CN115246758A - Preparation method of sulfurized isobutylene - Google Patents
Preparation method of sulfurized isobutylene Download PDFInfo
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- CN115246758A CN115246758A CN202210961731.7A CN202210961731A CN115246758A CN 115246758 A CN115246758 A CN 115246758A CN 202210961731 A CN202210961731 A CN 202210961731A CN 115246758 A CN115246758 A CN 115246758A
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- isobutylene
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- -1 nitrogen-containing cyclic thioether Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 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
- 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
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 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
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 preparation method of sulfurized isobutylene, liquid elemental sulfur and isobutylene in a compound NH X R (3‑X) Under the catalysis of the (A), the reaction is carried out to obtain sulfurized isobutylene, wherein X is 0, 1,2 or 3,R is substituted or unsubstituted C1-C6 alkyl, and the substituent of R is-OH and/or-NH 2 The substituent is mono-substituted or multi-substituted. The method has the advantages of simplicity, controllability, high safety and high sulfur content of the product.
Description
Technical Field
The invention belongs to the field of preparation of compounds, and particularly relates to a preparation method of sulfurized isobutylene.
Background
Dimethyl disulfide and sulfurized isobutylene can be used as a pre-sulfurization treating agent of a hydrogenation catalyst and a coking inhibitor of an ethylene pyrolysis furnace, and the dimethyl disulfide has the defects of low flash point, low safety, difficult transportation, high toxicity, bad smell and high production cost. The sulfurized isobutylene has high flash point (100-120 deg.C), and can be used as non-dangerous chemicalThe storage, transportation and use of the goods are common, thereby reducing the transportation, storage and use cost. The sulfurized isobutylene has no strong peculiar smell, reduces the pressure of production environmental protection and the body damage of operators in the use process, has low decomposition temperature (150-160 ℃), can greatly reduce the thermal risk caused by the concentrated decomposition and heat release in the pre-sulfurization process, and has more advantages compared with dimethyl disulfide as a pre-sulfurizing agent. The synthesis equation of sulfurized isobutylene is simple
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.
A number of publications also disclose the synthesis of sulfurized isobutenes. Chinese patent CN201110414953.9 discloses a synthesis process of sulfurized isobutylene by a gas phase method, wherein a gas phase mixture of elemental 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 pressure are too high. Chinese patent CN200610045249.X discloses a synthesis process of sulfurized isobutylene by one-step method, which takes 10% sodium carbonate solution as catalyst, the mass ratio of the catalyst amount to isobutylene is (0.5-2): 1, organic phase of reaction mixture is separated out, and then distillation and filtration are carried out to obtain the product sulfurized isobutylene, the sodium carbonate solution is recycled after separation, the method uses a larger amount of catalyst, and the product needs gas-liquid separation to recover the catalyst, so that the industrialization difficulty is large. Chinese patent CN201310488360.6 discloses a vulcanizing agent synthesis method, wherein inorganic weak base is used as a catalyst and can be recycled, and a vulcanizing product is subjected to reduced pressure distillation at 80 ℃ to obtain the vulcanizing agent. The method uses the aqueous solution of an alkaline compound as a catalyst, the dosage is large, the reaction product needs to be subjected to oil-water separation, and a large amount of wastewater needs to be treated.
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 provide a preparation method of sulfurized isobutylene. In the compound NH X R (3-X) Under the catalytic action, liquid elemental sulfur and isobutene are used as raw materials to react to prepare sulfurized isobutene, and the problems in the preparation of sulfurized isobutene are at least partially solved.
A method for preparing sulfurized isobutylene, namely 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 hydrocarbyl group, and the substituent of R is OH and/or NH 2 The substituent is mono-substituted or multi-substituted.
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 together with the low-boiling-point substances without separate separation operation. The low-boiling substance being mainly monosulfide (C) 4 H 9 ） 2 S and disulfide (C) 4 H 9 ） 2 S 2 Containing a small amount of trisulfide (C) 4 H 9 ） 2 S 3 The sulfur content is low, and the sulfur content of the product can be increased by separating the reactants, and the low-boiling-point substances can be generally removed by a method of reduced pressure distillation.
As a further improvement of the technical proposal, in order to improve the catalytic effect, a compound NH X R (3-X) Is NH 3 One or more of ethylenediamine, triethylamine, propylamine, 1,2-propanediamine, and 1,3-propanediamine.
As a further improvement of the technical proposal, in order to reduce the reaction pressure, and be beneficial to the operation control and the reaction safety, the reaction precursor system is pre-pumped with negative pressure, and the pressure of the negative pressure is-0.098 MPa to-0.095 MPa.
As a further improvement of the technical proposal, in order to improve the catalytic effect, a compound NH X R (3-X) The molar ratio to sulfur is (0.005-1): 1.
As a further improvement of the technical scheme, compound NH X R (3-X) The molar ratio to sulfur is (0.01-0.8): 1, more preferably (0.02-0.5): 1.
As a further improvement of the technical proposal, in order to improve the yield of polysulfide, the mass ratio of isobutene to sulfur is (0.3-3): 1.
As a further improvement of the technical scheme, the mass ratio of the isobutene to the sulfur is (0.4-2): 1, more preferably (0.5-1.2): 1.
As a further improvement of the solution, in order to balance the reaction time, the reaction temperature and the pressure, isobutene is continuously fed to the reaction during the preparation.
As a further improvement of the technical scheme, the feeding time of the isobutene is 0.1-8h.
As a further improvement of the technical proposal, the feeding time of the isobutene is 0.3 to 5h, and more preferably 0.5 to 3h.
As a further improvement of the technical scheme, in order to reduce the reaction cost, the reaction temperature of the preparation process is 120-300 ℃, and the reaction pressure is 0.5-4MPa.
The technology not mentioned in the present invention is referred to the prior art.
Compared with the prior art, the method has outstanding substantive characteristics and remarkable progress, and particularly, the method selects liquid ammonia or organic amine as the catalyst, has high catalytic activity, and the catalyst can react to generate nitrogenous cyclic thioether to be dissolved in reactants after the reaction is finished without separate separation treatment. Furthermore, the invention adopts continuous feeding reaction of isobutene, avoids hot air danger caused by a large amount of heat release, and can effectively control reaction pressure to ensure that the reaction is carried out under the control of temperature and pressure. Furthermore, the invention is operated by vacuumizing 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 simple and controllable operation, high safety and high sulfur content of the product.
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 gas, 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 composition of the sulfurized isobutylene sample was analyzed by Fuli 9790 II gas chromatograph with MEGA-5, 30m0.92mmx 0.25um, 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.
The sulfur content of the sulfurized isobutylene sample is determined by a ZDS-3000C ultraviolet fluorescence sulfur determinator according to the standard SH/T0689-2000
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 86g 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 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. Distilling and condensing to remove low-boiling-point substances in the reactants, 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 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 12g of liquid ammonia 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 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. Distilling and condensing to remove low-boiling-point substances in the reactants, 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 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. 54g of 1, 2-propanediamine is added, then 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. Distilling and condensing to remove low-boiling-point substances in the reactants, 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 62g of 1, 3-propanediamine was added, the reactor was heated, and the stirring apparatus was turned on when the temperature reached 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. Keeping the reaction temperature at 210-230 ℃ after the isobutene is completely fed, and keeping the pressure in the reaction kettle unchanged. Distilling and condensing to remove low-boiling-point substances in the reactants, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 4.
Example 5
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. And (3) adding 24g of liquid ammonia, then heating the reaction kettle, and opening the stirring device when the temperature reaches about 110 ℃. When the temperature of the reaction kettle is raised to 190 ℃, 290g 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 180-200 ℃, and the reaction pressure is 1.5-3.0MPa. Keeping the reaction temperature at 180-200 ℃ after the isobutene is completely fed, and keeping the pressure in the reaction kettle unchanged. Distilling and condensing to remove low-boiling-point substances in the reactants, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 5.
Example 6
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 the pressure of the vacuum kettle is reduced to normal pressure. 54g of 1, 2-propane diamine is added, then 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 ℃, the pressure of the reaction kettle is about 2.8MPa, 280g of isobutene is slowly pressed into the reaction kettle from a bottom inserting pipe, the feeding time is 1h, the feeding speed of the isobutene is controlled to maintain the reaction temperature at 190-210 ℃, and the reaction pressure is 2.8-3.8MPa. Keeping the reaction temperature at 190-210 ℃ after the isobutene is fed, and keeping the pressure in the reaction kettle unchanged. Distilling and condensing to remove low-boiling-point substances in the reactants, cooling, discharging and filtering to obtain a sulfurized isobutylene sample 6.
Comparative example
The preparation test is carried out according to the synthesis process of the sulfurized isobutylene disclosed by the Chinese patent CN200610045249.X by a one-step method, and the specific process is as follows: putting 300g of sulfur and 470g of 10% sodium carbonate solution into a 1L stainless steel reaction kettle, heating to 200 ℃, stirring for reaction for 0.5h, slowly adding 235g of isobutene into the reaction kettle, increasing the pressure to 8Mpa after adding, reacting for 5h, cooling to 70 ℃, pressing the reaction mixture out of the high-pressure kettle by using the residual pressure, standing for layering, separating an organic phase, and carrying out reduced pressure distillation and filtration to obtain a sulfurized isobutene sample 7.
The sulfur content and composition of samples 1-7 were determined separately as shown in tables 1 and 2.
TABLE 1 physicochemical parameter tables of examples and comparative examples
| Item | Sample 1 | Sample 2 | Sample 3 | Sample No. 4 | Sample No. 5 | Sample No. 6 | Sample 7 |
| Density, g * cm -3 | 1.090 | 1.105 | 1.095 | 1.097 | 1.100 | 1.092 | 1.087 |
| Viscosity (20 ℃ C.), mPa * s | 13 | 10 | 12 | 11 | 13 | 11 | 10 |
| Flash point (open mouth),. Degree.C | 114 | 116 | 115 | 112 | 115 | 113 | 114 |
| Sulfur content% | 50.2 | 54.8 | 56.4 | 52.1 | 55.9 | 56.2 | 45.8 |
As can be seen from Table 1: the density and viscosity of samples 1-6 are equivalent to that of sample 7, and the flash points of samples 1-7 are all more than 100 ℃, so that the samples can be transported and used as C-class materials. The sulfur content of samples 1-6 was higher than that of the comparative example, and the sulfur content of the sample obtained in sample 3 was the highest (56.4%), indicating that the ratio of the isobutylene and sulfur feeds had the greatest effect on the sulfur content of the sample. The sulfur content of sample 3 is equivalent to that of sample 6, which indicates that the reaction is not greatly affected by the pre-vacuum pumping of the reaction kettle. As is clear from the reaction processes of examples 3 and 6, in example 3, the reaction vessel was evacuated beforehand, and when the temperature of the reaction vessel was raised to 200 ℃, the pressure was about 1.5MPa, and the reaction pressure was 1.5 to 2.2MPa. The reaction kettle of the comparative example is not pre-vacuumized, the pressure is about 2.8MPa when the temperature of the reaction kettle is raised to 200 ℃, and the reaction pressure is 2.8-3.8MPa, so the pre-vacuuming of the reaction system can greatly reduce the pressure during the reaction.
TABLE 2 compositions of the examples and comparative examples
| Composition of | Sample 1 | Sample 2 | Sample 3 | Sample No. 4 | Sample No. 5 | Sample No. 6 | Sample 7 |
| Monosulfide (wt%) | 1.4 | 3.7 | 1.7 | 2.1 | 3.2 | 2.0 | 3.6 |
| Disulfide (wt%) | 17.4 | 19.6 | 18.0 | 17.6 | 18.8 | 18.4 | 21.3 |
| Trisulfide (wt%) | 30.2 | 26.2 | 25.8 | 27.5 | 25.1 | 26.2 | 34.5 |
| Tetrathioether (wt%) | 26.7 | 30.1 | 31.8 | 29.5 | 31.2 | 31.2 | 20.6 |
| Others (wt%) | 24.3 | 20.4 | 22.7 | 23.3 | 21.7 | 22.2 | 20.0 |
As can be seen from Table 2: the total amount of trisulfide and tetrasulfide in samples 1-6 was higher than that in comparative sample 7, and the tetrasulfide content in the samples was in direct proportion to the sulfur content.
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 present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (10)
1. A process for preparing sulfurized isobutylene features that the liquid elementary sulfur and isobutylene are mixed in NH compound X R (3-X) Wherein X is 0, 1,2 or 3,R is a substituted or unsubstituted C1-C6 hydrocarbyl group, and the substituent of R is-OH and/or-NH 2 The substituent is mono-substituted or multi-substituted.
2. The process for producing sulfurized isobutylene as defined in claim 1, wherein the compound NH is X R (3-X) Is NH 3 One or more of ethylenediamine, triethylamine, propylamine, 1,2-propanediamine, and 1,3-propanediamine.
3. The method for producing sulfurized isobutylene according to claim 1 or 2, wherein the reaction precursor system is preliminarily evacuated to a negative pressure of-0.098 MPa to-0.095 MPa.
4. Process for the preparation of sulfurized isobutylene according to claim 1 or 2, wherein the compound NH X R (3-X) The molar ratio to sulfur is (0.005-1): 1.
5. The process for producing sulfurized isobutylene as defined in claim 3, wherein the compound NH is X R (3-X) The molar ratio to sulfur is (0.01-0.8): 1.
6. the method for producing sulfurized isobutylene as claimed in claim 1 or 2, wherein the ratio of isobutylene to sulfur is (0.3-3): 1.
7. The process for the preparation of sulfurized isobutylene as defined in claim 1 or 2, wherein isobutylene is continuously fed to the reaction during the preparation.
8. The process for the preparation of sulfurized isobutylene as defined in claim 7, wherein the feeding time of isobutylene is 0.1 to 8 hours.
9. The process for the preparation of sulfurized isobutylene as claimed in claim 8, wherein the feeding time of isobutylene is 0.3 to 5 hours.
10. The process for the preparation of sulfurized isobutylene as defined in claim 1 or 2, wherein the reaction temperature in the preparation process is 120-300 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135670A (en) * | 1990-06-22 | 1992-08-04 | Mobil Oil Corporation | Sulfurized olefin extreme pressure/antiwear additives and compositions thereof |
| CN105037225A (en) * | 2015-05-28 | 2015-11-11 | 鄂尔多斯市鑫泰隆精细化工有限责任公司 | Preparation method of organic vulcanizing agent for hydrogenation catalyst pre-vulcanizing |
| CN108101815A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst vulcanizing agent and its preparation process |
| CN111072534A (en) * | 2019-12-26 | 2020-04-28 | 沈阳广达化工有限公司 | Synthetic process of sulfurized isobutylene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135670A (en) * | 1990-06-22 | 1992-08-04 | Mobil Oil Corporation | Sulfurized olefin extreme pressure/antiwear additives and compositions thereof |
| CN105037225A (en) * | 2015-05-28 | 2015-11-11 | 鄂尔多斯市鑫泰隆精细化工有限责任公司 | Preparation method of organic vulcanizing agent for hydrogenation catalyst pre-vulcanizing |
| CN108101815A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst vulcanizing agent and its preparation process |
| CN111072534A (en) * | 2019-12-26 | 2020-04-28 | 沈阳广达化工有限公司 | Synthetic process of sulfurized isobutylene |
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| 罗海棠等: "硫化异丁烯的制备工艺对其性能的影响", 合成润滑材料, vol. 46, no. 1, pages 26 - 29 * |
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