CN115159465B - Method for purifying crude sulfur - Google Patents
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- CN115159465B CN115159465B CN202211022834.3A CN202211022834A CN115159465B CN 115159465 B CN115159465 B CN 115159465B CN 202211022834 A CN202211022834 A CN 202211022834A CN 115159465 B CN115159465 B CN 115159465B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 155
- 239000011593 sulfur Substances 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000008096 xylene Substances 0.000 claims description 18
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000004062 sedimentation Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 22
- 239000012535 impurity Substances 0.000 abstract description 16
- 238000004090 dissolution Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003245 coal Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 14
- 238000000746 purification Methods 0.000 description 13
- 239000011269 tar Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 230000005672 electromagnetic field Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940074411 xylene Drugs 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010061307 Neck deformity Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000874 microwave-assisted extraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0232—Purification, e.g. degassing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of coal chemical industry, and particularly relates to a method for purifying crude sulfur. The invention provides a method for purifying crude sulfur, which comprises the following steps: the crude sulfur is melted and then settled to obtain sulfur liquid; and extracting the sulfur liquid by adopting an organic solvent under the microwave condition to obtain sulfur. The invention adopts a microwave heating mode, can lead energy to be concentrated in heating sulfur preferentially, so that the sulfur can be dissolved in a solvent rapidly, and the extraction efficiency is improved; the microwave has a weaker thermal effect on tar impurities in the crude sulfur, so that the dissolution of sulfur is ensured, and meanwhile, the tar is prevented from being dissolved in an organic solvent after being decomposed, thereby improving the purity of the sulfur.
Description
Technical Field
The invention belongs to the technical field of coal chemical industry, and particularly relates to a method for purifying crude sulfur.
Background
Crude sulfur as a byproduct of coke oven gas in a coke oven plant is obtained in a desulfurization section for purifying the coke oven gas, and the main production principle is that hydrogen sulfide in the coke oven gas is catalyzed and oxidized to obtain elemental sulfur. Because coke oven gas contains a large amount of coal tar and dust, the substances can enter into crude sulfur, so that the obtained crude sulfur has poor color and is black or black-yellow. The sulfur content of the crude sulfur is not high and is generally 30 to 60 percent according to the production condition, thereby limiting the application range of the byproduct crude sulfur in a coking plant, even being sometimes unusable due to poor color or low purity and being only stacked in the form of solid waste. And further bring adverse effects to economic benefits and ecological environment of the coking enterprises.
In order to improve the purity of the crude sulfur as a byproduct of the coking plant, the coking plant performs purification treatment on the crude sulfur. At present, the purification method adopted by coking enterprises mainly comprises a melting method, a solvent method and a gasification method. But the purity of the sulfur purified by the existing purification method is lower and is in the range of 50-90 percent.
Disclosure of Invention
In view of the above, the invention provides a method for purifying crude sulfur, and the purification method provided by the invention can be used for purifying the crude sulfur to obtain high-purity sulfur.
In order to solve the technical problems, the invention provides a method for purifying crude sulfur, which comprises the following steps:
the crude sulfur is melted and then settled to obtain sulfur liquid;
and extracting the sulfur liquid by adopting an organic solvent under the microwave condition to obtain sulfur.
Preferably, the power of the microwaves is 500-1000W; the extraction time is 5-20 min.
Preferably, the organic solvent includes one or more of tetrahydronaphthalene, decalin, styrene, carbon disulfide, benzene, toluene, xylene, tetrachloroethylene, and o-xylene.
Preferably, the organic solvent is a mixed solution of toluene, xylene and tetrahydronaphthalene, and the mass ratio of toluene to xylene to tetrahydronaphthalene is 1:1:1-15.
Preferably, the mass ratio of the organic solvent to the crude sulfur is 1-20:1.
Preferably, the extraction is followed by solid-liquid separation, the solid-liquid separation is performed under a heat preservation condition, and the heat preservation temperature is consistent with the extraction temperature.
Preferably, the solid-liquid separation further comprises:
crystallizing the liquid obtained by solid-liquid separation to obtain a solid;
and washing and drying the solid in sequence to obtain the sulfur.
Preferably, the crystallization is cooling crystallization, and the temperature of the cooling crystallization is-5-25 ℃.
Preferably, the method further comprises, before melting: crushing and screening the crude sulfur in sequence to obtain crude sulfur particles;
the average grain diameter of the coarse sulfur particles is 0.2-1 mm.
Preferably, the sedimentation treatment is heat preservation and standing at the melting temperature, and the standing time is 3-12 h.
The invention provides a method for purifying crude sulfur, which comprises the following steps: the crude sulfur is melted and then settled to obtain sulfur liquid; and extracting the sulfur liquid by adopting an organic solvent under the microwave condition to obtain sulfur. The invention can remove part of tar and most of ash and salt in the crude sulfur by sedimentation treatment after the crude sulfur is melted, and the purity of the crude sulfur is primarily improved. The invention adopts a microwave heating mode, can lead the energy to be concentrated in heating sulfur preferentially, so that the sulfur can be dissolved in the organic solvent rapidly, and the extraction efficiency is improved; meanwhile, the microwave has a weaker thermal effect on tar impurities in the crude sulfur, and can prevent tar from being dissolved in an organic solvent after being decomposed while ensuring sulfur melting, so that the purity of the sulfur is improved. The results of the examples show that the purification method provided by the invention can be used for purifying crude sulfur, and the purity of the purified sulfur is 96.82-99.98%.
Detailed Description
The invention provides a method for purifying crude sulfur, which comprises the following steps:
the crude sulfur is melted and then settled to obtain sulfur liquid;
and extracting the sulfur liquid by adopting an organic solvent under the microwave condition to obtain sulfur.
The invention obtains sulfur liquid by sedimentation treatment after crude sulfur is melted. In the invention, the crude sulfur is preferably a byproduct of a coking plant, and the mass percentage of tar in the crude sulfur accounting for the total mass of impurities is preferably 30-80%, more preferably 40-73%. In the present invention, the pre-melting preferably further comprises: and crushing and screening the crude sulfur in sequence to obtain crude sulfur particles. The crushing is not particularly limited as long as the coarse sulfur can be formed into small particles. In the present invention, the average particle diameter of the coarse sulfur particles is preferably 0.2 to 1.0mm, more preferably 0.3 to 0.8mm, and most preferably 0.4 to 0.6mm. The present invention has no particular requirement for the sieving, as long as the average particle diameter of the coarse sulfur particles can be brought into the above-mentioned range. The invention limits the average particle size of the coarse sulfur particles within the above range, which is beneficial to increasing the melting efficiency of sulfur and improving the precipitation efficiency of impurities. When the average particle size of the coarse sulfur particles is within the range, the coarse sulfur particles are quickly melted and the fine impurities in the coarse sulfur particles gradually settle, but when the average particle size is smaller than the range, the impurity particle size is too fine, the surface of floating liquid is difficult to settle, and the purity of sulfur is not beneficial to improvement.
In the present invention, the melting temperature is preferably 120 to 150 ℃, more preferably 130 to 140 ℃. In the invention, the liquid obtained by melting the crude sulfur at the above-defined temperature has low viscosity so as to have good fluidity, so that the sedimentation of impurities in the crude sulfur is facilitated, and if the melting temperature is higher than 150 ℃, the melt is sticky and is not beneficial to the sedimentation of impurities in the crude sulfur. In the present invention, the impurities preferably include one or more of tar, ash, and salt impurities. The melting method is not particularly limited, and a method conventional in the art may be employed. In an embodiment of the invention, the melting is performed in an electric heater.
In the present invention, the sedimentation treatment is preferably a heat-retaining and standing at the melting temperature, and the time of the standing is preferably 3 to 12 hours, more preferably 8 to 12 hours. In the present invention, the sedimentation treatment preferably further comprises: and (3) carrying out solid-liquid separation on the settled system. The invention has no special requirement on solid-liquid separation, and can be realized by adopting a conventional mode in the field. The invention can precipitate most of tar and inorganic salt impurities in the crude sulfur through sedimentation treatment, thereby removing and primarily improving the purity of the sulfur.
After the sulfur liquid is obtained, the invention adopts an organic solvent to extract the sulfur liquid under the microwave condition to obtain sulfur. In the present invention, the organic solvent preferably includes one or more of tetrahydronaphthalene, decalin, styrene, carbon disulfide, benzene, toluene, xylene, tetrachloroethylene, and o-xylene. More preferably one or more of toluene, xylene and tetrahydronaphthalene, most preferably toluene, xylene and tetrahydronaphthalene. In the invention, when the organic solvent is more than two specific substances, the invention has no special requirement on the mass ratio of the specific substances, and the specific substances can be mixed at random. In the present invention, when the organic solvent is toluene, xylene, and tetrahydronaphthalene, the mass ratio of toluene, xylene, and tetrahydronaphthalene is preferably 1:1:1 to 15, more preferably 1:1:4 to 9, and still more preferably 1:1:5 to 8. In the invention, the mixed solution of toluene, xylene and tetrahydronaphthalene has larger solubility for sulfur, but almost does not dissolve tar, and the mixed solution of toluene, xylene and tetrahydronaphthalene is used as an organic solvent to extract sulfur in crude sulfur, so that the sulfur dissolution rate can be improved, and the recovery rate of sulfur is improved.
In the present invention, the mass ratio of the organic solvent to the crude sulfur is preferably 1 to 20:1, more preferably 5 to 15:1, and still more preferably 6 to 10:1.
In the present invention, the power of the microwaves is preferably 500 to 1000W, more preferably 700 to 800W; the frequency of the microwaves is preferably 300MHz to 300GHz, more preferably 2450 to 2800MHz. In the present invention, the extraction time is preferably 5 to 20 minutes, more preferably 10 to 15 minutes; the extraction temperature is preferably 80 to 110 ℃, more preferably 80 to 105 ℃, and most preferably 90 to 95 ℃. In the present invention, the temperature of the extraction is ensured by microwaves. In the present invention, the pressure of the extraction is preferably an atmospheric pressure, and the pressure of the atmospheric pressure is preferably 0.1MPa. The mixed solution is heated by adopting a conventional heating mode, so that crude sulfur tar impurities are dissolved in an organic solvent together with sulfur, and the purity of the sulfur is reduced.
In the invention, the dielectric constant of sulfur is 5.5-16.5, and the dielectric constant of tar is 2.0-3.0; generally, a medium with a large dielectric constant is easy to be heated by microwaves, and a medium with a small dielectric constant is difficult to be heated by microwaves. The invention carries out extraction under the condition of microwave heating, can ensure that microwave radiation energy penetrates through a medium to reach the inside of a material, so that the temperature inside the matrix is rapidly increased, the solubility of sulfur in a solvent is increased, and then the diffusion of the sulfur into the solvent is accelerated by an electromagnetic field generated by microwaves. The invention adopts microwave heating, can lead the energy to be concentrated in heating sulfur preferentially, and can lead the sulfur to be dissolved in the organic solvent rapidly, thereby improving the extraction efficiency; meanwhile, the heating effect of the microwave on tar in the crude sulfur is small, so that the tar is very slightly dissolved in the organic solvent.
The microwave heating technology is related technology which heats the material by taking the principle that the material absorbs microwave energy as a result of interaction of polar molecules in the material and microwave electromagnetic fields, under the action of an external alternating electromagnetic field, the polar molecules in the material are polarized and are alternately oriented along with polarity change of the external alternating electromagnetic field, so that the polar molecules are frequently rubbed and lost, electromagnetic energy is converted into heat energy and the like. In general, the heating temperature is increased to increase the heating speed, but the heating material is easily burnt and burnt at the outside and unheated at the inside. The microwave energy penetrates through the interior of the object, the heating process is carried out in the whole object at the same time, the temperature is quickly raised, the temperature is uniform, the temperature gradient is small, the microwave energy is a 'body heat source', and the time of heat conduction in conventional heating is greatly shortened.
In the present invention, the extraction is preferably followed by solid-liquid separation, which is preferably performed under a heat-preserving condition, and the temperature of the heat-preserving is preferably consistent with the extraction temperature. In the present invention, the solid-liquid separation is preferably a warm filtration. The method for heat preservation and filtration is not particularly limited, and the method is a conventional method in the field. In an embodiment of the present invention, the insulation filtration is preferably suction filtration.
In the present invention, the solid-liquid separation preferably further comprises:
crystallizing the liquid obtained by solid-liquid separation to obtain a solid;
and washing and drying the solid in sequence to obtain the sulfur.
The invention crystallizes the liquid obtained by solid-liquid separation to obtain solid. In the present invention, the crystallization is preferably a reduced temperature crystallization, and the temperature of the reduced temperature crystallization is preferably-5 to 25 ℃, more preferably 0 to 15 ℃.
In the present invention, the crystallization preferably further comprises: the post-crystallization system was filtered. The invention has no special requirement on the filtration, and adopts the conventional filtration mode in the field. In the invention, the filtered filtrate is preferably recycled and mixed with the organic solvent for extraction and purification again.
In order to further improve the sulfur purity, the solid obtained by filtration is preferably recrystallized. In the present invention, the recrystallization preferably includes the steps of:
dissolving the solid in an organic solvent to obtain a solution;
and cooling and crystallizing the solution.
In the present invention, the organic solvent is preferably identical to the organic solvent for extraction, and the description thereof will not be repeated. In the present invention, the temperature of the dissolution is preferably 80 to 105 ℃, most preferably 90 to 95 ℃. In the present invention, the temperature of the reduced temperature crystallization is preferably-5 to 25 ℃, more preferably 0 to 15 ℃.
In the present invention, the cooling crystallization preferably further comprises: and filtering the system after cooling and crystallizing. The invention has no special requirement on the filtration, and adopts the conventional filtration mode in the field.
After the solid is obtained, the solid is washed and dried in sequence to obtain the sulfur. In the present invention, the washing solvent preferably includes ethyl acetate, ethanol, chloroform or quinoline, more preferably ethanol or chloroform. In the present invention, the ethanol is preferably absolute ethanol. In the present invention, the number of times of washing is preferably 2 to 5 times, more preferably 3 to 4 times. In the present invention, the drying is preferably a drying, and the temperature of the drying is preferably 50 to 80 ℃, more preferably 55 to 75 ℃; the drying time is preferably 3 to 12 hours, more preferably 6 to 12 hours.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking crude sulfur which is a byproduct of a Liuzhou steel coke plant as a purification object, wherein the sulfur content of the crude sulfur is 43%, and the tar in the crude sulfur accounts for 73% of the total mass of impurities;
crushing and screening the crude sulfur in sequence to obtain crude sulfur particles with the average particle diameter of 0.4 mm;
placing 200g of crude sulfur particles in an electric heater, heating to 130 ℃ for melting, preserving heat, standing for 8 hours, carrying out sedimentation treatment, and filtering after the sedimentation treatment to obtain sulfur liquid;
performing microwave extraction on the mixed solution of the sulfur solution and an organic solvent (toluene, xylene and tetrahydronaphthalene mixed solvent with the mass ratio of 1:1:7) under the conditions of the pressure of 0.1MPa, the frequency of 2450MHz, the power of 700W and the temperature of 85 ℃; the mass ratio of the organic solvent to the crude sulfur is 8:1; extracting for 10min, and performing heat preservation and suction filtration at 85 ℃ after extraction; cooling the filtrate obtained by suction filtration to 10 ℃ for cooling crystallization, and filtering to obtain a solid; washing the solid with chloroform for 3 times, and drying at 60 ℃ for 3 hours to obtain sulfur.
Examples 2 to 12
Purification was carried out as in example 1, except that table 1 was referred to.
Table 1 parameters of the purification methods of examples 1 to 13
Example 13
Crude sulfur is purified according to the method of example 1, except that the solid obtained by filtration after cooling crystallization is dissolved in a mixed solvent of toluene, xylene and tetrahydronaphthalene at 95 ℃ to obtain a dissolution solution, wherein the mass ratio of toluene, xylene and tetrahydronaphthalene is 1:1:7;
cooling the solution to 10 ℃ for recrystallization, filtering, washing the solid obtained by filtering with chloroform for 3 times, and drying at 60 ℃ for 3 hours to obtain sulfur.
Comparative example 1
Crude sulfur was purified as in example 1, except that oil bath heating was used instead of microwave heating for extraction.
Comparative example 2
Crude sulfur was purified according to the method of comparative example 1, except that toluene was used as the organic solvent for extraction.
Comparative example 3
Crude sulfur was purified according to the method of comparative example 1, except that the organic solvent used in the extraction was xylene.
Comparative example 4
Crude sulfur was purified according to the method of comparative example 1, except that the organic solvent used in the extraction was tetrahydronaphthalene.
The sulfur dissolution rates and the retention rates of the sulfur obtained in examples 1 to 13 and comparative examples 1 to 4 were calculated according to the formulas 1 and 2, and the results are shown in Table 2.
Sulfur dissolution rate= (S) 0 -S 1 )/S 0 X 100% formula 1;
sulfur extraction rate=s 2 /(S 0 -S 1 ) X 100% formula 2;
wherein S is 0 S is the mass/g of sulfur in the crude sulfur 1 S is the mass/g of sulfur in the residue after purification 2 The mass/g of sulfur obtained by purification.
The purities of the sulfur obtained in examples 1 to 13 and comparative examples 1 to 4 were examined as follows:
detection principle: heating sulfur and sodium sulfite solution, boiling together, converting into sodium thiosulfate, titrating with iodine standard titration solution, and masking excessive sodium sulfite with formaldehyde; the reaction equation is shown in formulas 3 to 5:
S+Na 2 SO 3 ＝Na 2 S 3 O 3 formula 3;
I2+2Na 2 SO 3 ＝Na 2 S 4 O 6 +2nai formula 4;
HCHO+Na 2 SO 3 +H 2 O＝H 2 C(OH)SO 3 Na+NaOH formula 5.
The detection step comprises: the mass of the sample to be measured (accurate to 0.0001 g) is weighed and placed in a 250mL conical flask, 25mL absolute ethyl alcohol is used for wetting, 50mL of water and 5g of absolute sodium sulfite are added, a short neck funnel is placed on the bottle mouth, the flask is heated to be boiling, the micro-boiling state is kept until sulfur is completely dissolved, and the conical flask is shaken from time to time during heating. The Erlenmeyer flask was removed, cooled to room temperature, transferred to a 250mL volumetric flask, diluted to 250mL with water, and shaken well. Accurately sucking 50mL of shaking solution, placing the shaking solution into a 250mL conical flask, adding 7mL of 40% formaldehyde (GB 685) solution by mass concentration, placing the shaking solution for 3-5 min, adding 2 drops of 5g/L phenolphthalein indicator by mass concentration, using 20% by volume of glacial acetic acid solution drop to disappear in red and excessively adding 4-5 drops, adding 3mL of starch indicator, and titrating the shaking solution with 0.1mol/L iodine standard titration solution until blue appears as an end point.
The sulfur purity was calculated according to formula 6 and the results are shown in Table 2:
wherein, C is the reagent concentration of the iodine standard titration solution and mol/L; v (V) 1 To consume the volume of the standard titration solution of iodine in titrating the sample, mL; v (V) 2 To titrate the volume of standard titration solution of iodine consumed in blank, mL; m is m 1 G is the mass of the sample; m is m 2 G is the mass of a blank sample; 0.03207A standard titration solution with 1.00mL iodineEquivalent mass of sulfur, g.
TABLE 2 Sulfur dissolution Rate, purity and Sulfur extraction Rate of Sulfur obtained in examples 1 to 13 and comparative examples 1 to 4
According to Table 2, it is known that the purification method provided by the invention can be used for purifying crude sulfur to obtain sulfur with higher purity, and the purity is 96.82-99.98%. The sulfur extraction rate is 90.47-93.23%.
Examples 1 to 3 show that the higher the extraction temperature, the higher the sulfur dissolution rate, but the higher the temperature is, the more the tar is dissolved by the solvent, and the impurities are easily encapsulated during crystallization.
From examples 4 to 6, it is understood that the higher the mass ratio of the organic solvent to the sulfur liquid, the higher the sulfur dissolution rate is, which is higher than 1: the solvent also dissolves the aromatic hydrocarbon at 8 to encapsulate part of the impurities by the crystals.
From examples 2, 7 and 8, it is understood that the higher the microwave power is, the higher the sulfur dissolution rate is.
According to examples 2, 9 and 10, the longer the extraction time is, the higher the sulfur dissolution rate is, and when the solvent is more than 10 minutes, the aromatic hydrocarbon is dissolved by the solvent to wrap part of impurities in the crystals.
From examples 2, 11, 12, it is seen that the mass ratio of toluene, xylene, and tetrahydronaphthalene has little effect on the extraction effect under microwave conditions.
It is known from example 2 and comparative example 1 that the microwave heating method has a better purification effect than the conventional heating method
Comparative examples 1 to 4 examined the effect of the mixed reagent and the single reagent on extraction, and it was found that the mixed reagent had a small effect on purity, though the sulfur dissolution rate was improved significantly as compared with toluene and xylene as the single reagent.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (7)
1. A method for purifying crude sulfur comprises the following steps:
the crude sulfur is melted and then settled to obtain sulfur liquid;
extracting the sulfur liquid by adopting an organic solvent under the microwave condition to obtain sulfur;
the melting temperature is 130-140 ℃;
the power of the microwaves is 500-1000W;
the extraction time is 10-15 min; the extraction temperature is 80-110 ℃; the extraction pressure is normal pressure;
the organic solvent is a mixed solution of toluene, xylene and tetrahydronaphthalene;
crushing and screening the crude sulfur before melting in sequence to obtain crude sulfur particles;
the average particle size of the coarse sulfur particles is 0.2-1 mm.
2. The method for purifying crude sulfur according to claim 1, wherein the mass ratio of toluene, xylene and tetrahydronaphthalene is 1:1:1-15.
3. The method for purifying crude sulfur according to claim 1, wherein the mass ratio of the organic solvent to the crude sulfur is 1-20:1.
4. The method for purifying crude sulfur according to claim 1, wherein the extraction further comprises solid-liquid separation, wherein the solid-liquid separation is performed under a heat preservation condition, and the heat preservation temperature is consistent with the extraction temperature.
5. The method for purifying crude sulfur according to claim 4, wherein the solid-liquid separation further comprises:
crystallizing the liquid obtained by solid-liquid separation to obtain a solid;
and washing and drying the solid in sequence to obtain the sulfur.
6. The method for purifying crude sulfur according to claim 5, wherein the crystallization is a temperature-reduced crystallization, and the temperature of the temperature-reduced crystallization is-5 to 25 ℃.
7. The method for purifying crude sulfur according to claim 1, wherein the sedimentation treatment is heat preservation and standing at a melting temperature, and the standing time is 3-12 hours.
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Citations (3)
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|---|---|---|---|---|
| US4923482A (en) * | 1986-04-15 | 1990-05-08 | Sulexport-Intertrade A.G. | Process for separating sulfur from ore |
| CN101698904A (en) * | 2009-08-14 | 2010-04-28 | 深圳市东江环保股份有限公司 | Method for extracting sulfide minerals of nonferrous metals and method for recycling sulfur in extracted filtered residues thereof |
| CN114314522A (en) * | 2021-12-01 | 2022-04-12 | 新疆中泰创新技术研究院有限责任公司 | Sulfur paste resource utilization device and treatment method |
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| US7635460B2 (en) * | 2007-08-17 | 2009-12-22 | Carrasco Robert M | Process for dissolving sulfur ore using diaryl disulfide |
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|---|---|---|---|---|
| US4923482A (en) * | 1986-04-15 | 1990-05-08 | Sulexport-Intertrade A.G. | Process for separating sulfur from ore |
| CN101698904A (en) * | 2009-08-14 | 2010-04-28 | 深圳市东江环保股份有限公司 | Method for extracting sulfide minerals of nonferrous metals and method for recycling sulfur in extracted filtered residues thereof |
| CN114314522A (en) * | 2021-12-01 | 2022-04-12 | 新疆中泰创新技术研究院有限责任公司 | Sulfur paste resource utilization device and treatment method |
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| 微波辐射在化工领域应用的新进展与发展趋势;郑大中, 刘红英;四川化工与腐蚀控制(第02期);28 * |
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