CN115340480A

CN115340480A - Method for removing mercaptan in sulfurized olefin

Info

Publication number: CN115340480A
Application number: CN202210982556.XA
Authority: CN
Inventors: 胡文敬; 李久盛; 郭凯; 李德胜
Original assignee: Shanghai Advanced Research Institute of CAS
Current assignee: Shanghai Advanced Research Institute of CAS
Priority date: 2022-08-16
Filing date: 2022-08-16
Publication date: 2022-11-15

Abstract

The invention provides a method for removing mercaptan from sulfurized olefin, which comprises the following steps: s1, adding alkali into water to prepare an alkali solution, and then adding a catalyst to prepare a composite eluent; s2, adding the composite eluent into a sulfurized olefin sample to be treated, and stirring at a certain temperature to obtain a mixed solution; s3, placing the mixed solution into a separating funnel, standing at a certain temperature, and separating an upper organic phase; and S4, washing the organic phase with water to be neutral, and then drying to obtain the mercaptan-removed sulfurized olefin. The method can effectively reduce the content of mercaptan in the sulfurized olefin, and can reduce the content of mercaptan sulfur in the sulfurized olefin sample by 95.5 percent at most; the treated sulfurized olefin has low odor and little corrosion to copper sheets, and the method has stronger adaptability and practicability; meanwhile, the mercaptan content of products such as sulfurized isobutylene and sulfurized isooctene can be effectively reduced, and the effect of reducing odor is achieved.

Description

Method for removing mercaptan in sulfurized olefin

Technical Field

The invention belongs to the field of lubricating additives, and particularly relates to a method for removing mercaptan from sulfurized olefin.

Background

The sulfurized olefin is one of important additives in a lubricating oil formula, has high active sulfur content in the structure, firmer sulfur bond, excellent heat stability and extreme pressure activity, can effectively prevent the tooth surface from being damaged under the condition of high-speed impact load, and is widely applied to modern gear oil. With the development of lubricating oil for mechanical equipment, the demand and the capacity of sulfurized olefin are continuously increased, at present, sulfurized olefin is mostly used as an extreme pressure antiwear agent in medium-high grade gear oil at home and abroad, but sulfurized olefin has the following defects and disadvantages, such as high production cost and high price; the three wastes generated in the production process are more and the pollution is great; sulfurized olefins are particularly odorous and present significant injury to the operating and user personnel.

Based on the requirements of environmental protection and health, the existing method for producing sulfurized olefin mainly adopts one-step method to synthesize the sulfoalkene under high pressure, the process is relatively simple, chlorine is not contained, three wastes are basically not generated, the catalyst can be recycled, and the production cost and the generation of the three wastes are reduced. In addition, although the odor of high pressure process olefins is relatively reduced, it still does not meet the needs of the operators and users and further processing is required to reduce the odor of sulfurized olefins. The high pressure limonene is a mixture whose main component is a dialkyl sulfide, which is the effective component in the limonene, and in addition, contains low levels of impurity components such as olefins, mercaptans, etc., which are by-products of the limonene.

Since mercaptan itself has foul smell and is highly corrosive to metals, the content of mercaptan in high-pressure mercaptan is reduced, and the reduction of the smell of sulfurized olefin and the improvement of corrosion are expected, and mercaptan removal methods mainly include an alkali washing method, a catalytic oxidation method and the like, but the methods can only remove part of mercaptan, and the effect of reducing the smell of sulfurized olefin is limited, especially for dioctyl polysulfide with relatively long alkyl chain, the effect of removing mercaptan by the traditional method is not obvious, so that an effective method needs to be developed to remove mercaptan in sulfurized olefin, so as to reduce the smell of sulfurized olefin and improve corrosion.

Disclosure of Invention

In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a method for removing mercaptans from sulfurized olefin, which solves the problems of the prior art that the effect of removing mercaptans is not obvious, the effect of reducing the odor of sulfurized olefin is limited, and the mercaptans in sulfurized olefin have strong corrosiveness to metals.

To achieve the above and other related objects, the present invention provides a method for removing mercaptans from sulfurized olefins, the method comprising the steps of:

s1, adding alkali into water to prepare an alkali solution, and then adding a catalyst to prepare a composite eluent;

s2, adding the composite eluent into a sulfurized olefin sample to be treated, and stirring at a certain temperature to obtain a mixed solution;

s3, placing the mixed solution in a separating funnel, standing at a certain temperature, and separating an upper organic phase;

and S4, washing the organic phase to be neutral by using water, and then drying to obtain the sulfurized olefin with mercaptan removed.

Preferably, the base in step S1 is one or a combination of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ethanolamine, diethanolamine, triethanolamine, pyridine and triethylamine.

Preferably, the concentration of the alkali solution in step S1 is 5% to 30%.

Preferably, the catalyst in step S1 is one or a combination of crown ether, ethanol, glycol, water-soluble polyether, polyethylene glycol, quaternary ammonium salt, quaternary ammonium base and amine salt.

Preferably, the mass ratio of the catalyst to the base in step S1 is 1% to 15%.

Preferably, the ratio between the volume of the composite eluent and the mass of the sulfurized olefin in step S2 is 3-20%.

Preferably, the ratio between the volume of the composite eluent and the mass of the sulfurized olefin in step S2 is 5-10%.

Preferably, the stirring temperature in the step S2 is 25-80 ℃, and the stirring time is 1-2 h.

Preferably, the stirring temperature in the step S2 is 35-60 ℃, and the stirring time is 1h.

Preferably, the temperature of the standing in the step S3 is 50-100 ℃.

As mentioned above, the method for removing mercaptan from sulfurized olefin in the present invention has the following beneficial effects:

according to the method, the catalyst is added into the alkali solution to prepare the composite eluent, and then the composite eluent is used for treating the sulfurized olefin sample so as to remove the mercaptan in the sulfurized olefin, so that the content of the mercaptan in the sulfurized olefin can be effectively reduced, and the content of the mercaptan in the sulfurized olefin sample can be reduced by 95.5% at most; the sulfurized olefin treated by the method provided by the invention has low smell and little corrosion to copper sheets, the method has stronger adaptability and practicability, and the raw materials and equipment are compatible with common chemical enterprises, and the disposal procedure is relatively simple and reliable; meanwhile, the mercaptan content of products such as sulfurized isobutylene and sulfurized isooctene can be effectively reduced, and the effect of reducing odor is achieved.

Drawings

FIG. 1 is a comparative gas chromatograph showing treated sulfurized isooctene sample I and untreated sulfurized isooctene obtained from example 1 of the present invention.

FIG. 2 shows a gas chromatogram comparison of a treated sulfurized isobutylene sample II obtained in example 2 of the present invention and untreated sulfurized isobutylene.

FIG. 3 is a comparative gas chromatograph showing sample III of treated sulfurized isooctenes obtained from example 3 of the present invention versus untreated sulfurized isooctenes.

FIG. 4 is a gas chromatograph comparing sample IV of treated sulfurized isooctenes with untreated sulfurized isooctenes obtained from example 4 of the present invention.

FIG. 5 shows the mass spectra of octanethiol for the treated sulfurized isooctenes and untreated sulfurized isooctenes of examples 1, 3 and 4 with a retention time of 2.99 min.

FIG. 6 shows the mass spectra of butanethiol at a retention time of 1.10min for sulfurized isobutylene with mercaptan removal and untreated sulfurized isobutylene in example 2.

Detailed Description

The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

Please refer to fig. 1-6. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.

According to the method, the catalyst is added into the alkali solution to prepare the composite eluent, and then the composite eluent is used for treating the sulfurized olefin sample so as to remove the mercaptan in the sulfurized olefin, so that the content of the mercaptan in the sulfurized olefin sample can be effectively reduced, and the content of the mercaptan in the sulfurized olefin sample can be reduced by 95.5% at most; the sulfurized olefin treated by the method provided by the invention has low smell and little corrosion to copper sheets, the method has stronger adaptability and practicability, and the raw materials and equipment are compatible with common chemical enterprises, and the disposal procedure is relatively simple and reliable; meanwhile, the mercaptan content of products such as sulfurized isobutylene and sulfurized isooctene can be effectively reduced, and the effect of reducing odor is achieved.

The invention aims to provide a method for removing mercaptan from sulfurized olefin based on environmental protection and health consideration of sulfurized olefin user, so as to reduce odor of sulfurized olefin and improve corrosion performance of sulfurized olefin to metal, wherein the method comprises the following steps:

s3, placing the mixed solution in a separating funnel, standing at a certain temperature, wherein the lower layer is a water phase, the upper layer is an organic phase, and separating the upper organic phase;

and S4, washing the organic phase with water to be neutral, and then drying to obtain the mercaptan-removed sulfurized olefin.

Specifically, the mercaptan can react with the alkali to generate water-soluble mercaptide, the mercaptide can be removed through water washing, so that the aim of removing the mercaptan is fulfilled, and the catalyst is used for promoting the reaction of the mercaptan and the alkali; among them, thiol means a kind of non-aromatic compound containing a mercapto functional group (-SH). Structurally, it can be seen that oxygen in a common alcohol is replaced by sulfur and then formed. In addition, the drying in step S4 is performed using anhydrous sodium sulfate, anhydrous magnesium sulfate, or anhydrous calcium chloride, and after drying, the drying agent is removed by filtration.

As an example, the base in step S1 is one or a combination of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ethanolamine, diethanolamine, triethanolamine, pyridine and triethylamine.

As an example, the concentration of the alkali solution in step S1 is 5% to 30%.

Specifically, the alkali solution in step S1 is an alkali aqueous solution, and the concentration of the alkali solution may include values in any range of 5%, 10%, 15%, 20%, 25%, 30%, and the like, which are specifically adjusted according to the actual conditions; wherein the concentration of the alkali solution is the ratio of the mass of the alkali to the mass of the total solution;

in the present embodiment, the concentration of the alkali solution is preferably 10%.

As an example, the catalyst in step S1 is one or a combination of crown ether, ethanol, ethylene glycol, water-soluble polyether, polyethylene glycol, quaternary ammonium salt, quaternary ammonium base and amine salt.

Specifically, the crown ether is a macrocyclic polyether containing a plurality of-oxy-methylene-structural units in a molecule, common crown ethers have 15-crown-5 and 18-crown-6, and the cavity structure of the crown ether has a selective effect on ions and can be used as a catalyst in an organic reaction.

The quaternary ammonium salt can be tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate and the like; the amine salt can be triethylamine hydrochloride, triethylamine sulfate, etc.

As an example, the mass ratio of the catalyst to the alkali in step S1 is 1% to 15%.

Specifically, the mass ratio of the catalyst to the base in step S1 may include values in any range of 1%, 3%, 5%, 7%, 9%, 11%, 13%, 15%, and the like, which are adjusted according to the actual conditions.

In this embodiment, the mass ratio of the catalyst to the base is preferably 1% to 5% (e.g., 1%, 2%, 3%, 4%, 5%, etc.).

As an example, the ratio between the volume of the composite eluent and the mass of the sulfurized olefin in step S2 is 3% to 20%.

Specifically, the ratio between the volume of the composite eluent and the mass of the sulfurized olefin in step S2 can include any range of values such as 3%, 5%, 10%, 15%, 20%, etc., and is specifically adjusted according to the actual application.

As an example, the ratio between the volume of the composite eluent and the mass of the sulfurized olefin in step S2 is 5% to 10%.

Specifically, the ratio between the volume of the composite eluent and the mass of the sulfurized olefin in step S2 can include values in any range of 5%, 6%, 7%, 8%, 9%, 10%, etc., and is adjusted according to practical application.

As an example, the stirring temperature in the step S2 is 25 ℃ to 80 ℃, and the stirring time is 1 to 2 hours.

Specifically, the stirring temperature in step S2 may include any value within any range, such as 25 ℃,30 ℃, 40 ℃, 50 ℃,60 ℃, 70 ℃, 80 ℃ and the like, and is specifically adjusted according to the actual conditions; the stirring time can include any range of values such as 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h and the like, and is adjusted according to actual conditions.

As an example, the stirring temperature in the step S2 is 35 ℃ to 60 ℃, and the stirring time is 1h.

Specifically, the stirring temperature in step S2 may include any value within any range, such as 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃ and the like, and is specifically adjusted according to the actual conditions.

As an example, the temperature of the standing in step S3 is 50 ℃ to 100 ℃.

Specifically, the temperature for standing in step S3 may include values in any range of 50 ℃,60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and the like, and is specifically adjusted according to the actual conditions.

In this embodiment, the temperature of the standing is preferably 80 ℃ to 90 ℃ (e.g., 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, etc.).

In order to better understand the method for removing the mercaptan from the sulfurized olefin, the invention also provides a method for rapidly detecting the mercaptan from the sulfurized olefin, and specifically, a certain amount of sulfurized olefin sample is added into a sealed bottle, the sealed bottle is heated to a certain temperature, and the gas in the bottle is taken to perform gas chromatography-mass spectrometry combined qualitative analysis on the mercaptan.

The process for removing mercaptans from sulfurized olefins according to the present invention is described below with reference to specific examples, which are intended to be illustrative only and not limiting in any way.

Example 1

This example provides a process for removing mercaptans from sulfurized isooctenes comprising the steps of:

s1, adding sodium carbonate into water to prepare a sodium carbonate solution with the concentration of 10%, and then adding 0.5g of 18-crown-6 serving as a catalyst to prepare a composite eluent A;

s2, adding 30.0g of sulfurized isooctene into a 100mL round-bottom flask, adding 5mL of composite eluent A into the round-bottom flask, and stirring for 1h at 40 ℃ to obtain a mixed solution;

s3, placing the mixed solution in a separating funnel, standing at 60 ℃, and separating an upper organic phase;

and S4, washing the organic phase by using 10mL of water until the organic phase is neutral, then drying the organic phase by using anhydrous sodium sulfate, and filtering to remove a drying agent to obtain a treated sulfurized isooctene sample I.

The invention also provides a rapid detection method of mercaptan in sulfurized olefin, which comprises the steps of adding a treated sulfurized isooctene sample I into a 2mL sealed bottle, heating to 60 ℃, extracting upper layer gas by using a trace sample injection needle after 30min, and carrying out GCMS analysis; similarly, rapid detection of mercaptan is also performed on an untreated sulfurized isooctene sample, and the specific method is the same as above and is not described again; the results are shown in FIG. 1.

As can be seen from FIG. 1, the untreated sulfurized isooctene sample is analyzed by gas chromatography-mass spectrometry, the peak with retention time of 1.0-1.5min is the solvent peak, the peak with retention time of 2.99min represents octanethiol, the mass spectrogram of the octanethiol is shown in FIG. 5, and the chromatographic peak of the octanethiol basically disappears after the treatment of the composite eluent A, which indicates that the method can effectively remove most of the mercaptan in the sample.

Performance testing

The sulfurized isooctene sample I and the untreated sulfurized isooctene sample of this example were tested for mercaptan sulfur content using GB/T1792-88 (2004) and the results are shown in Table 1. As can be seen from Table 1, the sulfurized isooctene sample treated with the composite eluent has a reduced mercaptan sulfur content of 88.9%.

TABLE 1 mercaptan sulfur content of treated sulfurized isooctene sample I and untreated sulfurized isooctene sample of example 1

Item	Untreated sulfurized isooctene sample	Treated sulfurized octene sample I
			Sulfur mercaptan content	0.6502％(m/m)	0.0724％(m/m)

Corrosivity test

The treated sulfurized isooctene sample I in the embodiment is subjected to a corrosivity test, the treated sulfurized isooctene sample I is added into 150N base oil in an amount of 1%, the mixture is stirred for 30min at 60 ℃, and then a copper sheet corrosion test is carried out at 100 ℃ for 3h. After the experiment is finished, cooling to room temperature, taking out the copper sheet, cleaning with petroleum ether, comparing with a standard colorimetric card, dividing the corrosion degree into 1-4 grades, wherein each grade comprises four grades of a, b, c and d, and the higher the grade is, the more serious the corrosion degree is represented. The corrosivity test of the untreated sulfurized isooctene sample is the same as the corrosivity test method and steps of the treated sulfurized isooctene sample I in the embodiment, and the details are not repeated herein; the corrosion result of the copper sheet is shown in table 2, and it can be seen from table 2 that the corrosion degree of the sulfurized isooctene sample I treated by the composite eluent on the copper sheet is reduced from 4c level to 3b level.

TABLE 2 Corrosion results on copper plaques for treated sulfurized isooctene sample I and untreated sulfurized isooctene sample of example 1

Item	Untreated sulfurized isobutylene sample	Treated sulfurized isobutylene sample I
			Corrosion results of copper sheet	4c	3b

Example 2

This example provides a method for removing mercaptans from sulfurized isobutylene, the method comprising the steps of:

s1, adding sodium carbonate into water to prepare a sodium carbonate solution with the concentration of 15%, and then adding 1g of 15-crown-5 serving as a catalyst to prepare a composite eluent B;

s2, adding 50.0g of sulfurized isobutylene into a 100mL round-bottom flask, adding 8mL of composite eluent B into the round-bottom flask, and stirring at 60 ℃ for 1h to obtain a mixed solution;

s3, standing the mixed solution at 70 ℃, removing a water solution layer, and separating an upper organic phase;

s4, washing the organic phase with 15mL of water to be neutral, then drying with anhydrous sodium sulfate, and filtering to remove the drying agent to obtain the mercaptan-removed sulfurized isobutylene sample II.

The invention also provides a rapid detection method of mercaptan in sulfurized olefin, which comprises the steps of adding a treated sulfurized isobutylene sample II into a 2mL sealed bottle, heating to 50 ℃, extracting upper layer gas by using a trace injection needle after 30min, and carrying out GCMS analysis; similarly, the rapid detection of mercaptan is also carried out on an untreated sulfurized isobutylene sample, and the specific method is the same as above and is not described again; the results are shown in FIG. 2.

As can be seen from FIG. 2, the untreated sulfurized isobutylene sample was analyzed by GC-MS, the peak at the retention time of 1.05-1.06min was the solvent peak, the peak at the retention time of 1.10min represented butanethiol, the mass spectrum of butanethiol is shown in FIG. 6, and the chromatographic peak of butanethiol substantially disappeared after treatment with the composite eluent B, indicating that the method can effectively remove most of the mercaptans in the sulfurized olefin sample.

Performance test

The mercaptan sulfur content of the treated sulfurized isobutylene sample II and the untreated sulfurized isobutylene sample II in this example were tested by GB/T1792-88 (2004), and the results are shown in Table 3. As can be seen from Table 3, the mercaptan sulfur content of the sulfurized isobutylene sample treated with the composite eluent was reduced by 90.1%.

TABLE 3 mercaptan sulfur content of treated sulfurized isobutylene sample II and untreated sulfurized isobutylene sample in example 2

Item	Untreated sulfurized isobutylene sample	Treated sulfurized isobutylene sample II
			Sulfur content of mercaptans	0.0414％(m/m)	0.0041％(m/m)

Corrosivity test

Carrying out a corrosivity test on the sulfurized isobutylene sample II treated in the embodiment, adding the treated sulfurized isobutylene sample II into 150N base oil in an addition amount of 3%, stirring for 30min at 60 ℃, and then carrying out a copper sheet corrosion experiment at 121 ℃ for 3h; the corrosivity test of the untreated sulfurized isobutylene sample is the same as the corrosivity test method and the steps of the treated sulfurized isobutylene sample II in the embodiment, and details are not repeated herein; the corrosion result of the copper sheet is shown in table 4, and as can be seen from table 4, the corrosion degree of the sulfurized isobutylene which is treated by the composite eluent to the copper sheet is reduced from 2c level to 2a level.

TABLE 4 Corrosion results on copper sheets for the treated sulfurized isobutylene sample II and the untreated sulfurized isobutylene sample in example 2

Item	Untreated sulfurized isobutylene sample	Treated sulfurized isobutylene sample II
			Corrosion results of copper sheet	2c	2a

Example 3

s1, adding sodium carbonate into water to prepare a sodium carbonate solution with the concentration of 20%, and then adding 1.0g of water-soluble polyether serving as a catalyst to prepare a composite eluent C;

s2, adding 40.0g of sulfurized isooctene into a 100mL round-bottom flask, adding 4mL of composite eluent C into the round-bottom flask, and stirring for 1h at 60 ℃ to obtain a mixed solution;

s3, standing the mixed solution at 60 ℃, removing a water solution layer, and separating an upper organic phase;

and S4, washing the organic phase with 15mL of water until the organic phase is neutral, drying the organic phase with anhydrous sodium sulfate, and filtering to remove a drying agent to obtain a treated sulfurized isooctene sample III.

The invention also provides a rapid detection method for mercaptan in sulfurized olefin, which comprises the steps of adding the treated sulfurized isooctene sample III into a 2mL sealed bottle, heating to 60 ℃, extracting upper layer gas by using a trace injection needle after 30min, and carrying out GCMS analysis; similarly, the rapid detection of mercaptan is also carried out on an untreated sulfurized isooctene sample, and the specific method is the same as above and is not described again; the results are shown in FIG. 3.

As can be seen from FIG. 3, the untreated sulfurized isooctene sample is analyzed by gas chromatography-mass spectrometry, the peak with retention time of 1.0-1.5min is the solvent peak, the peak with retention time of 2.99min represents octanethiol, the mass spectrogram of the octanethiol is shown in FIG. 5, and the chromatographic peak of the octanethiol basically disappears after the treatment of the composite eluent C, which indicates that the method can effectively remove most of the mercaptan in the sulfurized isooctene sample.

Performance testing

The treated sulfurized isooctene sample III and the untreated sulfurized isooctene sample of this example were tested for mercaptan sulfur content in GB/T1792-88 (2004), and the results are shown in Table 5. Table 5 shows that the sulfurized isooctene sample treated with the composite eluent has a reduced mercaptan sulfur content of 87.9%.

TABLE 5 mercaptan sulfur content of treated sulfurized isooctene sample III and untreated sulfurized isooctene sample of example 3

Item	Untreated sulfurized isooctene sample	Treated sulfurized octene sample III
			Sulfur mercaptan content	0.6502％(m/m)	0.0785％(m/m)

Corrosivity test

Carrying out a corrosion test on the treated sulfurized isooctene sample III in the embodiment, adding the treated sulfurized isooctene sample III into 150N base oil in an addition amount of 0.5%, stirring for 30min at 60 ℃, and then carrying out a copper sheet corrosion test at 100 ℃ for 3h h; the corrosivity test of the untreated sulfurized isooctene sample is the same as the corrosivity test method and steps of the treated sulfurized isooctene sample III in this example, and details are not repeated herein; the corrosion result of the copper sheet is shown in table 6, and as can be seen from table 6, the corrosion degree of the copper sheet by the isooctene sulfide treated by the composite eluent is reduced from 4c level to 3b level.

TABLE 6 Corrosion results on copper sheets for the treated sulfurized isooctene sample III and the untreated sulfurized isooctene sample of example 3

Item	Untreated sulfurized isooctene sample	Treated sulfurized octene sample III
			Corrosion results of copper sheet	4c	3b

Example 4

s1, adding pyridine into water to prepare a pyridine aqueous solution with the concentration of 15%, and then adding 1.5g of triethylamine hydrochloride serving as a catalyst to prepare a composite eluent D;

s2, adding 50.0g of sulfurized isooctene into a 100mL round-bottom flask, adding 6mL of composite eluent D into the round-bottom flask, and stirring for 1h at 80 ℃ to obtain a mixed solution;

s3, standing the mixed solution at 80 ℃, removing an aqueous solution layer, and separating an upper organic phase;

and S4, washing the organic phase with 20mL of water until the organic phase is neutral, drying the organic phase with anhydrous sodium sulfate, and filtering to remove the drying agent to obtain a treated sulfurized isooctene sample IV.

The invention also provides a rapid detection method of mercaptan in sulfurized olefin, which comprises the steps of adding a treated sulfurized isooctene sample IV into a 2mL sealed bottle, heating to 100 ℃, extracting upper layer gas by using a trace sample injection needle after 30min, and carrying out GCMS analysis; similarly, the rapid detection of mercaptan is also carried out on an untreated sulfurized isooctene sample, and the specific method is the same as above and is not described again; the results are shown in FIG. 4.

As can be seen from FIG. 4, the untreated sulfurized isooctene sample is analyzed by gas chromatography-mass spectrometry, the peak with retention time of 1.0-1.5min is the solvent peak, the peak with retention time of 2.99min represents octanethiol, the mass spectrogram of the octanethiol is shown in FIG. 5, and the chromatographic peak of the octanethiol basically disappears after the treatment of the composite eluent D, which indicates that the method can effectively remove most of the mercaptan in the sulfurized isooctene sample.

Performance testing

The mercaptan sulfur content of the treated sulfurized isooctene sample III and the untreated sulfurized isooctene sample of this example were tested by GB/T1792-88 (2004), and the results are shown in Table 7. It can be seen from Table 7 that the mercaptan sulfur content of the sulfurized isooctene sample treated with the composite eluent was reduced by 95.5%.

TABLE 7 mercaptan sulfur content of treated sulfurized isooctene sample IV and untreated sulfurized isooctene sample of example 4

Item	Untreated sulfurized isooctene sample	Treated sulfurized octene sample IV
			Sulfur mercaptan content	0.6502％(m/m)	0.0294％(m/m)

Corrosivity test

Carrying out a corrosion test on the treated sulfurized isooctene sample IV in the embodiment, adding the treated sulfurized isooctene sample IV into 150N of base oil by 0.5% of the addition amount, stirring for 30min at 60 ℃, and then carrying out a copper sheet corrosion test at 100 ℃ for 3h; the corrosivity test of the untreated sulfurized isooctene sample is the same as the corrosivity test method and steps of the treated sulfurized isooctene sample IV in the embodiment, and the details are not repeated herein; the corrosion result of the copper sheet is shown in table 8, and as can be seen from table 8, the corrosion degree of the copper sheet by the isooctene sulfide treated by the composite eluent is reduced from 4c level to 3b level.

TABLE 8 Corrosion results on copper plaques for treated sulfurized isooctene sample IV and untreated sulfurized isooctene sample of example 4

Item	Untreated sulfurized isooctene sample	Treated sulfurized octene sample IV
			Corrosion results of copper sheet	4c	3b

In conclusion, the catalyst is added into the alkali solution to prepare the composite eluent, and then the composite eluent is used for treating the sulfurized olefin sample so as to remove the mercaptan in the sulfurized olefin, so that the method can effectively reduce the content of the mercaptan in the sulfurized olefin and can reduce the content of the mercaptan sulfur in the sulfurized olefin sample by 95.5 percent at most; the sulfurized olefin treated by the method provided by the invention has low smell and little corrosion to copper sheets, the method has stronger adaptability and practicability, and the raw materials and equipment are compatible with common chemical enterprises, and the disposal procedure is relatively simple and reliable; meanwhile, the mercaptan content of products such as sulfurized isobutylene and sulfurized isooctene can be effectively reduced, and the effect of reducing odor is achieved. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A process for the removal of mercaptans from sulfurized olefins, the process comprising the steps of:

s3, placing the mixed solution in a separating funnel, standing at a certain temperature, and separating out an upper organic phase;

2. The method for removing mercaptans from sulfurized olefins according to claim 1, wherein: the alkali in the step S1 is one or a combination of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ethanolamine, diethanolamine, triethanolamine, pyridine and triethylamine.

3. A process for the removal of mercaptans in sulfurized olefins as claimed in claim 1, wherein: the concentration of the alkali solution in the step S1 is 5-30%.

4. The method for removing mercaptans from sulfurized olefins according to claim 1, wherein: the catalyst in the step S1 is one or a combination of crown ether, ethanol, glycol, water-soluble polyether, polyethylene glycol, quaternary ammonium salt, quaternary ammonium base and amine salt.

5. The method for removing mercaptans from sulfurized olefins according to claim 1, wherein: the mass ratio of the catalyst to the alkali in the step S1 is 1-15%.

6. The method for removing mercaptans from sulfurized olefins according to claim 1, wherein: the ratio of the volume of the composite eluent to the mass of the sulfurized olefin in the step S2 is 3-20%.

7. The method of claim 6 for removing mercaptans from sulfurized olefins, wherein: the ratio of the volume of the composite eluent to the mass of the sulfurized olefin in the step S2 is 5-10%.

8. The method for removing mercaptans from sulfurized olefins according to claim 1, wherein: in the step S2, the stirring temperature is 25-80 ℃, and the stirring time is 1-2 h.

9. The method for removing mercaptans from sulfurized olefins according to claim 8, wherein: in the step S2, the stirring temperature is 35-60 ℃, and the stirring time is 1h.

10. A process for the removal of mercaptans in sulfurized olefins as claimed in claim 1, wherein: the temperature of the standing in the step S3 is 50-100 ℃.