CN1020601C - Process for production of vulcanized olefine - Google Patents
Process for production of vulcanized olefine Download PDFInfo
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- CN1020601C CN1020601C CN 88100419 CN88100419A CN1020601C CN 1020601 C CN1020601 C CN 1020601C CN 88100419 CN88100419 CN 88100419 CN 88100419 A CN88100419 A CN 88100419A CN 1020601 C CN1020601 C CN 1020601C
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Abstract
The present invention relates to a method for preparing sulfurized olefin. The method comprises the steps: sulfur monochloride reacts with alkene for generating adducts with sulfur and chlorine, and then, sulfuration and dechlorination reaction is carried out twice. The present invention is characterized in that unmanageable waste alkali liquid with sulfur produced in the technical process is reused in the next primary sulfuration and dechlorination reaction; finally, acidic waste water with bivalent sulfur ions and dissolved sulfur is not discharged, so the chemical oxygen demand of the waste water is reduced, the waste water treatment is easy, simultaneously, the waste water discharge amount is lowered, and raw materials are saved. The sulfurized olefin prepared by the method can be used as extreme pressure additives of lubricating agents.
Description
The present invention relates to the preparation method of organic sulfide.What specifically, the present invention relates to is the method that sulfur monochloride and olefine reaction prepare olefine sulfide.
Olefine sulfide, because the sulphur content height, oil soluble is good, and is little to copper corrosion performance, and has good extreme pressure activity and thermostability, therefore, is widely used as the additive of gear oil, extreme pressure grease, metal working oil.
Usually preparing the method for olefine sulfide, is with sulfur monochloride and olefine reaction, generates the adducts that contains sulphur, chlorine and carries out sulfurizing dechlorination reaction with alkali metalsulphide and element sulphur.EP7, the method that No. 735 patents are introduced, be with sulfur monochloride and alkene in the presence of the lower alcohol catalyzer, carry out addition reaction, the adducts that generates in the presence of alcohol solution and alkali metalsulphide carry out sulfurizing dechlorination reaction twice, the olefine sulfide product of generation has improved the corrodibility to copper.USP4,563, No. 302 patent has proposed with sulfur monochloride and C3～C6 olefine reaction, the adducts that generates is in the presence of alcohol solution, carry out sulfurizing dechlorination reaction with sodium sulphite, Sodium sulfhydrate, sodium hydroxide, elementary sulfur, alkyl sulfhydryl, the olefine sulfide product that obtains has good oil soluble in lubricating oil.
The above-mentioned method for preparing olefine sulfide, the sulfur-bearing alkaline waste water of generation, owing to contain alkali metalsulphide and alkali metals polysulfide, Sulfothiorine, so the chemical oxygen demand height, alkalescence is strong, stink is big, has brought difficulty to wastewater treatment.
The objective of the invention is to overcome the shortcoming that above-mentioned prior art exists.Propose a kind of in the technological process of preparation olefine sulfide, with the reluctant sulfur-bearing alkaline waste water reuse that generates, to obtain the method for comparison easy to handle acid waste water.
The present invention adopts the method for twice sulfurizing dechlorination reaction in the prior art, is back to the primary vulcanization dechlorination reaction of next batch but principal feature of the present invention is sulfurizing dechlorination reaction is generated with the second time sulfur-containing waste lye.Concrete steps comprise:
(1) sulfur monochloride and alkene carry out addition reaction in the presence of low-carbon alcohol catalyst, generate the adducts that contains sulphur, chlorine;
(2) adducts that (1) is gone on foot is added drop-wise to and goes in Virahol, the sodium sulfide solution, carries out the primary vulcanization dechlorination reaction, discharging acid waste water;
(3) the olefine sulfide crude product that the reaction of (2) step is generated carries out the sulfurizing dechlorination reaction second time with sodium sulfide solution again, produces sulfur-containing waste lye.
Characteristics of the present invention are:
(2) sodium sulfide solution used of Bu primary vulcanization dechlorination reaction, all with (3) step for the second time the sulfur-containing waste lye that produces of sulfurizing dechlorination reaction replace and discharging acid waste water.
(3) Bu the sulfurizing dechlorination reaction second time, the concentration of sodium sulfide solution is 15～20%(weight), amount of sodium sulfide is 0.60～0.82 mole of sodium sulphite/1 mole sulfur monochloride, and the sulfur-containing waste lye that reaction produces (/ 1 mole of sulfur monochloride of 300～600 grams) fully recovering is in (2) the primary vulcanization dechlorination reaction in step.
Described addition reaction, used sulfur monochloride are the sulfur monochloride of technical grade or contain a spot of sulfur dichloride (SCl
2) sulfur monochloride; Alkene comprises C3～C6 alkene and its mixture, preferably iso-butylene; Used low-carbon alcohol catalyst is methyl alcohol, ethanol, preferably methyl alcohol.Sulfur monochloride: iso-butylene: methyl alcohol=1: 1.6～2.0: 0.08～0.11(mol ratio).
Because addition reaction is thermopositive reaction, temperature of reaction is too high, and product colour is dark, and productive rate reduces.Addition reaction temperature of the present invention is 30～70 ℃, and preferably 45～55 ℃, in 1～6 hour reaction times, reaction pressure is a normal pressure.The hydrogen chloride gas water absorption that discharges in the reaction process becomes hydrochloric acid and reclaims.
Described primary vulcanization dechlorination reaction step is that the adducts that contains sulphur, chlorine/1 mole of sulfur monochloride of 220～230 grams of above-mentioned addition reaction generation and the whole waste lyes that contain sodium sulphite, sodium polysulphide, Sulfothiorine, dissolve sulfur of sulfurizing dechlorination reaction generation are for the second time carried out the primary vulcanization dechlorination reaction in the presence of alcoholic solvent.Used alcoholic solvent is the technical grade Virahol, its consumption is 1.0～3.0 moles of Virahol/1 mole sulfur monochlorides, 1.36 moles of Virahol/1 mole sulfur monochlorides preferably, 70～82 ℃ of temperature of reaction, be preferably 78～82 ℃, reaction pressure is a normal pressure, and the reaction times depends on that reaction mixture becomes the acid needed time by alkalescence.With the pH value of usual method control reaction solution, stopped reaction when presenting acidity.Reaction mixture is isolated saliniferous acid waste water through cooling, standing demix.In temperature is under 85～90 ℃, reclaims isopropanol water solution and repeated use in the waste water.The cl content of the olefine sulfide crude product behind the primary vulcanization dechlorination reaction is 3～7 heavy %.The stink damp body and function 10～30%(weight that discharges in the sulfurizing dechlorination reaction process) aqueous sodium hydroxide solution absorbs, the recyclable repeated use of the sodium sulphite of generation.
Described second time, sulfurizing dechlorination reaction was to be that the olefine sulfide crude product of 3～7 weight % further reacts with sodium sulfide solution with the chlorinity that the primary vulcanization dechlorination reaction generates.Used sodium sulphite is industrial goods, wherein sodium sulfide content is not less than 60%, sodium sulfide solution concentration is 15～20 heavy %, and its consumption is 0.60～0.82 mole of sodium sulphite/1 mole sulfur monochloride, and preferably consumption is 0.75～0.80 mole of sodium sulphite/1 mole sulfur monochloride.Reaction pressure is a normal pressure, and 70～82 ℃ of temperature are preferably 78～82 ℃; 1～6 hour reaction times was preferably 2～4 hours, under 85～90 ℃ of temperature, reclaimed isopropanol water solution and repeated use in the reaction mixture.Reaction mixture is cooled to about 30 ℃, adds No. 120 industrial naptha, extracts with usual method, and isolated sulfur-containing waste lye is back to the primary vulcanization dechlorination reaction of next batch.The extraction liquid that contains olefine sulfide that extracts through washing, distillation, diatomite filtration, can obtain the olefine sulfide product of chlorinity less than 0.5 heavy %.
Advantage of the present invention: because the sulfur-containing waste lye reuse of adopting sulfurizing dechlorination reaction for the second time to generate, so just chocolate that can discharge common technological process or the dark brown big alkaline strong waste water of stink be converted into oyster white, smell be improved significantly acid waste water; Also reduced simultaneously discharged waste water (produce 1 ton of product and can reduce by 2 tons of waste water); Save starting material (produce 1 ton of product and can save 200～300 kilograms of sodium sulphite); Because acid waste water do not contain sulfidion and dissolve sulfur, so the chemical oxygen demand of acid waste water has more significantly than the chemical oxygen demand of sulfur-bearing alkaline waste water again and reduces, and this just provides advantageous conditions for wastewater treatment.
Further specify characteristics of the present invention with example below.
Example 1
This example is the sulfur-containing waste lye that Comparative Examples of the present invention and preparation are back to the primary vulcanization dechlorination reaction of next batch.
135 gram (1 mole) sulfur monochlorides are added in the reaction flask, add 106 gram (1.9 moles) iso-butylenes then, and add 3.5 gram (0.11 mole) methyl alcohol with 2 ml/min speed simultaneously, temperature of reaction is 48 ± 2 ℃, 1.5 hours time, obtain the bisque adducts of 226 grams.
With concentration is that sodium sulfide solution 321 gram (0.74 mole of sodium sulphite), Virahol 82 grams (1.36 moles) of 18 heavy % join in the reaction flask with reflux condensation mode water cooler.Under agitation, mixed solution is heated to 40 ℃,, 226 gram adductss is added drop-wise in the reaction flask with 0.75 hour.The temperature of reaction mixture is raised to 82 ℃ gradually from 40 ℃.After adducts drips, continue reaction and with the pH value of usual method assaying reaction mixed solution, stopped reaction when presenting acidity at 82 ℃.When question response liquid is cooled to 30 ℃, saliniferous acid waste water being collected in the waste water reclamation bottle, is 90 ℃ in normal pressure, temperature, reclaims isopropanol water solution, the acid waste water discharging.Gained contains the organic phase of Virahol, olefine sulfide crude product after filtration except that after desalting, and carries out the sulfurizing dechlorination reaction second time.
Whole organic phases that filtrate 347 grams (0.80 mole of sodium sulphite) and the primary vulcanization dechlorination reaction of the sodium sulfide solution of 18 heavy % are generated are added in the reaction flask, 82 ℃ of stirring reactions 3 hours, and then controlled temperature to 90 ℃ reclaims the isopropanol water solution in the reaction mixture.When reaction solution is cooled to 30 ℃, add No. 120 industrial naptha, from reaction mixture extraction olefine sulfide crude product.Standing demix is isolated sulfur-containing waste lye 385 grams, is used for the primary vulcanization dechlorination reaction of next batch.The extraction liquid that contains olefine sulfide cleans three times with 100 ml waters, removes water-soluble impurity and waste water, decompression (15 mmhg) distillation behind first normal pressure under 130 ℃ then, after steaming No. 120 industrial napthas, use diatomite filtration down, obtain 136 and restrain orange-yellow olefine sulfide product at 50 ℃.Product sulfur-bearing 42.7 heavy %, chlorine 0.23 heavy %.
Example 2
Be added in the reaction flask with reflux condensation mode water cooler with Virahol 82 grams (1.36 moles) with by the 385 gram sulfur-containing waste lyes that example 1 makes.Under agitation mixed solution is heated to 40 ℃, with 0.75 hour, being added drop-wise in the reaction flask according to 226 prepared gram adductss of the method for example 1.The temperature of reaction mixture rises to 82 ℃ gradually from 40 ℃.After adducts drips, keep 82 ℃ and continue reaction, stopped reaction when reaction solution is acidity.When question response liquid is cooled to 30 ℃, the acid waste water that closes salt being collected in the waste water reclamation bottle, is under 90 ℃ in normal pressure, temperature, reclaims isopropanol water solution, the acid waste water discharging.The organic phase of gained behind the desalination, is carried out the sulfurizing dechlorination reaction second time after filtration.
Sulfurizing dechlorination reaction step and condition are with example 1 for the second time.Obtain the orange-yellow olefine sulfide product of 148 grams, product sulfur-bearing 43.5 heavy %, chlorine 0.19 heavy %.
Example 3
Primary vulcanization dechlorination reaction step and condition are with example 2.The organic phase that obtains is carried out the sulfurizing dechlorination reaction second time.
For the second time sulfurizing dechlorination reaction is to be that sodium sulfide solution 341 grams (0.70 mole of sodium sulphite) of 16 heavy % and whole organic phases of primary vulcanization dechlorination reaction generation are added in the reaction flask with concentration, and all the other steps and condition are with example 1.Obtain the orange-yellow olefine sulfide product of 141 grams, product sulfur-bearing 41.8 heavy %, chlorine 0.44 heavy %.
Example 4
Replace 3.5 gram catalyst for methanol with 3.5 gram ethanol, remaining condition is with example 2.Finally obtain the orange-yellow olefine sulfide product of 146 grams.Product sulfur-bearing 42.5 heavy %, chlorine 0.27 heavy %.
Example 5
This example is the product performance evaluation result that obtains after the sulfur-containing waste lye reuse.
Test with lubricating oil is: the heavy % base oil in 5 heavy % olefine sulfide additives+95, the bright stock (120BS) that base oil is produced for the grand celebration paraffinic crude: neutral oil (500SN)=80: 20(is heavy).
Oil soluble test: sample is in room temperature or be heated to 80 ℃ and be cooled to room temperature again, and its transparency that detects by an unaided eye transparently is dissolving, mixes slightly or muddy for being partly dissolved or insoluble.
Copper sheet abrasion test: press ASTM D130 evaluation, test temperature 121 ± 1 ℃, 3 hours.
Extreme pressure property evaluation: press the GB3142-82 method and measure.
Evaluation result sees Table.
Table
The rotten extreme pressure property of additiveoil dissolubility film-making
Erosion level PB, ox PD, ox ZMZ, ox
The molten 1b 980 of example 1 product＞2,450 644
The molten 2a 1029 of example 2 products＞2,450 693
The molten 2c 980 of example 3 products＞2,450 639
The molten 2b 1029 of example 4 products＞2,450 683
Claims (5)
1, a kind of preparation is used for the preparation method of the sulfur-bearing extreme-pressure additive of lubricant, comprises the following steps:
(1) sulfur monochloride (S
2Cl
2) and alkene in the presence of the lower alcohol catalyzer, carry out addition reaction, generate a kind of adducts that contains sulphur, chlorine;
(2) adducts that (1) is gone on foot is added drop-wise to and goes in Virahol, the sodium sulfide solution, carries out the primary vulcanization dechlorination reaction, discharging acid waste water;
(3) the olefine sulfide crude product that the reaction of (2) step is generated carries out the sulfurizing dechlorination reaction second time with sodium sulfide solution again, produces sulfur-containing waste lye,
The invention is characterized in:
(2) sodium sulfide solution used of Bu primary vulcanization dechlorination reaction, all with (3) step for the second time the sulfur-containing waste lye that produces of sulfurizing dechlorination reaction replace and discharging acid waste water;
(3) Bu the sulphur dechlorination reaction second time, sodium sulfide solution concentration 15～20 heavy %, 0.60～0.82 mole of sodium sulphite/1 mole sulfur monochloride of amount of sodium sulfide, the sulfur-containing waste lye fully recovering of generation is in (2) the primary vulcanization dechlorination reaction in step.
2, in accordance with the method for claim 1, it is characterized in that primary vulcanization dechlorination reaction temperature is 70～82 ℃, be preferably 78～82 ℃.
3,, it is characterized in that the primary vulcanization dechlorination reaction time is reaction mixture needed time when becoming acidity by alkalescence according to claim 1 or 2 described methods.
4, in accordance with the method for claim 1, it is characterized in that the sulfurizing dechlorination reaction amount of sodium sulfide is preferably 0.75～0.80 mole of sodium sulphite/1 mole sulfur monochloride for the second time.
5, according to claim 1 or 4 described methods, it is characterized in that the sulfurizing dechlorination reaction temperature is 70～82 ℃ for the second time, the time is 1～6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100419 CN1020601C (en) | 1988-02-05 | 1988-02-05 | Process for production of vulcanized olefine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100419 CN1020601C (en) | 1988-02-05 | 1988-02-05 | Process for production of vulcanized olefine |
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| Publication Number | Publication Date |
|---|---|
| CN1034714A CN1034714A (en) | 1989-08-16 |
| CN1020601C true CN1020601C (en) | 1993-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100419 Expired - Fee Related CN1020601C (en) | 1988-02-05 | 1988-02-05 | Process for production of vulcanized olefine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065008C (en) * | 1994-09-06 | 2001-04-25 | 恩尼彻姆公司 | Process for the preparation of a flexible thermoplastic composite filament containing continuous fibres |
| CN1886462B (en) * | 2003-11-25 | 2010-04-14 | 吉田清和 | Composite synthetic resin composition and material therefrom |
-
1988
- 1988-02-05 CN CN 88100419 patent/CN1020601C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065008C (en) * | 1994-09-06 | 2001-04-25 | 恩尼彻姆公司 | Process for the preparation of a flexible thermoplastic composite filament containing continuous fibres |
| CN1886462B (en) * | 2003-11-25 | 2010-04-14 | 吉田清和 | Composite synthetic resin composition and material therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034714A (en) | 1989-08-16 |
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