CN115385766A - Synthetic method of sulfurized isobutylene - Google Patents
Synthetic method of sulfurized isobutylene Download PDFInfo
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- CN115385766A CN115385766A CN202210962218.XA CN202210962218A CN115385766A CN 115385766 A CN115385766 A CN 115385766A CN 202210962218 A CN202210962218 A CN 202210962218A CN 115385766 A CN115385766 A CN 115385766A
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 239000000126 substance Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract 2
- 238000009835 boiling Methods 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- -1 nitrogen-containing cyclic thioether Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 3
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 102100033925 GS homeobox 1 Human genes 0.000 description 1
- 101001068303 Homo sapiens GS homeobox 1 Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing sulfurized isobutylene, which is to add liquid elemental sulfur and isobutylene in a compound NH X R (3‑X) Wherein X is 0, 1,2 or 3, R is a substituted or unsubstituted C1-C6 hydrocarbon group, and the substituent of R is OH and/or NH 2 The substituent is mono-substituted or multi-substituted; wherein a low-boiling-point substance is added in the reaction, and the low-boiling-point substance is a distillate obtained by distilling a sulfurized isobutylene crude product. The method has the advantages of high yield, low energy consumption, safety and environmental protection.
Description
Technical Field
The invention belongs to the field of preparation of compounds, and particularly relates to a synthetic method of sulfurized isobutylene.
Background
Sulfurized isobutylene as presulfurizing agent of hydrogenating catalystAnd a coking inhibitor of the ethylene pyrolysis furnace, has the advantage of high flash point (100-120 ℃), can be used as a non-hazardous chemical substance, and can be used for storing, transporting and using common goods, thereby reducing the cost of transportation, storage and use. The one-step synthesis equation of sulfurized isobutylene is simple and is
However, the composition of sulfurized isobutylene is complicated and conforms to the structure (C) 4 H 8 ） 2 S N However, there are many possibilities of molecular weight and spatial structure. The biggest difference is N which can be 1-4; secondly is-C 4 H 8 The specific linking method may also be different, such as-C 4 H 8 Comprising two different structures-C (CH) 3 ) 2 CH 2 -and-CH 2 CH 2 CH(CH 3 ) Sulfurized isobutylene is therefore a mixture of many similar structures.
Chinese patent CN201110414953.9 discloses a synthesis process of sulfurized isobutylene by a gas phase method, wherein a gas phase mixture of single sulfur and a catalyst is introduced into a tubular reactor, the reaction is carried out for 10-20min at 450-500 ℃ and 2-9MPa, then the sulfurized isobutylene product is obtained by gas-liquid separation and filtration, and the production cost is increased by the method when the reaction temperature and the reaction pressure are too high. The applicant develops a liquid phase method for synthesizing sulfurized isobutylene, in particular to liquid elemental sulfur and isobutylene in a compound NH X R (3-X) Wherein X is 0, 1,2 or 3, R is a substituted or unsubstituted C1-C6 hydrocarbon group, and the substituent of R is OH and/or NH 2 The substituent is mono-substituted or multi-substituted. The process has the advantages of simple operation and lower temperature and pressure, but the product yield in the preparation process is still low.
In order to overcome the defects of the prior art, an ideal technical solution is always sought.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for synthesizing sulfurized isobutylene.
Sulfurized isobutyl etherProcess for the synthesis of alkenes, liquid elemental sulfur and isobutene in the compound NH X R (3-X) Wherein X is 0, 1,2 or 3, R is a substituted or unsubstituted C1-C6 hydrocarbon group, and the substituent of R is OH and/or NH 2 The substituent is mono-substituted or multi-substituted. Wherein a low-boiling-point substance is added in the reaction, and the low-boiling-point substance is a distillate obtained by distilling a crude sulfurized isobutylene product. The low-boiling substance being mainly monosulfide (C) 4 H 9 ） 2 S and disulfide (C) 4 H 9 ） 2 S 2 Also contains a small amount of trisulfide (C) 4 H 9 ） 2 S 3 . The sulfur content of the low-boiling-point substance is low, the sulfur content of the product can be improved only by separating the low-boiling-point substance from the reaction product, the low-boiling-point substance can be removed by a reduced pressure distillation method generally, and the low-boiling-point substance can only be treated as hazardous waste.
As a further improvement of the technical proposal, in order to improve the yield, the mass ratio of the low-boiling-point substance to the sulfur is (0.01-2): 1.
As a further improvement of the technical proposal, the mass ratio of the low-boiling-point substance addition to the sulfur is (0.02-1.5): 1.
as a further improvement of the technical proposal, the mass ratio of the low-boiling-point substance to the sulfur is (0.02-1): 1.
As a further improvement of the solution, in order to increase the catalytic efficiency, a compound NH X R (3-X) Is NH 3 One or more of ethylenediamine, triethylamine, propylamine, 1, 2-propylenediamine, and 1, 3-propylenediamine. Compound NH of the invention X R (3-X) The nitrogen-containing cyclic thioether is reacted with isobutyl mercaptan with low molecular weight to generate the nitrogen-containing cyclic thioether, the boiling point of the nitrogen-containing cyclic thioether is low, most of the nitrogen-containing cyclic thioether is dissolved in low-boiling-point substances, and the nitrogen-containing cyclic thioether can be separated from the low-boiling-point substances together without separate operation and separation.
The reaction system is cooled to normal temperature when the low-boiling-point substances are removed by reduced pressure distillation, and then the reduced pressure heating is carried out, so that the energy consumption is high, and a large amount of low-boiling-point substances are pumped out, namely, waste gas is generated, and the yield is reduced. As a further improvement of the technical scheme, in order to reduce energy consumption and improve yield, the temperature of the system after the reaction is finished is reduced to 100-250 ℃, and the low-boiling-point substances are collected by atmospheric distillation and condensation, preferably the distillation temperature is 120-220 ℃.
As a further improvement of the technical solution, in order to balance the reaction time, the reaction temperature and the pressure, isobutene is continuously added in the reaction.
As a further improvement of the technical proposal, the isobutene feeding time is 0.1 to 8h, preferably 0.3 to 5h, more preferably 0.5 to 3h. The faster the isobutene feed rate, the higher the reaction temperature and pressure.
In order to reduce the reaction pressure, facilitate the operation control and the reaction safety, the reaction precursor system is pre-pumped with negative pressure, preferably the negative pressure is-0.098 MPa to-0.095 MPa.
As a further improvement of the technical scheme, the reaction temperature of the reaction is 120-300 ℃, and the effect is better when the reaction temperature is 150-250 ℃.
The prior art is referred to in the art for techniques not mentioned in the present invention.
Compared with the prior art, the method has outstanding substantive characteristics and remarkable progress, and particularly, the method recycles low-boiling-point substances, so that the product yield is improved, and the generation of hazardous wastes is reduced. Furthermore, the invention improves the sulfur content of the product by atmospheric distillation in the cooling process after the reaction is finished, can reduce energy consumption, reduces waste gas and improves the yield. Furthermore, the invention pre-pumps negative pressure before reaction, which can greatly reduce the reaction pressure after temperature rise and is beneficial to operation control and reaction safety. The method has the advantages of high yield, low energy consumption, safety and environmental protection.
Drawings
FIG. 1 is a GC-MS chromatogram of the low boiling substance collected in example 3.
FIG. 2 is a gas chromatogram before distillation of the reaction product in example 3.
FIG. 3 is a gas chromatogram after distillation of the reaction product in example 3.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
Raw materials for examples and comparative examples: sulphur (flaky), jingling petrochemical, industrial grade, 99.8wt%; isobutylene, nanjing specialty gas, inc., technical grade, 99wt%; liquid ammonia, nanjing specialty gases, inc., technical grade, 99.999wt%; ethylenediamine, 1, 2-propylenediamine and 1, 3-propylenediamine are AR grades. The apparatus used in the examples and comparative examples was a 1L stainless steel reaction vessel GSH-1/25, 25MPa,350 ℃, wii chemical machinery Co., ltd.
The gas-mass spectrometry analysis of the sulfurized isobutylene sample adopts a GC6890 gas chromatograph and an MS5973 mass spectrometer of Agilent company, the chromatographic column is a ZB-5MS capillary column (30m0.25mm 0.5um), helium is used as carrier gas, and the constant flow rate is 0.6 mL/min -1 The injection inlet temperature is 265 ℃, the initial temperature is 30 ℃, the temperature is maintained for 3min, and then the temperature is controlled to be 20 ℃ per min -1 Raising the temperature to 240 ℃, keeping the temperature for 3min, injecting sample without shunting, wherein the injection volume is 2.0uL.
The composition of the sulfurized isobutylene sample was analyzed by Fuli 9790 II gas chromatograph with MEGA-5, 30m0.92mmx 0.25um column, air as carrier gas and flow rate of 0.1 mL/min -1 The injection inlet temperature is 265 ℃, the initial temperature of the column box is 100 ℃, the temperature is maintained for 3min, and then the temperature is maintained at 3 ℃ for min -1 Heating to 120 deg.C, and heating at 20 deg.C/min -1 Raising the temperature to 240 ℃, keeping the temperature for 3min, injecting sample without shunting, wherein the injection volume is 2.0uL.
Example 1
300g of sulfur is put into a 1L stainless steel reaction kettle, the reaction kettle is sealed and then is replaced by nitrogen for 3 times, and a vacuum pump is used for vacuumizing to reduce the pressure of the reaction kettle to-0.095 MPa. After 8g of low-boiling-point substances and 36g of ethylenediamine are added respectively, the reaction kettle starts to be heated, and the stirring device is opened when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is increased to 240 ℃, 360g of isobutene is slowly pressed into the reaction kettle from the bottom inserting pipe, the feeding time is 0.5h, the isobutene feeding speed is controlled to maintain the reaction temperature at 230-250 ℃, and the reaction pressure is 2-3.5MPa. Keeping the reaction temperature at 230-250 ℃ after the isobutene is fed, and keeping the pressure in the reaction kettle unchanged. And opening an outlet at the top of the reaction kettle after the temperature of the reaction kettle is reduced to 220 ℃ to condense and collect low-boiling-point substances in the reactants. And after the low-boiling-point substances are collected, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 1.
Example 2
300g of sulfur is put into a 1L stainless steel reaction kettle, the reaction kettle is sealed and then is replaced by nitrogen for 3 times, and a vacuum pump is used for vacuumizing to reduce the pressure of the reaction kettle to-0.095 MPa. After 40g of low-boiling-point substance and 36g of ethylenediamine are respectively added, the reaction kettle starts to be heated, and the stirring device is opened when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is raised to 150 ℃, 240g of isobutene is slowly pressed into the reaction kettle from the bottom inserting pipe, the feeding time is 3 hours, the isobutene feeding speed is controlled to maintain the reaction temperature at 150-170 ℃, and the reaction pressure is 1-2.5MPa. Keeping the reaction temperature at 150-170 ℃ after the isobutene is completely fed, and keeping the pressure in the reaction kettle unchanged. And opening an outlet at the top of the reaction kettle after the temperature of the reaction kettle is reduced to 120 ℃ to condense and collect low-boiling-point substances in the reactants. And after the low-boiling-point substances are collected, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 2.
Example 3
300g of sulfur is put into a 1L stainless steel reaction kettle, the reaction kettle is sealed and then replaced by nitrogen for 3 times, and a vacuum pump is used for vacuumizing to reduce the pressure of the reaction kettle to-0.095 MPa. After 35g of low-boiling-point substances and 36g of ethylenediamine are added respectively, the reaction kettle starts to be heated, and the stirring device is opened when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is raised to 200 ℃, 280g of isobutene is slowly pressed into the reaction kettle from the bottom inserting pipe, the feeding time is 1h, the isobutene feeding speed is controlled to maintain the reaction temperature at 190-210 ℃, and the reaction pressure is 1.5-2.2MPa. Keeping the reaction temperature at 190-210 ℃ after the isobutene is fed, and keeping the pressure in the reaction kettle unchanged. After the temperature of the reaction kettle is reduced to 190 ℃, an outlet at the top of the reaction kettle is opened to condense and collect low-boiling-point substances in the reactants. And after the low-boiling-point substances are collected, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 3.
Example 4
300g of sulfur is put into a 1L stainless steel reaction kettle, the reaction kettle is sealed and then is replaced by nitrogen for 3 times, and a vacuum pump is used for vacuumizing to reduce the pressure of the reaction kettle to-0.095 MPa. After 280g of low-boiling-point substance and 36g of ethylenediamine are respectively added, the reaction kettle starts to be heated, and the stirring device is opened when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is raised to 220 ℃, 300g of isobutene is slowly pressed into the reaction kettle from the bottom inserting pipe, the feeding time is 2 hours, the isobutene feeding speed is controlled to maintain the reaction temperature at 210-230 ℃, and the reaction pressure is 1.5-2.2MPa. After the isobutene is completely fed in, the reaction temperature is kept between 210 and 230 ℃ until the pressure in the reaction kettle is unchanged. And opening an outlet at the top of the reaction kettle after the temperature of the reaction kettle is reduced to 200 ℃ to condense and collect low-boiling-point substances in the reactants. And after the low-boiling-point substances are collected, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 4.
Comparative example 1
300g of sulfur is put into a 1L stainless steel reaction kettle, the reaction kettle is sealed and then is replaced by nitrogen for 3 times, and a vacuum pump is used for vacuumizing to reduce the pressure of the reaction kettle to-0.095 MPa. After 36g of ethylenediamine is added, the reaction kettle starts to be heated, and the stirring device is opened when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is raised to 200 ℃, 280g of isobutene is slowly pressed into the reaction kettle from the bottom inserting pipe, the feeding time is 1h, the isobutene feeding speed is controlled to maintain the reaction temperature at 190-210 ℃, and the reaction pressure is 1.5-2.2MPa. Keeping the reaction temperature at 190-210 ℃ after the isobutene is fed, and keeping the pressure in the reaction kettle unchanged. And opening an outlet at the top of the reaction kettle after the temperature of the reaction kettle is reduced to 190 ℃ to condense and collect low-boiling-point substances in the reactants. And after the low-boiling-point substances are collected, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 5.
Comparative example 2
300g of sulfur is put into a 1L stainless steel reaction kettle, the reaction kettle is sealed and then is replaced by nitrogen for 3 times, and a vacuum pump is used for vacuumizing to reduce the pressure of the reaction kettle to-0.095 MPa. After 35g of low-boiling-point substances and 36g of ethylenediamine are respectively added, the reaction kettle starts to be heated, and the stirring device is opened when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is raised to 200 ℃, 280g of isobutene is slowly pressed into the reaction kettle from the bottom inserting pipe, the feeding time is 1h, the isobutene feeding speed is controlled to maintain the reaction temperature at 190-210 ℃, and the reaction pressure is 1.5-2.2MPa. Keeping the reaction temperature at 190-210 ℃ after the isobutene is fed, and keeping the pressure in the reaction kettle unchanged. And (3) reducing the temperature of the reaction kettle to normal temperature, then carrying out reduced pressure distillation, condensation and collection on low-boiling-point substances, heating to 80 ℃ until no distillate is produced, and filtering to obtain a sulfurized isobutylene sample 6.
The samples of each example and comparative example were subjected to chromatography analysis, and the low boiling substances collected in the examples and comparative examples were weighed to calculate the yields of the examples and comparative examples, and the results are shown in Table 1.
TABLE 1 tables for low boiler collection and product yields for examples and comparative examples
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Low boiling point substance (g) | 65.2 | 12.4 | 48.3 | 56.2 | 43.2 | 4.2 |
| Yield (%) | 96.0 | 94.8 | 96.1 | 96.3 | 88.5 | 88.6 |
As can be seen from Table 1, the low boiling substance collected in the comparative example is very little, because the low boiling substance is difficult to condense by vacuum distillation, most of the low boiling substance is pumped into a vacuum system, which causes damage to the vacuum system and pollution of tail gas, and if a low temperature condensation system is added, the equipment investment and energy consumption are increased. Since the low boiling substances collected in examples 1 to 4 can be used as a raw material for the reaction without causing a loss of the raw material, the product yield was calculated by calculating the low boiling substance as the objective product. As can be seen from Table 1, the product yields in examples 1-4 are all higher than in the comparative example, indicating that the process raw materials provided by the present invention are effectively utilized. In the comparative example 1, if the low-boiling-point substance is recycled and counted as the target product, the product yield is 95.6 percent, which shows that the recycling of the low-boiling-point substance can improve the product yield.
As can be seen from FIG. 1, the low boiling substance, which is collected in example 3 and is composed of nitrogen-containing cyclic sulfide (5.197 min), a large amount of monosulfide and disulfide, a small amount of trisulfide and a very small amount of tetrasulfide, has a relatively low sulfur content, and must be separated from the reaction product to increase the sulfur content of the sulfurized isobutylene product. The separated low-boiling-point substances can continuously react with sulfur to generate high-order polysulfide ether, thereby improving the product yield and reducing the treatment cost of hazardous wastes.
As can be seen from FIGS. 2 and 3, the peaks at retention times of 1.973min and 2.566min are monosulfide, the peaks at retention times of 5.648min and 6.321min are disulfide, the contents of the monosulfide and disulfide before the reaction product is distilled are respectively 11.3% and 14.8%, the contents of the monosulfide and disulfide after the reaction product is distilled are respectively 2.2% and 12.0%, and the monosulfide and disulfide are main components of low boiling substance, thereby showing that the method of recovering low boiling substance by distillation and condensation using the residual heat of the reaction product can effectively reduce the content of low boiling substance in the reaction product, and the collected low boiling substance can be recycled as the reaction raw material. The composition of the sulfurized isobutylene product after the distillation of the reaction product is mainly trisulfide and tetrasulfide, which shows that the method for recycling the low-boiling-point substance has no influence on the composition of the sulfurized isobutylene product.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit the same; although the present invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; without departing from the spirit of the invention, it is intended to cover all modifications within the scope of the invention as claimed.
Claims (10)
1. The method for synthesizing sulfurized isobutylene is characterized in that liquid elemental sulfur and isobutylene are in a compound NH X R (3-X) Wherein X is 0, 1,2 or 3, R is a substituted or unsubstituted C1-C6 hydrocarbon group, and the substituent of R is OH and/or NH 2 The substituent is mono-substituted or multi-substituted; and adding a low-boiling-point substance into the reaction, wherein the low-boiling-point substance is a distillate obtained by distilling a sulfurized isobutylene crude product.
2. The method for synthesizing sulfurized isobutylene according to claim 1, wherein the mass ratio of the amount of the low boiling substance added to sulfur is (0.01-2): 1.
3. The method for synthesizing sulfurized isobutylene according to claim 2, wherein the mass ratio of the amount of the low boiling substance added to sulfur is (0.02-1.5): 1.
4. the method for synthesizing sulfurized isobutylene according to any one of claims 1 to 3, wherein the low boiling substance is collected by pressure distillation after the reaction is completed and the temperature of the system is lowered to 100 to 250 ℃.
5. The method for synthesizing sulfurized isobutylene according to claim 4, wherein the low boiling substance is collected by atmospheric distillation when the temperature of the system is reduced to 120 to 220 ℃ after the reaction is completed.
6. The process for the synthesis of sulfurized isobutylene as defined in claim 4, wherein the compound NH is X R (3-X) Is NH 3 Ethylenediamine, triethylamine,One or more of propylamine, 1, 2-propanediamine, and 1, 3-propanediamine.
7. The method for synthesizing sulfurized isobutylene as defined in claim 4, wherein isobutylene is continuously added during the reaction.
8. The method for synthesizing sulfurized isobutylene as recited in claim 7, wherein the feeding time of isobutylene is 0.1 to 8 hours.
9. The method for synthesizing sulfurized isobutylene according to claim 4, wherein the reaction precursor system is preliminarily evacuated to a negative pressure of-0.098 MPa to-0.095 MPa.
10. The method for synthesizing sulfurized isobutylene according to claim 4, wherein the reaction temperature of the reaction is 120 to 300 ℃.
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