CN115612559A - Treatment method of glycerin residue - Google Patents
Treatment method of glycerin residue Download PDFInfo
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- CN115612559A CN115612559A CN202211020015.5A CN202211020015A CN115612559A CN 115612559 A CN115612559 A CN 115612559A CN 202211020015 A CN202211020015 A CN 202211020015A CN 115612559 A CN115612559 A CN 115612559A
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- glycerin
- salt
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 238000000034 method Methods 0.000 title claims abstract description 92
- 150000003839 salts Chemical class 0.000 claims abstract description 124
- 235000011187 glycerol Nutrition 0.000 claims abstract description 68
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 49
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000007790 solid phase Substances 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 238000004821 distillation Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 18
- 239000004519 grease Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 28
- 239000011777 magnesium Substances 0.000 description 26
- 238000012812 general test Methods 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 16
- 238000009616 inductively coupled plasma Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000010561 standard procedure Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 238000011033 desalting Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- -1 fatty acid salt Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a treatment method of glycerin residue. A method for treating glycerin residues comprises the following steps: 1) Mixing an extracting agent and the glycerol residue to obtain a liquid-phase and solid-phase layered mixture; 2) Separating the liquid phase and solid phase layered mixture to obtain a crude salt solid phase and a crude glycerin liquid phase; 3) The crude salt solid phase is subjected to pyrolysis, dissolution, filtration and evaporation in sequence to obtain a refined salt product; and purifying the crude glycerin liquid phase to obtain purified glycerin and an extracting agent. The treatment method can carry out resource utilization on the byproduct glycerol residues in the grease industry, the obtained products are glycerol and refined salt, the purity of the glycerol product can reach more than 90%, and the sodium chloride content in the refined salt product can reach 99%.
Description
Technical Field
The invention relates to the technical field of solid waste resource utilization, in particular to a treatment method of glycerin residues.
Background
In the production process of grease chemical industry, the processes of grease hydrolysis, saponification and the like can obtain products such as fatty acid, fatty acid salt, soap granules and the like, and also have about 10wt% of glycerol sweet water. The sweet water of glycerol is further treated by evaporation, decoloration and distillation to obtain a large amount of glycerol residue. When the glycerin is purified in the glycerin refining industry, hydrochloric acid is added for acidification and oil removal, and excessive sodium hydroxide is added in the subsequent process, so that the residue contains a large amount of glycerin and sodium chloride, and the recycling value is high. Glycerol is a colorless, sweet and sticky liquid, has high calorific value and excellent solubility and wettability, and is widely applied to the fields of chemical industry, medicines, foods, cosmetics and the like. The glycerol residue can be recycled to obtain sodium chloride, and industrial salt is prepared by the sodium chloride, a large amount of sodium chloride is needed in the organic synthesis industry, and in addition, the main products of the basic chemical industry, such as hydrochloric acid, caustic soda, calcined soda, ammonium chloride, chlorine and the like, are mainly prepared by taking the industrial salt as a raw material.
Patent CN209173398U discloses a glycerin residue desalting system, which adopts a thin film evaporator, a centrifuge, a residue distillation tank and other equipment to evaporate and recover glycerin and carry out centrifugal desalting, so that the production amount of glycerin residue can be reduced, but the yield of glycerin, the glycerin purity and the salt purity are improved in a limited way, the process is complex, and the energy consumption is large.
The glycerin residue belongs to hazardous waste HW08, and most of the oil industry submits the glycerin residue to a hazardous waste disposal unit for disposal. The hazardous waste disposal unit carries out incineration disposal on the solid and semi-solid glycerol residues, the incineration cost is higher, and the treatment cost is about 3500-5000 yuan/ton. The glycerol resource utilization mostly adopts a direct distillation method, the comprehensive utilization rate is low, the yield of the glycerol product recovered from the glycerol resource utilization is low, the side reactions are more, and the sodium chloride in the glycerol residue is not recycled.
Disclosure of Invention
In order to solve the problem that the glycerol residue in the prior art cannot be effectively utilized, the invention aims to provide a treatment method of the glycerol residue.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a treatment method of glycerin residues comprises the following steps:
1) Mixing an extracting agent and the glycerol residues to obtain a liquid-phase and solid-phase layered mixture;
2) Separating the liquid phase and solid phase layered mixture to obtain a crude salt solid phase and a crude glycerin liquid phase;
3) The crude salt solid phase is subjected to pyrolysis, dissolution, filtration and evaporation in sequence to obtain a refined salt product; and purifying the crude glycerin liquid phase to obtain purified glycerin and an extracting agent.
The glycerin residue is generated in the palm oil hydrolysis process, and the residue obtained after the glycerin sweet water is subjected to purification, evaporation, bleaching, desalting, distillation and compression is black or brown viscous liquid or semisolid, is alkaline (pH = 13), and contains a large amount of glycerin, naCl, a small amount of sodium aliphatate, naOH and Ca (OH) 2 、CaCl 2 And the like. The glycerol residues of different processes are different, and the invention aims at the glycerol residues generated in the glycerol refining industry.
Preferably, in the method for treating glycerin residue, in step 1), the extractant comprises at least one of methanol, ethanol and ethyl acetate; further preferably, the extractant is at least one of methanol and ethanol; still further preferably, the extractant is methanol; one or more of methanol, ethanol and ethyl acetate are used as the extracting agent, so that the method is low in price and excellent in purification effect, the extracting agent can be recycled, and the recovery rate of the extracting agent can reach more than 88%.
Preferably, in the method for treating the glycerin residue, the volume mass ratio of the extracting agent to the glycerin residue is 1mL: (1.5-2.5) g; within the range, the separation effect of the salt and the glycerol is good, the purity of the prepared refined salt is high, and the product recovery rate is high.
Preferably, in the method for treating the glycerin residue, in the step 1), the extractant and the glycerin residue are mixed and then stirred, and a magnetic stirring mode can be adopted; further preferably, the stirring time is 5-15min; still more preferably, the stirring time is 8-12min; more preferably, the stirring time is 10min.
Preferably, in the step 2), the separation is performed by suction filtration.
Preferably, the glycerol residue is treated by the method, in the step 3), the pyrolysis temperature is 400-600 ℃; further preferably, the heating rate of pyrolysis is 10-20 ℃/min, and the final temperature is 400-600 ℃.
Preferably, in the step 3), the pyrolysis time is 1.5-2.5h; further preferably, the pyrolysis time is 2h.
Preferably, in the method for treating glycerin residue, in step 3), the pyrolyzed crude salt solid phase is dissolved by water, and then filtered, and the filtrate obtained by filtering is evaporated to obtain a refined salt product.
Preferably, in the step 3), the evaporation temperature is 100-110 ℃, the filtered filtrate is dried at 100-110 ℃, and high-temperature steam is generated in the evaporation process to obtain a refined salt product.
Preferably, the glycerol residue is treated by a method comprising, in step 3), purifying by distillation; further preferably, the distillation is atmospheric or vacuum distillation.
Further preferably, in the method for treating the glycerin residue, step 3), the high-temperature pyrolysis gas generated by pyrolysis is used as a heat source for distillation.
Further preferably, in the method for treating glycerin residue, in the step 3), high-temperature steam generated by evaporation is used as a heat source for distillation; high-temperature pyrolysis gas generated by pyrolysis and high-temperature steam generated by evaporation are used as heat sources for distillation, so that heat is recycled, and the production cost is greatly reduced.
Preferably, the step 3) of the method for treating the glycerin residue further comprises a step of measuring the components of a refined salt product; further preferably, the assay comprises Cl - 、Ca 2+ 、Mg 2+ 、SO 4 2- At least one of; cl - The determination refers to the national standard GB/T13025.5-2012 determination of chloride ions in general test method in salt industry, ca 2+ 、Mg 2+ The determination refers to the national standard GB/T13025.6-2012 determination of calcium and magnesium by salt industry general test method, SO 4 2- The determination of (2) is carried out according to the national standard GB/T13025.8-2012 determination of sulfate radical in the general test method of salt manufacturing industry, and the sodium chloride content is calculated according to the standard method of GB/T5462-2015 Industrial salt.
Preferably, in the treatment method of the glycerin residue, in the step 3), the sodium chloride content of the refined salt product is more than or equal to 98.5wt%; the refined salt obtained by the glycerol residue treatment method meets the first-grade standard of refined industrial dry salt in GB/T5462-2015 Industrial salt.
The invention has the beneficial effects that:
(1) The treatment method of the glycerol residue provided by the invention is simple to operate, short in flow, mild in condition, free of three-waste discharge and suitable for industrial production.
(2) The treatment method can carry out resource utilization on the byproduct glycerin residue in the grease industry, and the obtained products are glycerin and refined salt. The glycerol is widely applied to the fields of chemical industry, medicine, food, daily chemicals and the like, the purity of the glycerol product can reach more than 90%, and the content of sodium chloride in the refined salt product can reach 99%.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials or apparatuses used in the examples and comparative examples were obtained from conventional commercial sources or may be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
A method for treating glycerin residues comprises the following steps:
(1) 400mL of methanol was added to 200g of glycerin residue, followed by magnetic stirring and mixing for 10min with magnetons. The resulting mixture was separated into layers, with the lower layer of solids being crude salt and the upper layer being an alcoholic solution of crude glycerol. The mixture was separated by suction filtration and the filtrate was poured back several times to wash the crude salt thoroughly. The salt on the funnel and filter paper was collected and dried in a 105 ℃ oven and weighed to give 122.19g crude salt, the crude salt yield of glycerol residue was 61.10%.
(2) And (4) putting the dried crude salt into a muffle furnace for ash burning, and burning off organic matters remained on the crude salt. The rate of temperature rise was set at 10 ℃/min, the final temperature at 600 ℃ and the duration at 2h, giving an ash of 120.72g. Dissolving ash with pure water, filtering, and recrystallizing in oven at 105 deg.C to obtain refined salt 120.12g with glycerol residue refined salt yield of 60.06%.
(3) The method follows the silver content method in the national standard GB/T13025.5-2012 determination of chloride ions in the general test method of salt manufacturing industry to Cl - And (6) detecting. Taking 10.0456g of refined salt, diluting to a constant volume of 500mL, and calculating to obtain Cl in the refined salt by adopting an automatic titrator - The content was 59.98%. Ca is subjected to a volumetric method in GB/T13025.6-2012' determination of calcium and magnesium in general test method for salt industry 2+ And Mg 2+ And (4) detecting, wherein the result is not detected. In addition, ICP (inductively coupled plasma emission spectrometer) is adopted for Ca 2+ And Mg 2+ Detecting to obtain Ca in refined salt 2+ Content of 0.00108%, mg 2+ The content is 0.00018%. Simultaneous detection of Na in refined salt using ICP + The content was 32.32%. SO is subjected to gravimetric method and volumetric method in national standard GB/T13025.8-2012' determination of sulfate radical in general test method in salt industry 4 2- And (5) detecting, wherein the result is not detected. In addition, ultraviolet spectrophotometry is adopted to measure SO in refined salt 4 2- The content was 1.09%. The NaCl content in the refined salt was calculated following the standard method of GB/T5462-2015 Industrial salt, and the NaCl content was 98.84%. Namely, the mass ratio of the added methanol volume to the glycerol residue is 2:1, which can reach the first-grade standard of national standard refined industrial dry salt.
(4) And (2) collecting the mixture of the glycerol and the methanol in the filter flask in the step (1), and distilling under normal pressure to obtain the purified glycerol with the mass of 45.24g and the yield of 22.62 percent. 350mL of methanol was recovered, and the recovery rate of methanol was 87.5%. The calorific value of the purified glycerol was determined to be 3636.67cal/g. Taking 16.34g of the obtained glycerol, putting the glycerol into a muffle furnace, and burning ash, wherein the heating rate is 10 ℃/min, the final temperature is 600 ℃, and the duration is 2h, so that the mass of the ash content of the glycerol is 1.51g, and the ash content is 9.24%. Cl is measured according to the national standard GB/T13025.5-2012 determination of chloride ions in the general test method of salt manufacturing industry - And (6) detecting. Taking part of the glycerol ash 0.4900g, metering the volume to 250mL, and calculating to obtain Cl in the glycerol ash by adopting an automatic titrator - The content was 35.43%, converted to Cl in purified glycerin - The content was 3.27%. Ca is subjected to a volumetric method in GB/T13025.6-2012' determination of calcium and magnesium in general test method for salt industry 2+ And Mg 2+ And (4) detecting, wherein the result is not detected. In addition, ICP is adopted to Ca 2+ And Mg 2+ Detecting to obtain Ca in the glycerin ash 2+ Content of 0.077%, mg 2+ The content is 0.0085%. Conversion to Ca in purified Glycerol 2+ 0.0071% of Mg 2+ The content is 0.0008%. SO is subjected to gravimetric method and volumetric method in national standard GB/T13025.8-2012 determination of sulfate radical in general test method of salt industry 4 2- And (4) detecting, wherein the result is not detected. In addition, ultraviolet spectrophotometry is adopted to measure SO in the purified glycerol 4 2- The content was 1.47%. The NaCl content in the purified glycerol was calculated to be 5.40% following the standard method of GB/T5462-2015 Industrial salt.
Comparative example 1
A treatment method of glycerin residues comprises the following steps:
(1) 200mL of methanol was added to 200g of glycerin residue, followed by magnetic stirring and mixing for 10min with magnetons. The resulting mixture was layered with the lower layer being crude salt solids and the upper layer being crude glycerol alcoholic solution. The mixture was separated by suction filtration and the filtrate was poured back several times to wash the crude salt thoroughly. The salt content on the funnel and filter paper was collected and dried in an oven at 105 ℃ and weighed 121.68g of crude salt, giving a yield of 60.84% for the crude salt of glycerin residue, which was more yellow than in example 1.
(2) And (4) putting the dried crude salt into a muffle furnace for ash burning, and burning off organic matters remained on the crude salt. Setting the heating rate at 10 ℃/min, setting the final temperature at 600 ℃, keeping the temperature for 2h, dissolving the obtained ash by using pure water, filtering, putting the obtained ash into a 105 ℃ oven to evaporate water, and recrystallizing to obtain 120.90g of refined salt, wherein the refined salt yield of the glycerol residue is 60.45%.
(3) The method follows the silver content method in the national standard GB/T13025.5-2012 determination of chloride ions in the general test method of salt manufacturing industry to Cl - And (6) detecting. Taking 10.0771g of refined salt, diluting to a constant volume of 500mL, and calculating to obtain Cl in the refined salt by adopting an automatic titrator - The content was 59.56%. Ca is subjected to a volumetric method in GB/T13025.6-2012' determination of calcium and magnesium in general test method for salt industry 2+ And Mg 2+ And (4) detecting, wherein the result is not detected. In addition, ICP (inductively coupled plasma emission spectrometer) is adopted for Ca 2+ And Mg 2+ Detecting to obtain Ca in refined salt 2+ 0.0012% of Mg 2+ The content is 0.00020%. Simultaneous detection of Na in refined salt using ICP + The content was 33.99%. SO is subjected to gravimetric method and volumetric method in national standard GB/T13025.8-2012' determination of sulfate radical in general test method in salt industry 4 2- And (4) detecting, wherein the result is not detected. In addition, the ultraviolet spectrophotometry is adopted to measure the SO in the refined salt 4 2- The content was 1.51%. The NaCl content in the refined salt is calculated according to the standard method of GB/T5462-2015 Industrial salt, and the obtained NaCl content is 86.45%. Namely, the mass ratio of the volume of the added methanol to the glycerol residue is 1:1, which does not reach the secondary standard of national standard refined industrial dry salt.
(4) And (2) collecting the mixture of the glycerol and the methanol in the filter flask in the step (1), and distilling at normal pressure to obtain 57.16g of glycerol with the mass of 28.58% of the glycerol. 158mL of methanol was recovered, and the recovery of methanol was 79.0%. The calorific value of the purified glycerol was determined to be 3686.59cal/g. Taking part of glycerin, putting into a muffle furnace, burning ash, wherein the heating rate is 10 ℃/min, the final temperature is 600 ℃, and the duration is 2h, so that the ash content is 10.10%. The method follows the national standard GB/T13025.5-2012 determination of chloride ions in general test method in salt industry to Cl - And (6) detecting. Taking 0.5130g of partial glycerin ash, fixing the volume to 250mL, and calculating to obtain Cl in the glycerin ash by adopting an automatic titrator - The content was 42.00%, converted to Cl in purified glycerin - The content was 4.24%. Ca is subjected to a volumetric method in GB/T13025.6-2012' determination of calcium and magnesium in general test method for salt industry 2+ And Mg 2+ And (4) detecting, wherein the result is not detected. In addition, ICP is adopted to Ca 2+ And Mg 2+ Detecting, and converting into purified glycerol containing Ca 2+ The content is 0.0030 percent and Mg 2+ The content was 0.0005%. SO is subjected to gravimetric method and volumetric method in national standard GB/T13025.8-2012' determination of sulfate radical in general test method in salt industry 4 2- And (4) detecting, wherein the result is not detected. In addition, use of violetExternal spectrophotometry method for measuring SO in purified glycerol 4 2- The content was 1.19%. The NaCl content in the purified glycerol was calculated to be 6.99% following the standard method of GB/T5462-2015 Industrial salt. That is, the mass ratio of methanol volume to glycerin residue is 1:1, and the purified glycerin contains more NaCl, which affects the purity of the glycerin.
Comparative example 2
A method for treating glycerin residues comprises the following steps:
(1) 300mL of methanol was added to 200g of glycerin residue, followed by magnetic stirring and mixing for 10min with magnetons. The resulting mixture was layered with the lower layer being crude salt solids and the upper layer being an alcoholic solution of crude glycerol. The mixture was separated by suction filtration and the filtrate was poured back several times to wash the crude salt thoroughly. The salt on the funnel and filter paper was collected and dried in an oven at 105 ℃ and weighed 120.48g of crude salt, which gave a crude salt yield of 60.24% for glycerol residue, which was more yellow than example 1 but whiter than comparative example 1.
(2) And (4) putting the dried crude salt into a muffle furnace for ash burning, and burning off organic matters remained on the crude salt. The heating rate is set to be 10 ℃/min, the final temperature is 600 ℃, the duration is 2h, the obtained ash is dissolved by pure water, the obtained ash is filtered and put into a 105 ℃ oven to evaporate water for recrystallization, so that the refined salt 120.80g is obtained, and the refined salt yield of the glycerol residue is 60.40%.
(3) The method follows the silver content method in the national standard GB/T13025.5-2012 determination of chloride ions in the general test method of salt manufacturing industry to Cl - And (6) detecting. Calculating to obtain Cl in refined salt by using an automatic titrator - The content was 60.77%. Ca is subjected to a volumetric method in GB/T13025.6-2012' determination of calcium and magnesium in general test method for salt industry 2+ And Mg 2+ And (5) detecting, wherein the result is not detected. In addition, ICP (inductively coupled plasma emission spectrometer) is adopted for Ca 2+ And Mg 2+ Detecting to obtain Ca in refined salt 2+ 0.0012% of Mg 2+ The content is 0.00029%. Simultaneous detection of Na in refined salt using ICP + The content was 36.60%. Following the general test method of sulfate radical in salt industry of national standard GB/T13025.8-2012Gravimetric and volumetric methods for SO determination 4 2- And (4) detecting, wherein the result is not detected. The NaCl content in the refined salt was calculated following the standard method of GB/T5462-2015 Industrial salt, and the obtained NaCl content was 93.09%. Namely, the mass ratio of the volume of the added methanol to the glycerin residue is 1.5.
Comparative example 3
A method for treating glycerin residues comprises the following steps:
(1) 100mL of methanol was added to 200g of glycerin residue, followed by magnetic stirring and mixing for 10min with magnetons. The resulting mixture was layered with the lower layer being crude salt solids and the upper layer being an alcoholic solution of crude glycerol. The mixture was separated by suction filtration and the filtrate was poured back several times to wash the crude salt thoroughly. The salt on the funnel and filter paper was collected and dried in an oven at 105 ℃ and weighed 123.76g of crude salt, giving a yield of 61.88% crude salt for glycerin residue, which was more yellow than example 1 but more yellow than comparative example 1.
(2) And (4) putting the dried crude salt into a muffle furnace for ash burning, and burning off organic matters remained on the crude salt. Setting the heating rate at 10 ℃/min, setting the final temperature at 600 ℃, keeping the temperature for 2h, dissolving the obtained ash by using pure water, filtering, putting the obtained ash into a 105 ℃ oven to evaporate water, and recrystallizing to obtain 123.50g of refined salt, wherein the refined salt yield of the glycerol residue is 61.75%.
(3) The method follows the silver content method in the national standard GB/T13025.5-2012 determination of chloride ions in the general test method of salt manufacturing industry to Cl - And (6) detecting. Calculating to obtain Cl in refined salt by adopting an automatic titrator - The content was 59.84%. Ca is subjected to a volumetric method in GB/T13025.6-2012' determination of calcium and magnesium in general test method for salt industry 2+ And Mg 2+ And (4) detecting, wherein the result is not detected. In addition, ICP (inductively coupled plasma emission spectrometer) is adopted for Ca 2+ And Mg 2+ Detecting to obtain Ca in refined salt 2+ Content of 0.0022% and Mg 2+ The content was 0.00039%. Simultaneous ICP method of Na in refined salt + The content was 36.37%. Industrial general for salt production following national standard GB/T13025.8-2012Measurement of SO by gravimetric and volumetric methods in test methods sulfate 4 2- And (4) detecting, wherein the result is not detected. The NaCl content in the refined salt was calculated following the standard method of GB/T5462-2015 Industrial salt, and the obtained NaCl content was 92.50%. Namely, the mass ratio of the volume of the added methanol to the glycerin residue is 0.5.
As can be seen from the above examples and comparative examples, the ratio of the volume of the extractant added to the mass of the glycerin residue affects the purity and yield of NaCl and glycerin as products. In different proportions, the ratio of the volume of the extractant to the mass of the glycerol residue is 1:1, the purity of the glycerol and the refined salt is the lowest. When the mass ratio of the volume of the extractant to the glycerol residue is more than 1:1, the purity of glycerol and refined salt is improved with the increase of the extractant, but the cost of adding methanol at an excessively high ratio is also considered. When the mass ratio of the volume of the extractant to the glycerol residue is 2:1, the NaCl content in the refined salt is 98.84 percent and exceeds the primary standard of the Chinese standard refined industrial dry salt in GB/T5462-2015 Industrial salt, while the secondary standard of the Chinese standard refined industrial dry salt in other proportions cannot be reached. That is, the effect is optimal when the mass ratio of the volume of the extracting agent to the glycerol residue is 2:1, the cost of the methanol dosage is low, and the purity of the refined salt and the glycerol is high. The method can carry out resource utilization on a large number of byproduct residues in the grease industry, has simple flow, convenient operation and mild conditions, and is suitable for industrial production. The obtained product is glycerol and refined salt. Wherein, the glycerol is widely applied to the fields of chemical industry, medicine, food, daily chemical industry and the like, and the refined salt can reach the standard of industrial salt. The purity of the product glycerol can reach more than 90 percent, the content of sodium chloride in refined salt can reach 99.05 percent, and the recovery rate of the extracting agent is 88.50 percent. Meanwhile, high-temperature pyrolysis gas and steam generated by pyrolysis and evaporation are subjected to heat recovery and serve as heat sources for purification and distillation (normal pressure or reduced pressure) of the crude glycerol solution, so that the production cost is greatly reduced. The invention has better application prospect.
The above examples and comparative examples are only for helping understanding the method of the present application and the core idea thereof, and are not to be construed as limiting the present invention. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for treating glycerin residues is characterized by comprising the following steps:
1) Mixing an extracting agent and the glycerol residue to obtain a liquid-phase and solid-phase layered mixture;
2) Separating the liquid phase and solid phase layered mixture to obtain a crude salt solid phase and a crude glycerin liquid phase;
3) The crude salt solid phase is subjected to pyrolysis, dissolution, filtration and evaporation in sequence to obtain a refined salt product; and purifying the crude glycerin liquid phase to obtain purified glycerin and an extracting agent.
2. The method for treating glycerin residue according to claim 1, wherein in step 1), the extractant comprises at least one of methanol, ethanol, and ethyl acetate.
3. The method for treating glycerin residue according to claim 2, wherein the volume-to-mass ratio of the extraction agent to the glycerin residue is 1mL: (1.5-2.5) g.
4. The method for treating glycerin residue according to claim 1, wherein the temperature of the pyrolysis in step 3) is 400 to 600 ℃.
5. The method for treating glycerin residue according to claim 4, wherein the pyrolysis time is 1.5 to 2.5 hours.
6. The method for treating glycerin residue according to claim 1, wherein the purification in step 3) is distillation.
7. The method of treating glycerin residue according to claim 6, wherein the distillation is atmospheric or vacuum distillation.
8. The method for treating glycerin residue according to claim 6, wherein in step 3), high temperature pyrolysis gas generated by the pyrolysis is used as a heat source for the distillation.
9. The method for treating glycerin residue according to claim 6, wherein in step 3), high-temperature steam generated by the evaporation is used as a heat source for the distillation.
10. The method for treating glycerin residue according to claim 1, wherein in the step 3), the sodium chloride content of the refined salt product is not less than 98.5wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503014A (en) * | 2011-11-22 | 2012-06-20 | 浙江大学 | Treatment method of glycerin wastewater containing salt |
| CN103524066A (en) * | 2013-10-21 | 2014-01-22 | 江苏聚威新材料有限公司 | Glycerin distillation residue treatment method |
| US20160200652A1 (en) * | 2013-08-19 | 2016-07-14 | REG Life Sciences, LLC | Production of partially refined waste glycerol |
| CN109704335A (en) * | 2018-12-24 | 2019-05-03 | 宁波环洋新材料股份有限公司 | A kind of processing method of the bottoms generated in refining crude glycerin |
| CN215028729U (en) * | 2021-04-28 | 2021-12-07 | 宜昌七朵云环境治理有限公司 | Treatment device for distillation residues |
-
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- 2022-08-24 CN CN202211020015.5A patent/CN115612559A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503014A (en) * | 2011-11-22 | 2012-06-20 | 浙江大学 | Treatment method of glycerin wastewater containing salt |
| US20160200652A1 (en) * | 2013-08-19 | 2016-07-14 | REG Life Sciences, LLC | Production of partially refined waste glycerol |
| CN103524066A (en) * | 2013-10-21 | 2014-01-22 | 江苏聚威新材料有限公司 | Glycerin distillation residue treatment method |
| CN109704335A (en) * | 2018-12-24 | 2019-05-03 | 宁波环洋新材料股份有限公司 | A kind of processing method of the bottoms generated in refining crude glycerin |
| CN215028729U (en) * | 2021-04-28 | 2021-12-07 | 宜昌七朵云环境治理有限公司 | Treatment device for distillation residues |
Non-Patent Citations (1)
| Title |
|---|
| 魏代军, 李清明: "甘油蒸馏残渣的回收利用", 表面活性剂工业, no. 02, pages 23 - 25 * |
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