acid to be rapidly reduced. The complex extraction method is to extract succinic acid from a dilute solution in a complex forming mode, and has high efficiency (bioprocess Eng.2000,22: 477-481), but when a large amount of strong-acid inorganic anions exist in a crystallization mother liquor, the succinic acid can react with a common amine extractant, so that the complexing ability of the extractant on the succinic acid is reduced rapidly, and meanwhile, the binding ability of the complexing extractant and the succinic acid is high, alkali liquor is required to be used as a stripping agent to destroy the complexing action between the succinic acid and the extractant, but a product obtained by the stripping is succinate, and needs to be subjected to acidification treatment, and finally, high-concentration inorganic salt can be generated during crystallization, so that the complex extraction method is not suitable for a system containing high-concentration inorganic salt. Therefore, how to effectively avoid the interference of high-concentration inorganic salt on the extraction of the succinic acid is the key point for recovering the succinic acid crystallization mother liquor.
Therefore, the method for recovering residual succinic acid from the succinic acid crystallization mother liquor containing high-concentration inorganic salt is developed, so that the extraction yield of succinic acid can be improved, high-purity inorganic salt by-products can be obtained, the discharge of high-salt wastewater is reduced, and the method has important values for improving the economy of preparing succinic acid by a biological method and protecting the environment.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel method for recovering succinic acid by complexing and extracting from succinic acid crystallization mother liquor containing high-concentration inorganic salt.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for recovering succinic acid by complexation and extraction from succinic acid crystallization mother liquor containing high-concentration inorganic salt comprises the following steps:
(1) and (3) extraction: taking tributyl phosphate as a complexing extraction agent, and mixing the succinic acid crystallization mother liquor containing high-concentration inorganic salt with the complexing extraction agent according to the weight ratio of 1-5: 1, performing liquid-liquid extraction, splitting phases after the extraction is finished, and taking an extraction item;
(2) regeneration of an extracting agent: and (2) mixing the extraction phase obtained in the step (1) with a stripping agent according to the ratio of 1-10: 1, carrying out back extraction, carrying out phase separation after the back extraction is finished, recycling an organic phase as a complex extractant, obtaining an aqueous phase which is a succinic acid solution, and cooling, crystallizing or concentrating and crystallizing the succinic acid solution to obtain the succinic acid.
In the step (1), the succinic acid crystallization mother liquor containing high-concentration inorganic salt is a crystallization mother liquor obtained after the succinic acid fermentation liquor is subjected to crystallization separation and decoloration treatment in the process of preparing succinic acid by a fermentation method, and the pH value is 1.5-3.0.
In the step (1), the succinic acid crystallization mother liquor containing high-concentration inorganic salt is preferably a crystallization mother liquor formed by pretreating, crystallizing, separating and decoloring succinic acid fermentation liquor prepared by microbial fermentation, and the pH value is 1.5-3.0.
Wherein, the inorganic salt in the succinic acid crystallization mother liquor containing high-concentration inorganic salt is brought by an upstream fermentation step and is not added in the patent process.
Wherein the concentration of succinic acid in the crystallization mother liquor is 15-40 g/L.
The crystallization mother liquor contains inorganic salt which is any one or more of sodium chloride, sodium sulfate, magnesium chloride, magnesium sulfate, potassium chloride, potassium sulfate, ammonium chloride and ammonium sulfate, and the concentration of the inorganic salt is 80-300 g/L.
In the step (1), the liquid-liquid extraction process is single-stage or multi-stage extraction.
In the step (1), the temperature is 10-30 ℃ and the extraction time is 20-60 min in the liquid-liquid extraction process.
In the step (1), the extraction equipment used for the liquid-liquid extraction process is a mixer-settler, an extraction tower or a centrifugal extractor.
In the step (1), when the concentration of the inorganic salt in the raffinate phase is higher than 80g/L, the inorganic salt can be recovered by concentration and crystallization.
In the step (2), the stripping agent is water or succinic acid aqueous solution;
wherein,
in the succinic acid aqueous solution, the concentration of succinic acid is less than 3 g/L;
before back extraction, both a back extractant and an extract phase are preheated to 80-90 ℃.
In the step (2), the back extraction process is multi-stage back extraction, and preferably 4 stages;
wherein,
after each stage of back extraction, collecting an organic phase for next stage of back extraction, and collecting a water phase, namely a succinic acid aqueous solution; and (3) recycling an organic phase obtained by the last stage of back extraction as a complexing extraction agent, collecting and summarizing aqueous phases obtained at all stages, namely a succinic acid aqueous solution, and cooling, crystallizing or concentrating and crystallizing the succinic acid aqueous solution to obtain the succinic acid.
In the step (2), the back extraction temperature is 80-100 ℃, and the back extraction time is 20-60 min.
In the step (2), the extraction equipment used for carrying out the back extraction process is a mixer-settler, an extraction tower or a centrifugal extractor.
Has the advantages that: compared with the prior art:
1. the extraction-back extraction mode can realize the separation of residual succinic acid and high-concentration inorganic salt in the separation mother liquor after the crystallization of the inorganic salt with high concentration, the extraction and back extraction recovery rates of the succinic acid are both more than 90 percent, and the extraction yield of the succinic acid is obviously improved.
2. Compared with the amine extractant reported in domestic and foreign documents at present, the extraction efficiency is hardly interfered by the type and concentration of inorganic salt, and even if the concentration of the inorganic salt in the crystallization mother liquor reaches 300g/L, the extraction recovery rate of the succinic acid still reaches more than 90 percent, and higher separation efficiency can be maintained. Hot water is used as a stripping agent, so that succinic acid can be stripped, chemical agents are not needed, no waste water is discharged, the operation is simple and convenient, and the cost is low.
3. The raffinate phase formed by extracting the succinic acid crystallization mother liquor containing high-concentration inorganic salt can obtain inorganic salt as a byproduct through concentration and crystallization, not only can obtain certain economic value, but also avoids the discharge of a large amount of high-difficulty salt-containing wastewater, reduces the treatment cost, and is environment-friendly.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1:
in the embodiment, succinic acid crystallization mother liquor containing high-concentration sodium chloride, potassium chloride and potassium sulfate is respectively used as a raw material, wherein 32g/L of succinic acid, the concentrations of the sodium chloride, the potassium chloride and the potassium sulfate are respectively 156, 140 and 95g/L, the pH value is 1.8, tributyl phosphate and an amine complex extracting agent (the volume ratio of trioctylamine to n-octanol is 3: 7) are respectively used for extraction, and the specific extraction and recovery method is carried out according to the following steps.
(1) Performing two-stage liquid-liquid extraction on the succinic acid crystallization mother liquor and an extracting agent by adopting a mixer-settler at 25 ℃, wherein the extraction time of each stage is 40min, and the volume ratio is 1: 1, respectively collecting an extract phase and a raffinate phase after extraction is finished.
(2) Respectively preheating the extraction phase obtained in the step (1) and hot water to 90 ℃, and adding the extraction phase and the hot water into a mixer-settler for three-stage back extraction. The back extraction temperature of each stage is 90 ℃, and the volume ratio of the extraction phase to the hot water is 1: and 2, stirring and mixing for 30min, and collecting a lower-layer water phase formed after each stage of heat preservation and layering.
In this example, the extraction yield of succinic acid is the ratio of the succinic acid obtained by extraction to the initial succinic acid content in the mother liquid of the crystal. The succinic acid back extraction yield refers to the ratio of the succinic acid obtained by back extraction to the initial succinic acid content in the crystallization mother liquor. The results are shown in Table 1.
TABLE 1
| Kind of inorganic salt | Sodium chloride | Potassium chloride | Potassium sulfate |
| Extraction yield (%) of succinic acid from tributyl phosphate | 99.5 | 97.8 | 96.8 |
| Extraction yield (%) of succinic acid by amine complex extractant | 18.0 | 16.6 | 15.3 |
| Hot Water Back extraction yield (%) | 91.3 | 89.5 | 90.4 |
| Hot water back extraction yield (%) | 7.2 | 8.3 | 7.7 |
The amine complex extractant is seriously interfered by high-concentration inorganic salt, the extraction efficiency of tributyl phosphate exceeds 95 percent, the back extraction efficiency of the amine complex extractant is extremely low when hot water is used for back extraction of an organic phase, and the back extraction yield of the tributyl phosphate reaches about 90 percent, so that the method is suitable for recovering succinic acid from the crystallization mother liquor with high salt concentration.
Example 2:
in the embodiment, succinic acid crystal mother liquor containing high-concentration sodium sulfate is used as a raw material, wherein succinic acid is 26g/L, sodium sulfate is 84g/L, and the pH value is 2.5.
(1) Carrying out single-stage liquid-liquid extraction on the succinic acid crystallization mother liquor and fresh or recovered tributyl phosphate at 30 ℃ by adopting a mixing clarifier, wherein the extraction time is 60min, and the volume ratio is 1: 1 (500 mL each batch), and collecting the extract phase and the raffinate phase after the extraction is finished.
(2) Preheating the extraction phase and hot water obtained in the step (1) to 95 ℃ respectively, and adding the extraction phase and the hot water into a mixer-settler for four-stage back extraction (500 mL of extraction phase is processed in each batch). The back extraction temperature of each stage is 95 ℃, the stirring and mixing time is 40min, wherein the volume ratio of the extraction phase to the hot water of the back extraction of the first three stages is 2: 1, the volume ratio of the extraction phase of the fourth stage back extraction to the hot water is 1: and 1.5, collecting a lower-layer water phase formed after each stage of back extraction, heat preservation and layering, and taking an organic phase obtained after the third stage of back extraction as an extracting agent for circularly extracting fresh succinic acid crystallization mother liquor.
(3) And (3) decoloring the water phase obtained by the two-stage back extraction in the step (2) by 0.2% of activated carbon, concentrating the water phase until the concentration of succinic acid reaches 300g/L, and cooling and crystallizing to obtain succinic acid crystals. And the water phase obtained by the third stage back extraction is recycled as a back extractant.
In this example, the extraction yield of succinic acid is the mass ratio of the extracted succinic acid to the initial succinic acid in the mother liquid of the crystallization. The succinic acid back extraction yield refers to the mass ratio of the succinic acid obtained by back extraction to the succinic acid obtained by extraction. The recovery rate of the succinic acid in the mother liquor refers to the mass ratio of the succinic acid obtained by back extraction to the initial succinic acid in the crystallization mother liquor. The results of the whole extraction and stripping are shown in Table 2.
TABLE 2
| Succinic acid extraction yield (%) | 92.2 |
| Succinic acid back extraction yield (%) | 96.2 |
| Recovery ratio of succinic acid in mother liquor (%) | 88.7 |
| Purity of the resulting succinic acid product (%) | 99.5, meets the quality requirement |
Example 3:
in the embodiment, 120L of succinic acid crystallization mother liquor containing high-concentration ammonium chloride is used as a raw material, wherein 35g/L of succinic acid, 300g/L of ammonium chloride and pH2.0 are adopted, and the specific extraction and recovery method is carried out according to the following steps.
(1) Performing three-stage liquid-liquid extraction on succinic acid crystallization mother liquor and fresh or recovered tributyl phosphate at 30 ℃ by using a centrifugal extractor, and controlling two-phase feeding speeds in each stage of extraction (the crystallization mother liquor is 60L/h, the tributyl phosphate is 30L/h, each crystallization mother liquor is processed by 30L in each batch, and the extraction time is 30 min) to ensure that the volume ratio in contact is 2: 1, respectively collecting an extract phase and a raffinate phase after extraction is finished. Wherein the extract phase obtained by the third-stage extraction is used as an extracting agent for recycling and is used for extracting fresh succinic acid crystallization mother liquor.
(2) Preheating the extraction phase and hot water obtained in the step (1) to 85 ℃, and adding the extraction phase and the hot water into a centrifugal extractor for four-stage back extraction (30L of extraction phase is processed in each batch). The stripping temperature of each stage is 85 ℃, wherein the feeding speeds of the extraction phase and the hot water or the stripping agent of the previous stage of stripping are respectively 30L/h and 10L/h, so that the volume ratio of the contact is 3: 1, the back extraction time is 60 min; the speed of the extraction phase and the hot water of the fourth stage stripping is 30L/h, so that the volume ratio of the extraction phase and the hot water in contact is 1: 1, the back extraction time is 60 min. And collecting a lower water phase formed after each stage of back extraction, heat preservation and layering, and taking an organic phase obtained after the fourth stage of back extraction as an extracting agent for circularly extracting fresh succinic acid crystallization mother liquor. Preheating all solvents to 85 deg.C before back-extraction
(3) And (3) decoloring the water phase obtained by the first three-stage back extraction in the step (2) by using 0.2% of activated carbon, concentrating the water phase until the concentration of succinic acid reaches 300g/L, and cooling and crystallizing to obtain succinic acid crystals. And the water phase obtained by the fourth stage stripping is used as a stripping agent for recycling.
(4) And (3) concentrating and crystallizing the raffinate phase obtained in the step (1) (to 1/6 of the original volume), and cooling and crystallizing to obtain ammonium chloride crystals.
In this example, the extraction yield of succinic acid is the mass ratio of the extracted succinic acid to the initial succinic acid in the mother liquid of the crystallization. The succinic acid back extraction yield refers to the mass ratio of the succinic acid obtained by back extraction to the succinic acid obtained by extraction. The recovery rate of the succinic acid in the mother liquor refers to the mass ratio of the succinic acid obtained by back extraction to the initial succinic acid in the crystallization mother liquor. The recovery rate of ammonium chloride refers to the mass ratio of the ammonium chloride product obtained by final extraction to the initial ammonium chloride in the crystallization mother liquor. The results of the whole extraction and stripping are shown in Table 3.
TABLE 3
Example 4:
in the embodiment, 120L of succinic acid crystallization mother liquor containing high-concentration magnesium sulfate is used as a raw material, wherein 35g/L of succinic acid, 180g/L of magnesium sulfate and pH value are 3.0, and the specific extraction and recovery method is carried out according to the following steps.
(1) The succinic acid crystallization mother liquor and fresh or recycled tributyl phosphate are subjected to two-stage liquid-liquid extraction at 10 ℃ by adopting an extraction tower, and the volume ratio of the succinic acid crystallization mother liquor to the fresh or recycled tributyl phosphate is 1: 1, respectively collecting an extract phase and a raffinate phase after extraction is finished. Wherein the extract phase obtained by the second-stage extraction is used as an extractant for recycling and is used for extracting fresh succinic acid crystallization mother liquor.
(2) Respectively preheating the extraction phase obtained in the step (1) and hot water to 90 ℃, and adding the extraction phase and the hot water into an extraction tower for six-stage back extraction. The stripping temperature of each stage is 100 ℃, the feeding speed ratio of the extraction phase of each stage of stripping to hot water or a stripping agent is 60L/h and 12L/h (the extraction phase of each batch is 30L), and the volume ratio of the extraction phase to the hot water or the stripping agent is 5: 1, the back extraction time is 30 min. And collecting a lower water phase formed after each stage of back extraction, heat preservation and layering, and taking an organic phase obtained after the sixth stage of back extraction as an extracting agent for extracting fresh succinic acid crystallization mother liquor.
(3) And (3) concentrating the water phase obtained by the first three-stage back extraction in the step (2) until the concentration of the succinic acid reaches 300g/L, and cooling and crystallizing to obtain succinic acid crystals. The water phase obtained by the back three-stage back extraction is used as a back extractant for recycling.
(4) And (3) concentrating and crystallizing the raffinate phase obtained in the step (1) (1/5 concentrated to the original volume), and cooling and crystallizing to obtain magnesium sulfate crystals.
In this example, the extraction yield of succinic acid is the mass ratio of the extracted succinic acid to the initial succinic acid in the mother liquid of the crystallization. The succinic acid back extraction yield refers to the mass ratio of the succinic acid obtained by back extraction to the succinic acid obtained by extraction. The recovery rate of the succinic acid in the mother liquor refers to the mass ratio of the succinic acid obtained by back extraction to the initial succinic acid in the crystallization mother liquor. The magnesium sulfate recovery rate refers to the ratio of the magnesium sulfate product obtained in the final extraction to the initial magnesium sulfate content in the crystallization mother liquor. The results of the whole extraction and stripping are shown in Table 4.
TABLE 4
Example 5:
in the embodiment, 120L of succinic acid crystallization mother liquor containing high-concentration magnesium chloride is used as a raw material, wherein the concentration of succinic acid is 24g/L, the concentration of magnesium chloride is 250g/L, and the pH value is 2.2.
(1) Performing four-stage liquid-liquid extraction on the succinic acid crystallization mother liquor and fresh or recovered tributyl phosphate at 10 ℃ by adopting a mixing clarifier, wherein the ratio of the crystallization mother liquor to the tributyl phosphate in each stage of extraction is 5: 1, treating 30L of crystallization mother liquor in each batch, wherein the extraction time is 30min, and collecting an extract phase and a raffinate phase respectively after extraction is finished. Wherein the extract phase obtained by the fourth-stage extraction is used as an extracting agent for recycling and is used for extracting fresh succinic acid crystallization mother liquor.
(2) Respectively preheating the extraction phase and hot water obtained in the step (1) to 80 ℃, and adding the extraction phase and the hot water into a mixer-settler for four-stage back extraction. The stripping temperature of each stage is 100 ℃, and the volume ratio of the extraction phase to the hot water or the stripping agent of each stage is 1: 1 (the extraction phase processed in each batch is 18L), the back extraction time is 35min, the lower aqueous phase formed after the back extraction at each stage is insulated and layered is collected, and the organic phase after the fourth stage back extraction is used as an extractant for extracting fresh succinic acid crystallization mother liquor.
(3) And (3) concentrating the water phase obtained by the first three-stage back extraction in the step (2) until the concentration of the succinic acid reaches 350g/L, and cooling and crystallizing to obtain succinic acid crystals. And the water phase obtained by the fourth stage stripping is recycled as a stripping agent.
(4) And (3) concentrating and crystallizing the raffinate phase obtained in the step (1) (to 1/6 of the original volume), and crystallizing to obtain magnesium chloride crystals.
In this example, the extraction yield of succinic acid is the mass ratio of the extracted succinic acid to the initial succinic acid in the mother liquid of the crystallization. The succinic acid back extraction yield refers to the mass ratio of the succinic acid obtained by back extraction to the succinic acid obtained by extraction. The recovery rate of the succinic acid in the mother liquor refers to the mass ratio of the succinic acid obtained by back extraction to the initial succinic acid in the crystallization mother liquor. The recovery rate of magnesium chloride refers to the ratio of the magnesium chloride product obtained by final extraction to the initial magnesium chloride content in the crystallization mother liquor. The results of the whole extraction and stripping are shown in Table 5.
TABLE 5
Example 6:
in the present example, 80L of succinic acid crystal mother liquor containing high concentration ammonium sulfate was used as a raw material, wherein 15g/L of succinic acid, 170g/L of ammonium sulfate and ph2.0 were used, and the specific extraction and recovery method was performed as follows.
(1) Performing two-stage liquid-liquid extraction on succinic acid crystallization mother liquor and fresh or recovered tributyl phosphate at 30 ℃ by adopting a mixer-settler, wherein the ratio of the crystallization mother liquor to the tributyl phosphate is 1: 1, treating 20L of crystallization mother liquor each time, wherein the extraction time is 20min, and collecting an extraction phase and a raffinate phase respectively after extraction is finished. Wherein the extract phase obtained by the second-stage extraction is used as an extractant for recycling and is used for extracting fresh succinic acid crystallization mother liquor.
(2) Respectively preheating the extraction phase and hot water obtained in the step (1) to 90 ℃, and adding the extraction phase and the hot water into a mixer-settler for three-stage back extraction. The stripping temperature of each stage is 90 ℃, and the volume ratio of the extraction phase to the hot water or the stripping agent of each stage is 1: 1 (the extraction phase processed in each batch is 20L), the back extraction time is 25min, the lower aqueous phase formed after the back extraction at each stage is insulated and layered is collected, and the organic phase after the back extraction at the third stage is used as an extractant for extracting fresh succinic acid crystallization mother liquor.
(3) And (3) concentrating the water phase obtained by the two-stage back extraction in the step (2) until the concentration of the succinic acid reaches 350g/L, and cooling and crystallizing to obtain succinic acid crystals. And the water phase obtained by the third stage of back extraction is recycled as a back extractant.
(4) And (3) concentrating and crystallizing the raffinate phase obtained in the step (1) (to 1/10 of the original volume), and crystallizing to obtain ammonium sulfate crystals.
In this example, the extraction yield of succinic acid is the mass ratio of the extracted succinic acid to the initial succinic acid in the mother liquid of the crystallization. The succinic acid back extraction yield refers to the mass ratio of the succinic acid obtained by back extraction to the succinic acid obtained by extraction. The recovery rate of the succinic acid in the mother liquor refers to the mass ratio of the succinic acid obtained by back extraction to the initial succinic acid in the crystallization mother liquor. The recovery rate of ammonium sulfate refers to the ratio of the ammonium sulfate product obtained by final extraction to the initial ammonium sulfate content in the crystallization mother liquor. The results of the whole extraction and stripping are shown in Table 6.
TABLE 6
Claims (9)
1. A method for recovering succinic acid by complexing and extracting from succinic acid crystallization mother liquor containing high-concentration inorganic salt is characterized by comprising the following steps:
(1) and (3) extraction: taking tributyl phosphate as a complexing extraction agent, and mixing the succinic acid crystallization mother liquor containing high-concentration inorganic salt with the complexing extraction agent according to the weight ratio of 1-5: 1, performing liquid-liquid extraction, splitting phases after the extraction is finished, and taking an extraction phase;
(2) regeneration of an extracting agent: and (2) mixing the extraction phase obtained in the step (1) with a stripping agent according to the ratio of 1-10: 1, carrying out back extraction, carrying out phase separation after the back extraction is finished, recycling an organic phase as a complex extractant, obtaining an aqueous phase which is a succinic acid solution, and concentrating, decolorizing, cooling and crystallizing the succinic acid solution to obtain succinic acid.
2. The method according to claim 1, wherein in the step (1), the succinic acid crystallization mother liquor containing high-concentration inorganic salts is a crystallization mother liquor obtained after the succinic acid fermentation liquor is subjected to crystallization separation and decoloration treatment in the process of preparing succinic acid by a fermentation method, and the pH value is 1.5-3.0;
wherein the concentration of succinic acid in the crystallization mother liquor is 15-40 g/L;
the crystallization mother liquor contains inorganic salt which is any one or more of sodium chloride, sodium sulfate, magnesium chloride, magnesium sulfate, potassium chloride, potassium sulfate, ammonium chloride and ammonium sulfate, and the concentration of the inorganic salt is 80-300 g/L.
3. The method of claim 1, wherein in step (1), the liquid-liquid extraction process is a single-stage or multi-stage extraction.
4. The method according to claim 1, wherein in the step (1), the temperature is 10-30 ℃ and the extraction time is 20-60 min during the liquid-liquid extraction process.
5. The method of claim 1, wherein in step (1), the liquid-liquid extraction process is carried out using a mixer-settler, an extraction column or a centrifugal extractor.
6. The process according to claim 1, wherein in step (1), the inorganic salt is recovered by concentration crystallization when the concentration of the inorganic salt in the raffinate phase is higher than 80 g/L.
7. The method of claim 1, wherein in step (2), the stripping agent is water or an aqueous solution of succinic acid;
wherein,
in the succinic acid aqueous solution, the concentration of succinic acid is less than 3 g/L;
before back extraction, both a back extractant and an extract phase are preheated to 80-90 ℃.
8. The method according to claim 1, wherein in the step (2), the stripping process is multi-stage stripping; wherein the back extraction temperature is 80-100 ℃, and the back extraction time is 20-60 min.
9. The method according to claim 1, wherein in the step (2), the extraction equipment used for carrying out the back extraction process is a mixer-settler, an extraction tower or a centrifugal extractor.
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