CN112028029A - Quenching production method of insoluble sulfur - Google Patents
Quenching production method of insoluble sulfur Download PDFInfo
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- CN112028029A CN112028029A CN202010720145.4A CN202010720145A CN112028029A CN 112028029 A CN112028029 A CN 112028029A CN 202010720145 A CN202010720145 A CN 202010720145A CN 112028029 A CN112028029 A CN 112028029A
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- sulfur
- insoluble
- insoluble sulfur
- water
- quenching
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 99
- 239000011593 sulfur Substances 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000010791 quenching Methods 0.000 title claims abstract description 20
- 230000000171 quenching effect Effects 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract 2
- 238000002309 gasification Methods 0.000 description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 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
- C01B17/12—Insoluble sulfur (mu-sulfur)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
A method for producing insoluble sulfur by quenching is characterized in that sulfur is used as a raw material, the sulfur is heated to 200-300 ℃, the temperature is kept for 1-120 minutes, then the sulfur is led into a leakage groove with densely distributed sieve pores at the bottom, the sulfur flows out from the pores at the bottom of the leakage groove and flows into water at the lower part of the leakage groove, and the sulfur which forms a thin strip shape is separated from the water; cutting the long and thin sulfur strip into 2-30cm long sulfur, and drying the cut sulfur in a dryer at 40-80 deg.C for 3-10 hr.
Description
Technical Field
The invention belongs to the field of non-metallic elements and compounds thereof, and relates to a quenching production method of insoluble sulfur. The international patent classification belongs to C01B 17/12.
Background
Insoluble Sulfur (IS) IS also called mu-type sulfur, which IS long-chain polymerized sulfur formed by ring-opening polymerization of ordinary sulfur and IS named because it IS Insoluble in carbon disulfide. The insoluble sulfur is mainly used as a vulcanizing agent of rubber, is widely used for the production of radial tires, has high dispersibility and high-temperature stability, can effectively avoid the blooming of rubber materials when being used for rubber mixing, and has good vulcanizing effect. With the increasing demand for radial tires in China, the demand for insoluble sulfur is increasing day by day. The production of insoluble sulfur by using common sulfur has high economic benefit and social benefit.
At present, the preparation method of insoluble sulfur mainly comprises a contact method, a gasification method, a melting method and the like. The contact method is mainly a method for preparing insoluble sulfur products by taking hydrogen sulfide as a raw material and carrying out catalytic oxidation reaction in an acidic medium reactor. The gasification method and the melting method both take common sulfur as raw materials, and utilize the thermal activation ring-opening polymerization mechanism of the sulfur to prepare insoluble sulfur.
(1) Contact method
The contact method is with H2S as a raw material, dependent on NOx+Fe3+Method for producing insoluble sulfur by catalytic oxidation[30]. The method comprises the following specific steps: high content of H2S gas (concentration greater than 70%) and O2Introducing HNO containing strong oxidant3And FeCl3The water solution generates insoluble sulfur under the oxidation-reduction action. The reaction mechanism for preparing insoluble sulfur by the contact method is as follows: h2S in strong oxidant HNO3And Fe3+Is partially oxidized to SO3 2-And reduction product NO; SO (SO)3 2-And H2S reacts to generate insoluble sulfur, and O is introduced into reduction product NO2Oxidation to NO2，NO2Followed by reaction with H2S, reacting to generate insoluble sulfur; fe3+Is also reacted with H2S reaction to generate insoluble sulfur and Fe2+In which Fe2+Is also NO2Is oxidized into Fe3+Thereby realizing FeCl3And recycling the aqueous solution.
Compared with the traditional method for producing insoluble sulfur, the contact method avoids the advantage of high-temperature corrosion of production equipment, and provides a new treatment H for petrochemical and coal chemical enterprises2S waste gas. But H2S is extremely toxic, has high requirement on the sealing property of production equipment, is difficult to realize large-scale production due to the limitation of an air source, has certain defects in the technology, and needs to be further explored and researched.
(2) Gasification process
Gasification and melting processes are the most traditional processes for producing insoluble sulfur. Wherein the gasification method comprises mixing common sulfur and appropriate amount of stabilizer, addingThe molten sulfur is put into a reactor and is put into a closed tubular heating furnace for melting, the temperature is increased to 500-700 ℃, superheated sulfur vapor is sprayed into a cooling medium containing a stabilizer at a high speed by utilizing the pressure of the reactor for quenching, and plastic sulfur can be obtained. Since the polymerization reaction is reversible, after quenching, part of the polymerized sulfur is converted into soluble sulfur, so that the obtained plastic sulfur product is a mixture. Then the plastic sulfur is solidified under a certain temperature and then crushed. To obtain a high insoluble sulphur product, CS is generally used2Extracting the mixture with the solution, then carrying out suction filtration or centrifugal separation to remove the carbon disulfide serving as the extractant, and drying the remaining particles to obtain the product.
Compared with other processes, the gasification process is mature, and the most outstanding advantage of the gasification process is that the insoluble sulfur contained in the obtained product is high, so that the process is the first choice of manufacturers at home and abroad. The disadvantages are that the reaction is in a high-temperature state, the equipment requirement is high, the energy consumption is high, the corrosion is serious, and a certain safety problem exists in the production process. The carbon disulfide used as an extractant in the process can cause certain damage to nerves and blood vessels of people, can cause poisoning, and is an explosive dangerous product.
(3) Melting process
The most significant difference between the melting process and the gasification process is the difference in the state of the sulfur when it is quenched. Since the gasification method is a steam sulfur quench method and the melting method is a liquid sulfur quench method, the quench temperature is not as high as the temperature required for the gasification method. The specific operation process for preparing insoluble sulfur by the melting method comprises the following steps: when the sulfur begins to melt at 130-180 ℃, adding a proper amount of stabilizer, and heating the melt to 180-210 ℃. In order to convert common sulfur into insoluble sulfur to the maximum extent, the sulfur melt is stirred for a period of time and then is rapidly cooled to room temperature by water, the water is separated, the obtained substance is put into the air for solidification, and the obtained solid block is subjected to a series of technological operations such as crushing, grinding and filtering to obtain a crude product of the insoluble sulfur.
The quenching process is an important part of all insoluble sulfur production. The melting method production process has the advantages of low operation temperature, light corrosion to equipment, low energy consumption, high safety and the like, but in the quenching process, the conversion rate of insoluble sulfur is reduced due to improper quenching method. In addition, the existing quenching method has the disadvantages of large manpower usage, high labor intensity and difficult continuity, so the development of an efficient quenching method has important practical significance.
Disclosure of Invention
The invention aims to provide a quenching method for producing insoluble sulfur, which reduces the labor intensity and improves the conversion rate of the insoluble sulfur by a melting method. The invention has the following characteristics:
(1) heating sulfur to 200-;
(2) separating the sulfur formed into thin strips from the water;
(3) cutting long strip-shaped sulfur into sulfur with length of 2-30 cm;
(4) feeding the cut sulfur into a dryer, and drying for 3-10 hours at 40-80 ℃.
In the above-mentioned launder, the diameter of each screen hole at the bottom thereof may be 0.2-5mm, preferably 0.5-2 mm. In the above method, the water temperature is 0-40 deg.C, preferably 0-20 deg.C.
ADVANTAGEOUS EFFECTS OF INVENTION
The insoluble sulfur is produced according to the method, the continuous operation can be realized, the obtained insoluble sulfur has stable quality, the yield is higher than that of other methods, the stability is good, and the labor intensity of workers is reduced in the production process. The method can make sulfur easy to quench, prevent the content of insoluble sulfur from reducing due to internal overheating, and can maintain high conversion rate without adding a stabilizer in the sulfur in advance, thereby reducing the production cost.
Detailed Description
The process of the present invention is further illustrated below with reference to examples.
Example 1:
a small experimental device is prepared in a laboratory according to the characteristics of the invention, sulfur is heated to 200 ℃, kept for 10 minutes, then introduced into a leak groove with a plurality of sieve holes at the bottom, a water pool is arranged at the lower part of the leak groove, the temperature of the water pool is 0.5 ℃, the diameter of the leak hole at the bottom of the leak groove is 1mm, the number of the leak holes is 30, the side length of the leak groove is 80mm, the leaked sulfur is taken out of water by a conveyor belt at the bottom of the water pool, the sulfur is cut into short strips with the length of 2-30cm by a cutting machine, and then the short strips are placed into a drying oven to be dried for 6 hours at the temperature of 50 ℃, so that the insoluble sulfur. The experimental device shows that the method can realize the quenching production of insoluble sulfur without adding a stabilizer.
Example 2:
in industrial production, a device is prepared according to the characteristics of the invention, sulfur is heated to 250 ℃ and kept for 120 minutes, then the sulfur is introduced into a leak groove with a plurality of sieve holes at the bottom, the lower part of the leak groove is a water tank, the temperature of the water tank is 15 ℃, the diameter of the leak hole at the bottom of the leak groove is 0.5mm, the number of the leak holes is 300, the side length of the leak groove is 80cm, the leaked sulfur is taken out of water by a conveyor belt at the bottom of the water tank and cut into short strips with the length of 2-30cm by a cutting machine, and then the short strips are placed into a drying box to be dried for 6 hours at the temperature of 60 ℃, so that the insoluble. The experimental device shows that the method can realize the quenching production of insoluble sulfur without adding a stabilizer.
Example 3:
in industrial production, a device is prepared according to the characteristics of the invention, sulfur is heated to 300 ℃ and kept for 30 minutes, then the sulfur is introduced into a leak groove with a plurality of sieve holes at the bottom, the lower part of the leak groove is provided with a water pool, the temperature of the water pool is 40 ℃, the diameter of the leak hole at the bottom of the leak groove is 0.2mm, the number of the leak holes is 300, the side length of the leak groove is 120cm, the height of the leak groove is 1000mm, the leaked sulfur is taken out of the water by a conveyor belt at the bottom of the water pool, the sulfur is cut into short strips with the length of 2-30cm by a cutting machine, and then the short strips are placed into a drying box to be dried for 3.
Example 4:
in industrial production, a device is prepared according to the characteristics of the invention, sulfur is heated to 230 ℃ and kept for 1 minute, then the sulfur is introduced into a leak groove with a plurality of sieve holes at the bottom, the lower part of the leak groove is a water pool, the temperature of the water pool is 40 ℃, the diameter of the leak hole at the bottom of the leak groove is 5mm, the number of the leak holes is 300, the side length of the leak groove is 120cm, the height of the leak groove is 1000mm, the leaked sulfur is taken out of water by a conveyor belt at the bottom of the water pool, the sulfur is cut into short strips with the length of 2-30cm by a cutting machine, and then the short strips are placed into a drying box to be dried for 10 hours at.
Example 5:
in industrial production, a device is prepared according to the characteristics of the invention, sulfur is heated to 260 ℃, and then the sulfur is introduced into a leaking groove with a plurality of sieve holes at the bottom, the lower part of the leaking groove is provided with a water pool, the temperature of the water pool is 10 ℃, the diameter of the leaking hole at the bottom of the leaking groove is 2mm, the number of the leaking holes is 300, the side length of the leaking groove is 120cm, the height of the leaking groove is 1000mm, the leaked sulfur is taken out of water by a conveyor belt at the bottom of the water pool, the sulfur is cut into short strips with the length of 2-30cm by a cutting machine, and then the short strips are placed into a drying box to be dried for 6 hours.
Comparative example:
heating sulfur to 260 ℃, directly pouring the sulfur into a water pool without a leakage groove, wherein the temperature of the water pool is 10 ℃, fishing out the sulfur from the water pool, and drying the sulfur in a drying box at 60 ℃ for 6 hours to obtain insoluble sulfur with the content of only 14%. The method of the invention can improve the yield of insoluble sulfur.
More experimental devices were not made due to equipment limitations, but the principle was similar. As can be seen from the above examples, continuous production can be achieved by the method, the labor intensity is reduced, and meanwhile, the yield of insoluble sulfur can be still kept high without adding a stabilizer into the sulfur. It should be understood, however, that the above description is only one embodiment of the present invention, and it should be understood that a person skilled in the art may make several modifications and improvements without departing from the principle of the present invention, and the modifications and improvements are within the scope of the claims of the present invention.
Claims (6)
1. A quenching production method of insoluble sulfur is characterized by comprising the following steps:
(1) heating sulfur to 200-;
(2) separating the sulfur formed into thin strips from the water;
(3) cutting long strip-shaped sulfur into sulfur with length of 2-30 cm;
(4) feeding the cut sulfur into a dryer, and drying for 3-10 hours at 40-80 ℃.
2. The method of claim 1, wherein a tip groove is used in the quenching process.
3. A method according to claims 1 and 2, characterized in that the diameter of the sieve openings of the launder is 0.2-5 mm.
4. A method according to claims 1 and 2, characterized in that the diameter of the sieve openings of the launder is 0.5-2 mm.
5. The method of claim 1, wherein the water temperature is 0-40 ℃.
6. A method according to claims 1 and 4, characterized in that the water temperature is 0-20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010720145.4A CN112028029A (en) | 2020-07-24 | 2020-07-24 | Quenching production method of insoluble sulfur |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010720145.4A CN112028029A (en) | 2020-07-24 | 2020-07-24 | Quenching production method of insoluble sulfur |
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| Publication Number | Publication Date |
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| CN112028029A true CN112028029A (en) | 2020-12-04 |
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| CN202010720145.4A Pending CN112028029A (en) | 2020-07-24 | 2020-07-24 | Quenching production method of insoluble sulfur |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401945A (en) * | 2014-10-20 | 2015-03-11 | 江西恒兴源化工有限公司 | High-temperature molten sulfur porous spraying type chilling quenching method |
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2020
- 2020-07-24 CN CN202010720145.4A patent/CN112028029A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401945A (en) * | 2014-10-20 | 2015-03-11 | 江西恒兴源化工有限公司 | High-temperature molten sulfur porous spraying type chilling quenching method |
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Application publication date: 20201204 |
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