Continuous photochemical production of high-purity linear mercaptans and sulfide compositions

Abstract

Continuous photochemical production of high purity linear mercaptan and sulfide-containing compositions.

Description

[Technical Field]

[0001] This invention relates to the continuous photochemical production of high-purity linear mercaptan and sulfide-containing compositions. [Background technology]

[0002] Mercaptans are useful in a wide range of technological fields, including as biological corrosion inhibitors, antifungal agents, chain transfer agents in polymerization, coatings for metal surfaces, and vulcanization accelerators for rubber. Sulfides are important intermediates in organic synthesis and are key components in many fine chemicals, such as perfumes and cosmetics. In some of these applications, high purity of the mercaptan or sulfide is important.

[0003] There is always a need to improve the large-scale preparation of high-purity mercaptans and sulfides, particularly without relying on the presence of various reaction accelerators or photoinitiators. [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention achieves these objectives, which is to provide high-purity mercaptans and sulfides as described herein. [Means for solving the problem]

[0005] In particular, the present invention provides a method for producing high-purity product thiols from hydrogen sulfide and olefins. The method for producing high-purity thiols comprises the following steps: Feeding hydrogen sulfide and olefins to a reactor system. The reactor system is configured to form a reactor effluent containing product thiols, unreacted hydrogen sulfide, unreacted olefins, and other components. Recirculating a first portion of the reactor effluent to the reactor system. Feeding a second portion of the reactor effluent to a flash vaporizer. The flash vaporizer is configured to produce a hydrogen sulfide recirculation flow containing at least a portion of the unreacted hydrogen sulfide, as well as a crude thiol flow containing product thiols, unreacted olefins, and other components. Feeding the hydrogen sulfide recirculation flow to the reactor system. Feeding the crude thiol flow to a crude thiol separation system. The crude thiol separation system is configured to separate at least a portion of the unreacted olefins from the crude thiol flow. The separation process generates an olefin recirculation stream containing unreacted olefins, a first byproduct stream containing a first portion of other components, and a crude thiol product stream containing the product thiol and a second portion of other components. The olefin recirculation stream is returned to the reactor system and supplied. The crude thiol product stream is supplied to a product thiol purification unit. The product thiol purification unit is configured to generate a thiol product stream containing purified product thiol with at least 90 weight percent of product thiol, and a second byproduct stream containing a second portion of other components.

[0006] An apparatus for producing high-purity product thiols from hydrogen sulfide and olefins is provided. The apparatus includes a reactor system configured to receive hydrogen sulfide and olefins and generate a reactor effluent. The reactor effluent contains the product thiols, unreacted hydrogen sulfide, unreacted olefins, and other components. The reactor system is further configured to recirculate a first portion of the reactor effluent back into the reactor system. The apparatus also includes a flash vaporizer communicating with the reactor system. The flash vaporizer is configured to receive a second portion of the reactor effluent and generate a hydrogen sulfide recirculation flow containing at least some of the unreacted hydrogen sulfide. The flash vaporizer also generates a crude thiol flow containing the product thiols, unreacted olefins, and other components. The flash vaporizer is configured to return and supply the hydrogen sulfide recirculation flow back into the reactor system. For producing purified thiols, the apparatus also includes a crude thiol separation system communicating with the flash vaporizer and the reactor system. The crude thiol separation system is configured to receive the crude thiol flow. The crude thiol separation system is configured to separate at least a portion of unreacted olefins from the crude thiol stream to produce an olefin recirculation stream containing unreacted olefins, a first byproduct stream containing a first portion of other components, and a crude thiol product stream containing product thiols and a second portion of other components. The crude thiol separation system is also configured to supply the olefin recirculation stream to the reactor system. The apparatus for producing purified thiols includes a product thiol purification unit in communication with the crude thiol separation system. The product thiol purification unit is configured to receive the crude thiol product stream and produce a product thiol stream containing purified product thiols and a second byproduct stream containing a second portion of other components. The purified product thiol stream contains at least 98.5 weight percent of product thiols.

[0007] Hydrogen sulfide or R 1 SH and formula C x H (2x)A method for producing a high purity product sulfide from an olefin is provided. This method for producing a high purity product sulfide includes the following steps. Hydrogen sulfide or R 1 SH, and an olefin of the formula C x H (2x) are fed into a reactor system. The reactor system is configured to form a reactor effluent stream that includes the product sulfide, unreacted hydrogen sulfide or unreacted olefin of the formula C x H (2x) , unreacted R 1 SH, and other components. Recirculating a first portion of the reactor effluent stream back to the reactor system. Feeding a second portion of the reactor effluent stream to a sulfide separation system. The sulfide separation system is configured to produce at least one recirculation stream that includes at least a portion of the unreacted hydrogen sulfide, unreacted olefin of the formula C x H (2x) , unreacted R 1 SH, and other components, and to produce a product stream that includes a high purity product sulfide.

[0008] An apparatus for producing a high purity product sulfide from hydrogen sulfide or R 1 SH, and an olefin of the formula C x H (2x) is provided. This apparatus for producing a high purity sulfide includes a reactor system. This reactor system is configured to receive hydrogen sulfide or R 1 SH, and an olefin of the formula C x H (2x) and to form a reactor effluent stream. The reactor effluent stream includes the product sulfide, unreacted hydrogen sulfide or unreacted olefin of the formula C x H (2x) , unreacted R 1 SH, and other components. The reactor system is also configured to return and recirculate a first portion of the reactor effluent stream back to the reactor system. This apparatus for producing a purified sulfide includes a sulfide separation system in communication with the reactor system. This sulfide separation system receives a second portion of the reactor effluent stream from the reactor system and also x H (2x)Olefin, unreacted R 1 It is configured to produce at least one recirculating stream containing SH and at least a portion of other components, and a product stream containing high-purity product sulfides.

[0009] The following figures are merely illustrative of various specific embodiments of the present invention and are not intended to limit the scope of the invention as described herein. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 shows an exemplary method for producing high-purity linear thiols according to one embodiment of the present invention. [Figure 2] Figure 2 shows an exemplary method for producing high-purity linear thiols according to another embodiment of the present invention. [Figure 3] Figure 3 shows an exemplary method for producing high-purity linear thiols according to yet another embodiment of the present invention. [Figure 4] Figure 4 shows an exemplary method for producing high-purity linear thiols according to yet another embodiment of the present invention. [Figure 5] Figure 5 shows an exemplary method for producing high-purity sulfides according to one embodiment of the present invention. [Figure 6] Figure 6 shows an exemplary method for producing high-purity sulfides according to another embodiment of the present invention. [Modes for carrying out the invention]

[0011] Figure 1 shows a first embodiment of a method for producing high-purity primary thiols. As shown in Figure 1, hydrogen sulfide and alpha-olefin are supplied to the reaction system. The olefin is preferably a straight-chain alpha-C4-C18 olefin, i.e., the double bond is at the terminal of the straight-chain hydrocarbon, and is preferably n-dodeca-1-ene. The reaction system may include an absorber and at least one reactor. The absorber is configured to dissolve gaseous hydrogen sulfide in a liquid olefin, and then supply the hydrogen sulfide dissolved in the olefin to a reactor, or a bank or multiple reactors, as shown in Figure 1. The reactor system is configured to form a reactor effluent stream containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components. Non-limiting examples of other components include secondary thiols, unreacted olefin, and impurities from the incoming olefin feed stream, as well as sulfides. Impurities include, for example, branched primary thiols (vinylidene mercaptan, 2-ethyl 1-decyl mercaptan, 2-butyl 1-octyl mercaptan), sulfides (for example, (C) 12 H 25 )S(C 12 H 25 ), (C8H 17 )S(C8H 17 )); disulfide (e.g. (C 12 H 25 )SS(C 12 H 25 ), (C8H 17 )SS(C8H 17 This may include secondary thiols (e.g., 2-octanthiol, 2-dodecanethiol), saturated hydrocarbons or paraffins (e.g., octane, decane, dodecane, tetradecane), and internal olefins.

[0012] A portion of the reactor effluent is immediately recirculated into the reactor system. In one embodiment, the reactor recirculation flow is returned to the absorber via a recirculation tank communicating with the absorber. The remaining portion of the reactor effluent is then fed to a flash evaporator. The flash evaporator is configured to flash off hydrogen sulfide from the reactor effluent to produce a hydrogen sulfide recirculation flow and a crude thiol flow. The hydrogen sulfide recirculation flow is recirculated into the reactor system. In one embodiment, the hydrogen sulfide recirculation flow is fed to an absorber where it is dissolved in olefins. The crude thiol flow is then fed to a crude thiol separation system. As shown in Figure 1, the crude separation system may include a series of separation units, which are the olefin separation unit and secondary separation unit in Figure 1. These separation units are distillation columns, also called "towers" as labeled in Figure 1. The olefin separation unit is configured to produce an olefin recirculation flow as overhead from the column and a secondary flow from the bottom of the column. The secondary stream may contain secondary thiols, i.e., undesirable thiol components where the -SH group is not at the terminal position of the hydrocarbon group. The olefin recirculation stream contains unreacted olefins and is returned to the reactor system. As shown in Figure 1, a purge stream can be taken out from the olefin recirculation stream. The purge stream is intended to remove, for example, inert substances and undesirable heavy olefins. The secondary stream is fed to a secondary separation unit. In this embodiment, the secondary stream contains the desired product thiols and secondary thiols, i.e., those where the -SH group is not terminal. The secondary separation unit is configured to separate the secondary stream to produce a first byproduct stream containing undesirable secondary thiols as an overhead and a crude thiol product stream as a bottom. This crude product thiol stream is fed to a product thiol purification unit. The product thiol purification unit is a distillation column (labeled "product tower" in Figure 1) and is configured to produce a thiol product stream, which is the purified product thiol, as an overhead. The product thiol purification unit also generates a second byproduct stream at the bottom of the column, which contains other byproduct components such as sulfides. This second byproduct stream can be fed to the sulfide cracking and stripping unit.The sulfide cracking and stripping unit is configured to recover thiols in the second byproduct stream, convert at least a portion of the sulfides to olefins and thiols, and further generate a third byproduct stream containing the remaining sulfides and other impurities. Sulfohydrolysis of sulfides to mercaptans (thiols) and olefins is well known and can be carried out at high temperatures by an acid catalyst (e.g., zeolite). Complete details are described in U.S. Patents 4,313,006 and 4,396,778, which are incorporated herein by reference in their entirety for all purposes. The olefins and thiols thus recovered are then returned to the crude thiol separation system.

[0013] Figure 2 shows the same method as shown in Figure 1, but in this embodiment, a sulfide cracking and stripping apparatus is not used.

[0014] Figure 3 shows another exemplary embodiment of a method for producing high-purity thiols. In this embodiment, the reactor system and the product thiol purification system are the same as those shown in Figure 1. However, the crude thiol separation system has a different configuration than that shown in Figure 1. In this embodiment, the crude thiol separation system includes an olefin separation unit and a crude thiol separation unit. These two separation units are, in this embodiment, a distillation column (also called a tower in Figure 3). As shown in this embodiment, the crude thiol stream coming out of the flash vaporizer is fed into the crude thiol separation unit. The crude thiol separation unit is configured to produce a crude thiol product stream from the bottom of the column and an olefin and first byproduct stream from the top as an overhead. The overhead olefin and first byproduct stream coming out of the crude thiol separation unit is fed into the bottom of the olefin separation unit. The olefin separation unit is configured to separate the olefin stream to produce a byproduct stream at the bottom of the column and an olefin recirculation stream as an overhead. The olefin recirculation stream is returned to the reactor system. As shown in this embodiment, the crude thiol product stream exiting the bottom of the crude thiol separation unit is fed to the bottom of the product thiol purification unit (distillation column, also called the "tower" in Figure 3), which is configured in the same way as in Figure 1. The product thiol purification unit is configured to separate the pure product thiol as overhead and separate the secondary by-product at the bottom of the column. In this embodiment, a sulfide cracking and stripping unit is not used to further separate the bottom of the column from the product purification unit, but it may be used in another embodiment.

[0015] Figure 4 shows an embodiment similar to the embodiment shown in Figure 3, but in this embodiment, the sulfide cracking and stripping unit described in the embodiment of Figure 1 is used.

[0016] Figure 5 shows equation C x H (2x) Along with the olefin (where x is an integer from 2 to 18), hydrogen sulfide or structure R 1An exemplary embodiment of a method for producing a high-purity product sulfide from any thiol having SH is shown. As can be seen from Figure 5, the method of this embodiment is similar to the methods of Figures 1-4, except that it does not produce a thiol as the desired product and remove unwanted sulfides as impurities or by-products. The reactor system is operated using conditions that produce the sulfide as the desired product, and the thiol as a by-product produced in the reactor system is removed or recycled for further reactions that produce the desired sulfide. Hydrogen sulfide is of formula C x H (2x) When supplied to the reactor system together with olefins, the structure S(C x H (2x+1) A sulfide having )2 is produced, R 1 SH is formula C x H (2x) When supplied to the reactor system together with olefins, S(C x H (2x+1) )(R 1 ) Sulfides are generated. As shown in the embodiment of Figure 5, hydrogen sulfide or R 1 SH is formula C x H (2x) It is supplied to the reactor system along with the olefin. As in the embodiments described above, the reactor system may include an absorber and at least one or more reactors called a reactor bank. As described in other embodiments disclosed herein, the absorber is supplied with gaseous hydrogen sulfide or liquid R 1 SH is formula C x H (2x) It dissolves in liquid olefin, then formula C x H (2x) Hydrogen sulfide or R dissolved in olefin 1 It is configured to supply SH to the reactor.

[0017] In this embodiment shown in Figure 5, the reactor produces sulfide [S(C) x H (2x+1) )2 or S(C x H (2x+1) )(R 1 ), unreacted hydrogen sulfide or unreacted R 1SH, unreacted formula C x H (2x) It is configured to form a reactor effluent stream containing olefins and other components. These other components include unreacted thiols R 1 SH or unreacted hydrogen sulfide, and other components produced as by-reactions in the reactor, as well as other impurities such as heavier or lighter components present as impurities in the feedstream.

[0018] As shown in Figure 5, the first portion of this reactor effluent is returned to the reactor system and recirculated, and in the embodiment shown in Figure 5, it is also returned to the reactor circulation tank which communicates with the absorber and recirculated. The second portion of the reactor effluent is supplied to the sulfide separation system. The sulfide separation system is supplied with unreacted hydrogen sulfide or unreacted R 1 SH, unreacted formula C x H (2x) The system is configured to produce at least one recirculating flow containing olefins and at least a portion of other components. The sulfide separation system also produces high-purity sulfides, [S(C) x H (2x+1) )2 or S(C x H (2x+1) )(R 1 This generates a product stream containing )]. As shown in Figure 5, the sulfide separation system includes two separation units, which may be distillation columns referred to as the "tower" in Figure 5. The first separation unit is a distillation column, the "tower," configured to receive the reactor effluent from the reactor system into the bottom of the column. The first separation unit also receives, as overhead, unreacted hydrogen sulfide or unreacted R 1 The first separation unit is configured to produce a recirculating flow containing SH (depending on which was supplied to the reactor system) and at least some of the other light boiling point components. The first separation unit produces a crude sulfide flow from the bottom of the column containing the product sulfide that is supplied to the product sulfide purification system. The product sulfide purification system may be a distillation column, which is labeled "product tower" in Figure 5. The distillation column of the product sulfide purification system contains unreacted C x H (2x)A second recycle stream as overheads containing at least a portion of the olefin and the higher-boiling components that were at the bottom of the first separation unit, and a sulfide product stream as bottoms containing the purified product sulfide are produced. As described above, the purified product sulfide is hydrogen sulfide or R 1 SH, depending on whether either is fed to the reactor system along with the olefin of formula C x H (2x) , to be either S(C x H (2x+1) )2 or S(C x H (2x+1) )(R 1 ). In the embodiment of FIG. 5, R 1 SH is fed to the reactor system, and thus the product stream is S(C x H (2x+1) )(R 1 ) sulfide.

[0019] FIG. 6 shows another embodiment of a method for producing sulfide as the desired product. In this exemplary embodiment, hydrogen sulfide and an olefin of formula C x H (2x) are fed to the reactor system, and thus the desired product sulfide is S(C x H (2x+1) )2. Of course, one skilled in the art will understand that R 1 SH may be fed to the reactor system, and thus the product stream will be R 1 SR 2 sulfide as in FIG. 5. In this exemplary embodiment shown in FIG. 6, a flash vaporizer is in communication with the sulfide separation system and the reactor system. The flash vaporizer is configured to receive a second portion of the reactor effluent, i.e., the portion of the reactor effluent stream that was not immediately returned to and recycled by the reactor system. The flash vaporizer, as is known in the art, flash-off the light components in the reactor effluent stream by reducing the pressure and / or raising the temperature of a portion of the reactor effluent stream, and thus unreacted R 1 SH and unreacted olefin of formula C x H (2x)Depending on the relative boiling point of the olefin, unreacted hydrogen sulfide or unreacted R 1 SH or unreacted formula C x H (2x) It is configured to produce a light recirculation flow containing at least a portion of the olefins. Also, what comes out of the flash vaporizer is a crude sulfurized flow. This crude sulfurized flow contains unreacted R 1 SH and unreacted formula C x H (2x) Depending on the relative boiling points of the olefin and other components (e.g., impurities such as reaction by-products), the product sulfide and unreacted C x H (2x) Olefins, or unreacted R 1 There are heavier (higher boiling point) components, including SH, that were not removed by the flash vaporizer. This crude sulfide flow is supplied to the sulfide separation system. As shown in Figure 6, the sulfide separation includes a first separation unit (labeled "tower" in Figure 6, which is a distillation column) that communicates with the reactor system, and a product sulfide purification system that communicates with the first separation unit.

[0020] The first separation unit is configured to receive the reactor effluent from the reactor system. The first separation unit then generates the first portion of the recirculated flow as overhead. This first portion of the recirculated flow contains unreacted hydrogen sulfide or unreacted R 1 It contains SH (depending on which was supplied to the reactor system) and at least some of the other components. The bottom of the first separation unit is a crude sulfide flow containing the product sulfide and higher boiling point components that were supplied to the first separation unit and not removed as overhead in that column. This crude sulfide flow containing the product sulfide is supplied to the product sulfide purification system. As shown in Figure 6, the product sulfide purification system is a distillation column (indicated as the “product sulfide tower”). The product sulfide purification system is configured to generate a second portion of the recirculation flow as overhead. This second portion of the recirculation contains higher boiling point components from the first separation unit, but these components have lower boiling points than the product sulfide removed from the bottom of the product sulfide purification system. As shown in Figure 6, formula Cx H (2x) Since olefins and hydrogen sulfide were supplied to the reactor system, the product sulfide was S(C x H (2x+1) )2. However, a person skilled in the art would know to use R instead. 1 SH and formula C x H (2x) When the olefin is supplied to the reactor system, this process scheme is used for S(C x H (2x+1) )(R 1 You will understand that it is possible to generate ).

[0021] The following descriptions are merely illustrative and are not intended to limit the application or use of this disclosure.

[0022] The synthesis of linear mercaptans by catalytic addition of hydrogen sulfide to terminal olefins is represented by formula (1).

[0023] [ka]

[0024] The object of the present invention is to produce n-dodecyl mercaptans, having less than 1000 ppm of tetradecyl mercaptans and less than 1000 ppm of sulfides as impurities, starting from a 1-dodecene raw material containing up to 2% 1-tetradecene and other C14 olefins, on a reproducible basis.

[0025] In exemplary embodiments of the present invention, H2S and linear alpha-olefins (both from fresh and recirculated flows) are mixed before being supplied to the reactor system. This mixture is pumped into the reactor of the reactor system and exposed to UV light. The supply flow through the reactor can be varied to pass through any number of banks or combinations of tubes in either series or parallel, thereby changing the conversion rate in the method (process). The light in each tube can be turned on or off individually.

[0026] Phosphine-based or phosphite-based photoinitiators or accelerators are preferably not used in the methods disclosed herein. Non-limiting examples of phosphite compounds not included are triaryl phosphites, trimethyl phosphites, triethyl phosphites, and tributyl phosphites. An important feature of the method for preparing thiols according to the present invention is that the purified thiols may have phosphorus in amounts of less than 15 ppm by weight, e.g., less than 10 ppm by weight or less than 5 ppm by weight, as measured by inductively coupled plasma analysis.

[0027] According to some exemplary embodiments, the yield of the thiol product can be adjusted by changing the amount of reactor effluent that is returned to the reactor and recycled. In certain embodiments, the amount of reactor recirculation can be adjusted to maintain the total weight of the product thiol (e.g., n-octyl mercaptan or n-dodecyl mercaptan) present in the reactor loop at 30–40 weight percent. Lowering the concentration of the product thiol reduces the amount of unwanted sulfide byproducts generated by the method according to formula (2), thus affecting the overall selectivity of the continuous process.

[0028] [ka]

[0029] When generating the desired thiol, increasing the conversion by means of other means, such as increasing the reactor temperature or residence time exposed to UV light, can undesirably lead to an increase in the formation of undesirable sulfides in the reactor.

[0030] Another object of the present invention is to limit the effluent entering the distillation series by utilizing the reactor recirculation flow so as not to overload the downstream rectification (separation) equipment. A further object is to maintain a high H2S / alpha-olefin ratio (i.e., a molar ratio higher than 3:1, 5:1, 7:1, 10:1 and up to 20:1) within the reaction zone by using the reactor recirculation flow without the need to recompress large amounts of H2S. In certain embodiments, the single-pass olefin conversion through the reactor system is maintained at approximately 40-50% to limit the formation of sulfide byproducts within the reactor. According to some embodiments, the majority of the reactor effluent (80-90%) is returned to the absorber recirculation tank and recirculated via the reactor recirculation flow. The recirculation line at the outlet of the reactor system allows approximately 65% ​​or 70% or 75% or 80% or 85% or 90% or 95% by weight of the reactor effluent to be returned to a recirculation tank connected to the absorber and recirculated there, where the new olefins and recirculated olefins are mixed before re-entering the reactor system. H2S is also recirculated in a separate flow from the reactor effluent recirculation flow, so both new and recirculated H2S are introduced into the absorber.

[0031] In exemplary embodiments, the absorber has a recirculation tank in communication with it, and according to some embodiments, new and recirculated reactants are introduced into the recirculation tank before being supplied to the absorber and then the reactor system. Typically, the absorber and recirculation tank are maintained under high pressure. H2S is absorbed into the liquid phase (usually a mixture mainly of olefins and thiols). The recirculation tank collects the reactor recirculated liquid, vaporizer recirculated gas (and some liquids), and recirculated olefins from the olefin separation unit and recirculates them to the reactor.

[0032] One embodiment of the present invention is a method for producing a high-purity linear thiol product from hydrogen sulfide and a linear alpha-olefin, The method is: A step of supplying hydrogen sulfide and olefin to a reactor system, wherein the reactor system is configured to form a reactor effluent containing: product thiols, unreacted hydrogen sulfide, unreacted olefin and other components; A process of recirculating the first portion of the reactor effluent into the reactor system; The process involves supplying a second portion of the reactor effluent to a flash vaporizer, the flash vaporizer being: A process configured to produce a hydrogen sulfide recirculation stream containing at least a portion of unreacted hydrogen sulfide and a crude thiol stream containing product thiols, unreacted olefins, and other components; The process of supplying a recirculating hydrogen sulfide flow to the reactor system; A step of supplying a crude thiol stream to a crude thiol separation system, wherein the crude thiol separation system is: Separate at least a portion of the unreacted olefin from the crude thiol stream: A process configured to produce an olefin recirculation stream containing unreacted olefins, a first byproduct stream containing a first portion of other components, and a crude thiol product stream containing the product thiol and a second portion of other components; A step of supplying a recirculating olefin flow to the reactor system; A step of supplying a crude thiol product stream to a product thiol purification unit, wherein the product thiol purification unit is: A process configured to produce a thiol product stream containing purified product thiols with at least 98.2 weight percent of product thiols, and a second byproduct stream containing residual product thiols of a second portion of other components, Includes.

[0033] In one embodiment of this method, the linear alphaolefin includes, is essentially, or consists of a C4-C18 linear alphaolefin.

[0034] In one embodiment of this method, the alphaolefin includes, is essentially, or consists of a C12 linear alphaolefin.

[0035] In one embodiment of this method, the product thiol comprises, essentially consists of, or comprises n-dodecyl mercaptan, tetradecyl mercaptan in less than 1000 ppm by weight, and a sulfide in less than 1000 ppm.

[0036] In one embodiment of this method, the amount of the first portion of the reactor effluent that is recycled back into the reactor system maintains an amount of 20% to 70% by weight of the product thiols in the reactor system.

[0037] In one embodiment of this method, the crude thiol separation system includes an olefin separation unit and a secondary separation unit. The crude thiol stream is supplied to the olefin separation unit. The olefin separation unit is: Generates olefin recirculation flow and secondary flow; It is configured to supply the secondary flow to the secondary separation unit. The secondary separation unit is: The system is configured to separate the secondary flow and generate a primary byproduct flow and a crude thiol product flow.

[0038] The secondary stream contains the crude thiol product and by-products of the reaction.

[0039] In one embodiment of this method, a second byproduct stream containing a second portion of other components contains sulfides, and the second byproduct stream is supplied to a sulfide cracking and stripping unit, which: Convert sulfides into olefins and thiols; It generates a third byproduct stream containing sulfides; The system is configured to supply the olefin and thiol to a crude thiol separation system.

[0040] In one embodiment of this method, the crude thiol separation system includes an olefin separation unit and a crude thiol separation unit, where, The crude thiol stream is supplied to the crude thiol separation unit, which then: A crude thiol product stream and an olefin stream containing the first byproduct are generated; It is configured to supply an olefin stream containing the first byproduct to the olefin separation unit; The olefin separation unit is: The system is configured to separate the olefin stream containing the first byproduct and generate a first byproduct stream and an olefin recirculation stream.

[0041] In one embodiment of this method, the reactor system includes an absorption unit communicating with the reactor bank, wherein the absorption unit is: Accepting hydrogen sulfide and olefins, A liquid reactor bank feed stream is formed containing at least a portion of the hydrogen sulfide dissolved in the olefin. The liquid reactor bank supply flow is configured to supply the reactor bank; The reactor bank is: The first recirculation portion of the reactor outflow and the liquid reactor bank supply flow are received. It is configured to form a reactor effluent stream containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components.

[0042] The olefin stream may contain reaction byproducts that can be removed from the olefin separation unit as a first byproduct stream.

[0043] In one embodiment of this method, the reactor effluent contains 20% to 60% by weight of the product thiol.

[0044] In one embodiment of this method, the reactor effluent contains 20% to 55% by weight of the product thiol.

[0045] In one embodiment of this method, the reactor effluent contains 20% to 45% by weight of the product thiol.

[0046] In one embodiment of this method, the reactor system further includes: The reactor is configured to use electromagnetic radiation to form product thiols from hydrogen sulfide and olefins, and the reactor effluent contains less than 5% by weight of an accelerator compound and / or less than 5% by weight of an initiator compound based on the weight of the olefin.

[0047] In one embodiment of this method, the wavelength of electromagnetic radiation is 100 nm to 400 nm, or similar.

[0048] In one embodiment of this method, the accelerator compound and / or initiator compound is selected from the group consisting of alkyl and aryl phosphites, phosphines, azobisisobutyronitrile, benzophenone and its derivatives, thiobenzophenone, xanthene compounds, alkylboranes, and mixtures thereof.

[0049] In one embodiment of this method, the purified thiol product contains less than 10 ppm of phosphorus. In various embodiments, the amount of phosphorus is, for example, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, less than 1 ppm, 0 ppm to less than 10 ppm, between 1 and 9 ppm, between 1 and 7 ppm, between 2 and 8 ppm, between 4 and 7 ppm, between 1 and 5 ppm, between 2 and 6 ppm, between 1 and 4 ppm, between 1 and 3 ppm, between 2 and 4 ppm, etc. The amount of phosphorus was determined by inductively coupled plasma (ICP) mass spectrometry. The samples were decomposed with sulfuric acid and nitric acid in a Milestone UltraWAVE microwave decomposition system. The decomposed samples were diluted by gravimetric analysis. Reagent blanks were carried with the samples, and the sample results were corrected with the blanks. The samples were analyzed for trace metals relative to the calibration curve using an Agilent 7700xICP-MS. The instrument was background-corrected. Subsequent dilutions can be performed to bring the target element into the calibration range.

[0050] In one embodiment of this method, the product thiol purification unit includes at least one distillation column containing structured packing.

[0051] One embodiment of the present invention is a composition of a purified product thiol produced according to one embodiment of a method for producing purified thiols disclosed herein.

[0052] According to some embodiments of the purified product thiols produced according to one embodiment of the present method for the production of purified thiols, the purified product thiols contain, are essentially composed of, or consist of less than 10 ppm of phosphorus. In various embodiments of the composition of the purified product thiols, the amount of phosphorus is less than 9 ppm, for example, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, less than 1 ppm, 0 ppm to less than 10 ppm, between 1 and 9 ppm, between 1 and 7 ppm, between 2 and 8 ppm, between 4 and 7 ppm, between 1 and 5 ppm, between 2 and 6 ppm, between 1 and 4 ppm, between 1 and 3 ppm, between 2 and 4 ppm, etc. The amount of phosphorus was determined by inductively coupled plasma (ICP) mass spectrometry. Samples were decomposed with sulfuric acid and nitric acid in a Milestone UltraWAVE microwave decomposition apparatus. The decomposed samples were diluted by gravimetric method. A reagent blank was carried with the sample, and the sample results were corrected with the blank. The sample was analyzed for trace metals relative to the calibration curve using an Agilent 7700xICP-MS. The instrument was corrected for background. Subsequent dilutions can be performed to bring the desired elements into the calibration range. According to some embodiments of the purified product thiol composition, the product thiol contains, is essentially derived from, or consists of n-dodecyl mercaptan (NDM). According to some embodiments of the purified product thiol, the product thiol contains, is essentially derived from, or consists of n-octyl mercaptan. According to some exemplary embodiments of the purified product thiol composition, the purified product thiol contains, is essentially derived from, or consists of n-dodecyl mercaptan and tetradecyl mercaptan and sulfides less than 1000 ppm by weight.

[0053] One embodiment of the present invention is an apparatus for producing high-purity linear thiol products from hydrogen sulfide and linear alpha-olefins, wherein the apparatus is: A reactor system configured to accept hydrogen sulfide and linear alpha-olefins and generate a reactor effluent containing product linear thiols, unreacted hydrogen sulfide, unreacted linear alpha-olefins, and other components, further configured to return and recirculate a first portion of the reactor effluent back into the reactor system; A flash vaporizer in communication with a reactor system, the flash vaporizer being configured to receive a second portion of the reactor outflow and produce a hydrogen sulfide recirculation flow containing at least a portion of unreacted hydrogen sulfide and a crude thiol flow containing product linear thiols, unreacted linear alpha-olefins and other components, and the flash vaporizer being configured to supply the hydrogen sulfide recirculation flow to the reactor; A crude thiol separation system communicating with a flash vaporizer and reactor system, wherein the crude thiol separation system is configured to receive a crude thiol stream, and the crude thiol separation system is: A crude thiol separation system configured to separate at least a portion of unreacted linear alpha-olefins from a crude thiol stream to produce an olefin recirculation stream containing unreacted linear alpha-olefins, a first byproduct stream containing a first portion of other components, and a crude thiol product stream containing product linear thiols and a second portion of other components; and to supply the olefin recirculation stream to the reactor system; A product thiol purification unit that communicates with a crude thiol separation system, wherein the product thiol purification unit is: Accept the crude thiol product stream; A product thiol purification unit configured to produce a product thiol stream containing purified product thiols containing at least 90 weight percent of product linear thiols, and a second byproduct stream containing a second portion of other components, This includes. In one embodiment of the apparatus for producing a purified thiol composition, the purified product thiol stream may contain at least 95% by weight of product thiol, at least 96% by weight, at least 97% by weight, at least 98% by weight, at least 98.5% by weight, at least 99.0% by weight, and at least 99.5% by weight of product thiol.

[0054] In one embodiment of this apparatus, the crude thiol separation system includes an olefin separation unit that communicates with a secondary separation unit, where, The olefin separation unit is in communication with the flash vaporizer, and: Accept the crude thiol flow; Generates olefin recirculation flow and secondary flow; It is configured to supply the secondary flow to the secondary separation unit; Here, the secondary separation unit is in communication with the product thiol purification unit, and: Accept secondary flow; The system is configured to separate the secondary flow and generate a primary byproduct flow and a crude thiol product flow.

[0055] In one embodiment of this apparatus, the thiol product purification unit is in communication with the crude thiol separation unit, and: The crude thiol product is received from the secondary separation unit; It is configured to produce a second byproduct stream containing a pure product thiol and several residual product thiols.

[0056] In one embodiment of the apparatus, the apparatus further includes a sulfide cracking and stripping unit communicating with a thiol product purification unit and a crude thiol separation unit, wherein the sulfide cracking and stripping unit is: Accept a second byproduct stream containing a second portion of other components, including sulfides; Convert at least a portion of the sulfides into olefins and thiols; A third byproduct stream containing unconverted sulfides is generated; The system is configured to supply olefins and unconverted thiols to a crude thiol separation unit.

[0057] The conversion of sulfides to olefins and thiols may involve cracking.

[0058] One embodiment of this apparatus includes a crude thiol separation system comprising an olefin separation unit communicating with a crude thiol separation unit, the crude thiol separation unit communicating with a flash vaporizer and a product thiol purification unit, The crude thiol separation unit is: Accept the crude thiol flow; This generates a crude thiol stream and an olefin stream containing the first by-product; It is configured to supply an olefin stream containing the first byproduct to the olefin separation unit; The olefin separation unit is: Separate the olefin stream containing the first byproduct; It is configured to generate a first byproduct flow and an olefin recirculation flow.

[0059] One embodiment of this apparatus includes a reactor system comprising an absorption unit communicating with a reactor bank, wherein the absorption unit is: Accepting hydrogen sulfide and linear alpha-olefins, A liquid reactor bank feed stream is formed containing at least a portion of the hydrogen sulfide dissolved in the linear alpha-olefin. The liquid reactor bank supply flow is configured to supply the reactor bank; The reactor bank is: The first recirculation portion of the reactor outflow and the liquid reactor bank supply flow are received. It is configured to form a reactor effluent containing product thiols, unreacted hydrogen sulfide, unreacted linear alpha-olefins, and other components.

[0060] In one embodiment of the apparatus, the product purification unit includes at least one distillation column containing structured packing.

[0061] One embodiment of the present invention relates to hydrogen sulfide or formula R 1 -SH thiols, and formula C x H (2x) A method for producing a high-purity product sulfide from alpha-olefin, wherein the method is: A step of supplying hydrogen sulfide or thiol and alpha-olefin to a reactor system, wherein the reactor system is: A step configured to form a reactor effluent containing product sulfides, unreacted hydrogen sulfide or unreacted alpha-olefins, unreacted linear thiols, and other components; A process of recirculating the first portion of the reactor effluent into the reactor system; A step in which a second portion of the reactor effluent is supplied to a sulfide separation system, the sulfide separation system being: A step configured to produce at least one recirculation stream containing at least a portion of unreacted hydrogen sulfide, unreacted alpha-olefin, unreacted linear thiol, and other components, and a product stream containing high-purity product sulfide, Includes.

[0062] In various embodiments, the thiol is a linear thiol, and / or the alphaolefin is a linear alphaolefin.

[0063] In one embodiment of the sulfide process, the sulfide separation system includes a first separation unit communicating with a reactor system and a product sulfide purification system communicating with the first separation unit, where, The first separation unit is: Accepting the reactor outflow from the reactor system, A first portion of at least one recirculating flow containing unreacted hydrogen sulfide, unreacted thiols, and at least a portion of other components, and a crude sulfide flow containing product sulfides are produced; The crude sulfide logistics containing the product sulfide are configured to be supplied to the product sulfide purification system, and the product sulfide purification system is: It is configured to produce at least one second portion of a recirculating stream containing at least a portion of unreacted alpha-olefins, and a sulfide product stream containing purified product sulfides.

[0064] In one embodiment of the sulfide process, the method includes a flash vaporizer in communication with a reactor system and a sulfide separation system, the flash vaporizer being: Accept the second portion of the reactor effluent; A light recirculation flow containing at least a portion of unreacted hydrogen sulfide, unreacted thiols, or unreacted alpha-olefins is generated, along with a crude sulfide flow containing product sulfides, unreacted alpha-olefins, or unreacted thiols, and other components; It is configured to supply crude sulfide logistics to a sulfide separation system.

[0065] In one embodiment of the sulfide process, hydrogen sulfide is supplied to the reactor system, and high-purity sulfide is produced using the formula S(C) x H (2x+1) )2.

[0066] In one embodiment of the sulfide process, linear thiols are supplied to the reactor system, and high-purity sulfides are produced using the formula S(C) x H (2x+1) )2, S(R 1 )2 and S(C x H (2x)+1) )(R 1 It is one or more of the following.

[0067] In one embodiment of the sulfide process, R 1 -SH thiol R 1These are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-methylpentyl, other branched hexyl, n-octyl, sec-octyl, 2-ethylhexyl, n-nonyl, branched nonyl, n-decyl, branched decyl, n-undecyl, branched undecyl, n-dodecyl, branched dodecyl, n-tridecyl, branched tridecyl, n-tetradecyl, branched tetradecyl, n-pentadecyl, branched pentadecyl, n-hexyldecyl, branched hexyldecyl, n-heptadecyl, branched heptadecyl, n-octadecyl, or branched octadecyl. In one embodiment of the sulfide process, the R of thiol 1 This may include a carboxyl functional group, a carboxylate functional group, an amide functional group, or an epoxide functional group.

[0068] In one embodiment of the sulfide process, formula C x H (2x) The value of x in the alpha-olefin is 2 to 18. The olefin is an alpha-olefin, but it is not necessarily linear; for example, it is a class called 2-ethylhexene-1, 2-butyloctene-1, 2-ethyldecene-1, or vinylidene olefin. In one embodiment of the sulfide process, the alpha-olefin may contain a carboxyl functional group, a carboxylate functional group, an amide functional group, or an epoxide functional group. In one embodiment of the sulfide process, the carboxyl, carboxylate, and amide functional groups are preferably not conjugated to the double bond of the alpha-olefin.

[0069] One embodiment of the present invention relates to hydrogen sulfide or formula R 1 -SH thiols, and formula C x H (2x) An apparatus for producing high-purity sulfide products from alpha-olefins, wherein the apparatus is: A reactor system, and the reactor system is: Accepts hydrogen sulfide or linear thiols, and alpha-olefins; Forms a reactor effluent containing product sulfides, unreacted hydrogen sulfide or unreacted alpha-olefins, unreacted thiols, and other components; A reactor system configured to recirculate the first portion of the reactor effluent into the reactor system; A sulfide separation system, wherein the sulfide separation system is in communication with a reactor system, and Accept the second portion of the reactor effluent flow from the reactor system; A sulfide separation system configured to produce at least one recirculation stream containing at least a portion of unreacted hydrogen sulfide, unreacted alpha-olefins, unreacted thiols, and other components, and a product stream containing high-purity product sulfides. The apparatus may be configured to produce high-purity linear sulfides from hydrogen sulfide or linear thiols together with linear alpha-olefins.

[0070] In one embodiment of the sulfide apparatus, the sulfide separation system includes a first separation unit communicating with a reactor system and a product sulfide purification system communicating with the first separation unit. Here, the first separation unit is: Accept the reactor effluent from the reactor system; A first portion of at least one recirculating flow containing unreacted hydrogen sulfide, unreacted thiols or unreacted alpha-olefins, and at least a portion of other components, and a crude sulfide flow containing product sulfides are produced; It is configured to supply a crude sulfide transport system containing product sulfides to a product sulfide purification system. Here, the product sulfide purification system is: The system is configured to produce at least one second portion of a recirculating stream containing at least a portion of unreacted alpha-olefins or unreacted thiols, and a sulfide product stream containing purified product sulfides.

[0071] In one embodiment of a sulfide apparatus, the apparatus includes a flash vaporizer in communication with a reactor system and a sulfide separation system, the flash vaporizer being: Accept the second portion of the reactor effluent; A light recirculation flow containing at least a portion of unreacted hydrogen sulfide or unreacted thiols; or unreacted alpha-olefins; and a crude sulfide flow containing product sulfides, unreacted alpha-olefins or unreacted thiols, and other components are produced; It is configured to supply crude sulfide logistics to a sulfide separation system.

[0072] In various embodiments, high-purity linear product thiols are isolated with purities (wt%) such as at least 98.2%, for example, at least 98.4%, at least 98.6%, at least 98.8%, at least 99.0%, at least 99.2%, at least 99.4%, at least 99.6%, at least 99.8%, 98.2%~99.8%, 98.2%~99.6%, 98.2%~99.4%, 98.2%~99.2%, 98.4%~99.6%, 98.4%~99.2%, 98.6%~99.6%, 98.8%~99.6%, and 99.0%~99.6%. For example, the thiol purity in wt% may be higher than 90%, preferably higher than 95%, and most preferably higher than 98%. The purity may be higher than 91%, higher than 92%, higher than 93%, higher than 94%, higher than 95%, higher than 96%, higher than 96%, or higher than 98%.

[0073] In various embodiments, the high-purity linear product thiol (also called "mercaptan") is n-octyl mercaptan, n-nonyl mercaptan, n-decyl mercaptan, n-undecyl mercaptan, n-dodecyl mercaptan, n-tridecyl mercaptan, n-tetradecyl mercaptan, n-pentadecyl mercaptan, n-hexyldecyl mercaptan, n-heptadecyl mercaptan, or n-octadecyl mercaptan.

[0074] In various embodiments, the linear alphaolefin is 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, or 1-octadecene.

[0075] In various embodiments, the amount of tetradecyl mercaptan impurities is less than 1000 ppm, for example, less than 800 ppm, less than 600 ppm, less than 400 ppm, less than 200 ppm, less than 100 ppm, less than 80 ppm, less than 50 ppm, less than 1000 ppm but more than 50 ppm, less than 500 ppm but more than 50 ppm, less than 200 ppm but more than 50 ppm, etc.

[0076] In various embodiments, the amount of sulfide impurities is less than 1000 ppm, for example, less than 800 ppm, less than 600 ppm, less than 400 ppm, less than 200 ppm, less than 100 ppm, less than 80 ppm, less than 50 ppm, less than 1000 ppm but more than 50 ppm, less than 500 ppm but more than 50 ppm, less than 200 ppm but more than 50 ppm, etc.

[0077] In various embodiments, the sulfide impurities are n-octyl sulfide, n-nonyl sulfide, n-decyl sulfide, n-undecyl sulfide, n-dodecyl sulfide, n-tridecyl sulfide, n-tetradecyl sulfide, n-pentadecyl sulfide, n-hexyldecyl sulfide, n-heptadecyl sulfide, or n-octadecyl sulfide. In some embodiments, the sulfide impurities may be any of several sulfides produced from secondary mercaptans generated as by-products of reactions during the process, such as 2-alkyl mercaptans produced from vinylidene olefins in the feed alpha-olefin.

[0078] In various embodiments, the amount of linear product thiols present in the first portion of the reactor effluent is 20-70% by weight, for example, 20-60% by weight, 20-55% by weight, 20-45% by weight, 20-40% by weight, etc.

[0079] In various embodiments, the accelerator compound is present in an amount less than 5% by weight of the linear alphaolefin or alphaolefin, for example, less than 3%, less than 1%, etc. In certain embodiments, the accelerator compound is not present in the method of the present invention as described herein.

[0080] In various embodiments, the electromagnetic radiation is ultraviolet radiation, and the radiation source is not particularly limited and may include conventional radiation sources such as mercury arc lamps and light-emitting diodes that produce ultraviolet radiation. Furthermore, the radiation source can be located inside or outside the reactor, and if the radiation source is located outside the reactor, the reactor may be transparent in whole or in part and may be made of Pyrex®, Bycor, quartz, or other suitable material.

[0081] In various embodiments, the electromagnetic emission wavelength is 10-600 nm, for example, 50-600 nm, 50-400 nm, 100-400 nm, 10-300 nm, 50-300 nm, 100-300 nm, etc.

[0082] In various embodiments, the molar ratio of H2S to linear alphaolefin starting material is 20:1 to 3:1, for example, 10:1, 7:1, 5:1, 4:1, 3:1, etc.

[0083] In various embodiments, the reactor system operates in a temperature range of -10 to 120°C and a pressure range of 10 to 1,000 psig. In various embodiments, the temperature range is -10 to 100°C, for example, -10 to 80°C, -5 to 60°C, 0 to 100°C, 0 to 80°C, 0 to 60°C, 10 to 100°C, 10 to 80°C, 10 to 60°C, 20 to 100°C, 20 to 80°C, 20 to 60°C, 30 to 100°C, 30 to 80°C, 30 to 60°C, etc. In various embodiments, the pressure is in the range of 10-800 psig, for example, 10-600 psig, 10-400 psig, 50-800 psig, 50-600 psig, 50-400 psig, 100-800 psig, 100-600 psig, 100-400 psig, 200-1,000 psig, 200-800 psig, 200-600 psig, 200-500 psig, 300-800 psig, 300-600 psig, 400-800 psig, 500-800 psig, etc.

[0084] In various embodiments, the crude thiol separation unit operates in a temperature range of 50 to 260°C and a pressure range of -14.7 to 0 psig.

[0085] In various embodiments, the thiol purification unit operates in a temperature range of 0 to 500°C and a pressure range of -14.7 to 100 psig. In various embodiments, the temperature range is 0 to 400°C, for example, 0 to 300°C, 0 to 200°C, 50 to 400°C, 50 to 300°C, 50 to 200°C, 75 to 400°C, 75 to 300°C, 75 to 200°C, 100 to 400°C, 100 to 300°C, etc. In various embodiments, the pressure is in the range of -14.7 to 15 psig, for example, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -14.7 to 15 psig, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to 10 psig, -10 to 15 psig, -10 to 10 psig, -10 to 0 psig, 0 to 15 psig, 0 to 10 psig, etc.

[0086] In various embodiments, the olefin separation unit operates in a temperature range of 0 to 500°C and a pressure range of -50 to 15 psig. In various embodiments, the temperature range is 0 to 400°C, for example, 0 to 300°C, 0 to 200°C, 50 to 400°C, 50 to 300°C, 50 to 200°C, 75 to 400°C, 75 to 300°C, 75 to 200°C, 100 to 400°C, 100 to 300°C, etc. In various embodiments, the pressure is in the range of -14.7 to 15 psig, for example, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -14.7 to 15 psig, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -10 to 15 psig, -10 to 10 psig, -10 to 0 psig, -10 to 10 psig, 0 to 15 psig, 0 to 10 psig, etc.

[0087] In various embodiments, the secondary separation unit operates in a temperature range of 0 to 500°C and a pressure range of -14.7 to 15 psig. In various embodiments, the temperature range is 0 to 400°C, for example, 0 to 300°C, 0 to 200°C, 50 to 400°C, 50 to 300°C, 50 to 200°C, 75 to 400°C, 75 to 300°C, 75 to 200°C, 100 to 400°C, 100 to 300°C, etc. In various embodiments, the pressure is in the range of -14.7 to 15 psig, for example, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -14.7 to 15 psig, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -10 to 15 psig, -10 to 10 psig, -10 to 0 psig, -10 to -10 psig, 0 to 15 psig, 0 to 10 psig, etc.

[0088] In various embodiments, the sulfide cracking and stripping unit operates in a temperature range of 50 to 500°C and a pressure range of -50 to 15 psig. In various embodiments, the temperature range is 50 to 400°C, for example, 50 to 300°C, 50 to 200°C, 100 to 400°C, 100 to 300°C, 150 to 400°C, 150 to 300°C, 200 to 500°C, 200 to 400°C, 300 to 500°C, etc. In various embodiments, the pressure ranges from -14.7 to 15 psig, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -14.7 to 15 psig, -14.7 to 10 psig, -14.7 to 0 psig, -14.7 to -10 psig, -10 to 15 psig, -10 to 10 psig, -10 to 0 psig, -10 to -10 psig, 0 to 15 psig, 0 to 10 psig, etc.

[0089] In various embodiments, one or more of the thiol separation unit, thiol purification unit, olefin separation unit, and secondary separation unit include at least one distillation column containing structured packing. Suitable packing materials include, but are not limited to, metal packing (e.g., grid packing, plate packing, gauze packing), ceramic packing, and plastic packing. Examples of distillation columns include, but are not limited to, continuous columns, batch columns, and HiGee (rotating packed bed) columns.

[0090] In various embodiments, the fluid stream of hydrogen sulfide and linear alpha-olefin reactants supplied to the reactor system includes, but is not limited to, one or more organic solvents such as hydrocarbon solvents, aromatic solvents, ketone solvents, alcohol solvents, ether solvents, or combinations thereof. Saturated hydrocarbons and solvents that do not absorb or interfere with UV light of the above-mentioned specific wavelength range are suitable.

[0091] Exemplary embodiments of the present invention can be summarized as follows: Embodiment 1: A method for producing a high-purity thiol product from hydrogen sulfide and an olefin, wherein the method is: A step of supplying the hydrogen sulfide and the olefin to a reactor system, wherein the reactor system is: The process is configured to form a reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components; A step of recirculating a first portion of the reactor outflow into the reactor system; A step of supplying a second portion of the reactor outflow to a flash vaporizer, wherein the flash vaporizer is: A process configured to produce a hydrogen sulfide recirculation stream containing at least a portion of the unreacted hydrogen sulfide, and a crude thiol stream containing the product thiol, the unreacted olefin, and the other components; The process of supplying the hydrogen sulfide recirculation flow to the reactor system; The process involves supplying the crude thiol stream to a crude thiol separation system, wherein the crude thiol separation system is: Separate at least a portion of the unreacted olefin from the crude thiol stream: A process configured to produce an olefin recirculation stream containing the unreacted olefin, a first byproduct stream containing a first portion of the other components, and a crude thiol product stream containing the product thiol and a second portion of the other components; The process of supplying the olefin recirculation flow to the reactor system; The process involves supplying the crude thiol product stream to a product thiol purification unit, wherein the product thiol purification unit comprises: A process configured to produce a thiol product stream containing purified product thiol, which contains at least 90 weight percent of the product thiol, and a second byproduct stream containing the second portion of the other components, A method that includes this.

[0092] Embodiment 2: The method of Embodiment 1, wherein the olefin comprises a linear hydrocarbon of a C4-C18 linear alpha-olefin.

[0093] Embodiment 3: The method of Embodiment 1 or 2, wherein the olefin comprises a linear hydrocarbon of a C12 linear alpha-olefin, and the product thiol comprises n-dodecyl mercaptan, tetradecyl mercaptan in less than 1000 ppm by weight, and a sulfide in less than 1000 ppm.

[0094] Embodiment 4: Any of Embodiments 1 to 3, wherein the amount of the first portion of the reactor effluent recirculated into the reactor system maintains an amount of 20% to 60% by weight of the product thiol in the reactor system.

[0095] Embodiment 5: The crude thiol separation system includes an olefin separation unit and a secondary separation unit, The crude thiol stream is supplied to the olefin separation unit. The olefin separation unit is: The aforementioned olefin recirculation flow and secondary flow are generated; The system is configured to supply the secondary flow to the secondary separation unit. The aforementioned secondary separation unit is: A method in any of embodiments 1 to 4, configured to separate the secondary flow and generate the first byproduct flow and the crude thiol product flow.

[0096] Embodiment 6: The second byproduct stream, which includes the second portion of the other components, contains a sulfide, and the second byproduct stream is supplied to a sulfide cracking and stripping unit, the sulfide cracking and stripping unit: The sulfide is converted to an olefin and a thiol; a third byproduct stream containing the sulfide is generated; A method in any of embodiments 1 to 5, configured to supply the olefin and thiol to the crude thiol separation system.

[0097] Embodiment 7: The crude thiol separation system includes an olefin separation unit and a crude thiol separation unit, The crude thiol stream is supplied to the crude thiol separation unit, and the crude thiol separation unit: The crude thiol product stream and the olefin stream are generated; The olefin stream is configured to be supplied to the olefin separation unit; The olefin separation unit is: A method according to any one of embodiments 1 to 6, configured to separate the olefin stream (including the first by-product) to generate the first by-product stream and the olefin recirculation stream.

[0098] Embodiment 8: The reactor system includes an absorption unit communicating with a reactor bank, wherein the absorption unit is: The hydrogen sulfide, the olefin, and the first recirculation portion of the reactor outflow are received. A liquid reactor bank supply flow containing at least a portion of the hydrogen sulfide dissolved in the olefin and the first recirculation portion of the reactor outlet flow are formed. The liquid reactor bank supply flow is configured to supply the reactor bank; The reactor bank is: The first recirculation portion of the reactor outflow and the liquid reactor bank supply flow are received, A method in any of embodiments 1 to 7, configured to form the reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components.

[0099] Embodiment 9: The method according to any one of Embodiments 1 to 8, wherein the reactor effluent contains 20% to 70% by weight of the product thiol.

[0100] Embodiment 10: The method according to any of Embodiments 1 to 9, wherein the first portion of the reactor effluent constitutes at least 70 weight percent of the total reactor effluent.

[0101] Embodiment 11: The method according to any one of Embodiments 1 to 10, wherein the conversion of linear alphaolefins to the product thiols in the reactor system is 50 weight percent or less, and the amount of sulfides in the reactor is less than 10 weight percent.

[0102] Embodiment 12: The reactor system is further configured to use electromagnetic radiation with a wavelength of 100 nm to 600 nm to form the product thiol from the hydrogen sulfide and the olefin, and the reactor effluent contains less than 5 weight percent of an accelerator compound and / or less than 5 weight percent of an initiator compound selected from the group consisting of alkylboranes, phosphites, azobisisobutyronitriles, benzophenones and their derivatives, thiobenzophenones, xanthene compounds, and mixtures thereof, according to any of Embodiments 1 to 11.

[0103] Embodiment 13: The method according to any one of Embodiments 1 to 12, wherein the purified product thiol contains phosphorus at a concentration of less than 10 ppm by weight.

[0104] Embodiment 14: The method according to any one of Embodiments 1 to 13, wherein the product thiol purification unit includes at least one distillation column containing structured packing.

[0105] Embodiment 15: Apparatus for producing high-purity thiol products from hydrogen sulfide and olefin, wherein the apparatus is: A reactor system configured to receive the hydrogen sulfide and the olefin and to generate a reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin and other components, further configured to return and recirculate a first portion of the reactor effluent back into the reactor system; A flash vaporizer in communication with the reactor system, the flash vaporizer being configured to receive a second portion of the reactor outflow and generate a hydrogen sulfide recirculation flow containing at least a portion of the unreacted hydrogen sulfide and a crude thiol flow containing the product thiol, the unreacted olefin and the other components, and the flash vaporizer being configured to supply the hydrogen sulfide recirculation flow to the reactor system; A crude thiol separation system communicating with the flash vaporizer and the reactor system, wherein the crude thiol separation system is configured to receive the crude thiol stream, and the crude thiol separation system is configured to: A crude thiol separation system configured to separate at least a portion of the unreacted olefin from the crude thiol stream to produce an olefin recirculation stream containing the unreacted olefin, a first byproduct stream containing a first portion of the other components, and a crude thiol product stream containing the product thiol and a second portion of the other components; and to supply the olefin recirculation stream to the reactor system; A product thiol purification unit that communicates with the crude thiol separation system, wherein the product thiol purification unit comprises: The crude thiol product stream is accepted; A product thiol purification unit configured to produce a product thiol stream containing purified product thiol with at least 98.5 weight percent of the product thiol, and a second byproduct stream containing the second portion of the other components, A device including a device.

[0106] Embodiment 16: The crude thiol separation system includes an olefin separation unit communicating with a secondary separation unit, the olefin separation unit communicating with the flash vaporizer and configured to receive the crude thiol flow; generate the olefin recirculation flow and secondary flow; and supply the secondary flow to the secondary separation unit; The apparatus of embodiment 15, wherein the secondary separation unit is in communication with the product thiol purification unit and is configured to receive the secondary flow and separate the secondary flow to produce the first byproduct flow and the crude thiol product flow.

[0107] Embodiment 17: Further comprising a sulfide cracking and stripping unit communicating with the thiol product purification unit and the crude thiol separation unit, The aforementioned sulfide cracking and stripping unit is: Accept the second byproduct stream, which includes the second portion of the other components containing sulfides; An apparatus according to embodiment 15 or 16, configured to convert the sulfide into an olefin and a thiol; generate a third byproduct stream containing the sulfide; and supply the olefin and thiol to the crude thiol separation system.

[0108] Embodiment 18: The crude thiol separation system includes an olefin separation unit that communicates with a crude thiol separation unit, the crude thiol separation unit communicates with the flash vaporizer and the product thiol purification unit, The crude thiol separation unit is: Accept the aforementioned rough stream; The crude product thiol stream and olefin stream are generated; The olefin stream is configured to be supplied to the olefin separation unit; The olefin separation unit is: The aforementioned olefin stream is separated; An apparatus according to any of embodiments 15 to 17, configured to generate the first byproduct flow and the olefin recirculation flow.

[0109] Embodiment 19: The reactor system comprises an absorption unit communicating with a reactor bank, wherein the absorption unit is: The hydrogen sulfide, the olefin, and the first recirculation portion of the reactor outflow are received. A liquid reactor bank supply flow is formed, which includes at least a portion of the hydrogen sulfide dissolved in the olefin and the first recirculation portion of the reactor outflow. The liquid reactor bank supply flow is configured to supply the reactor bank; The reactor bank is: The first recirculation portion of the reactor outflow and the liquid reactor bank supply flow are received, An apparatus according to any one of embodiments 15 to 18, configured to form the reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components.

[0110] Embodiment 20: The apparatus according to any of Embodiments 15 to 19, wherein the product thiol purification unit includes at least one distillation column containing structured packing.

[0111] Embodiment 21: Hydrogen sulfide or R 1 SH and formula C x H (2x) A method for producing a high-purity product sulfide from an olefin, wherein the method is: The hydrogen sulfide or the R 1 SH, and the aforementioned formula C x H (2x) A step of supplying the olefin to a reactor system, wherein the reactor system is: The aforementioned sulfide product, unreacted hydrogen sulfide, or unreacted C x H (2x) Olefin, unreacted R 1 A process configured to form a reactor effluent flow containing SH and other components; A step of recirculating a first portion of the reactor outflow into the reactor system; A step of supplying a second portion of the reactor effluent to a sulfide separation system, wherein the sulfide separation system is: Unreacted hydrogen sulfide, unreacted C x H (2x) The olefin, the unreacted R 1 A process configured to produce at least one recirculating stream containing SH and at least a portion of other components, and a product stream containing the high-purity product sulfide, A method that includes this.

[0112] Embodiment 22: The sulfide separation system includes a first separation unit communicating with the reactor system and a product sulfide purification system communicating with the first separation unit, The first separation unit is: The reactor outflow from the reactor system is received; Unreacted hydrogen sulfide or unreacted R 1 SH or the unreacted C of the above formula x H (2x)A first portion of the recirculating flow comprising at least a portion of the olefin and other components, and a crude sulfide flow comprising the product sulfide; The crude sulfide flow containing the product sulfide is configured to be supplied to the product sulfide purification system. The aforementioned sulfide purification system is: Unreacted C x H (2x) The olefin or unreacted R 1 The method of embodiment 21, configured to produce at least one second portion of the recirculation flow including at least a portion of the other SH, and a sulfide product flow containing the purified product sulfide.

[0113] Embodiment 23: Includes a flash vaporizer in communication with the reactor system and the sulfide separation system, wherein the flash vaporizer is: The second portion of the reactor effluent is received; Unreacted hydrogen sulfide or unreacted R 1 SH or unreacted formula C x H (2x) A light recirculating flow containing at least a portion of the olefin, and the product sulfide and the unreacted R 1 SH or the unreacted C of the above formula x H (2x) A crude sulfurized liquid is produced containing the other olefin and the aforementioned other components; The method according to embodiment 21 or 22, configured to supply the crude sulfide logistics to the sulfide separation system.

[0114] Embodiment 24: Hydrogen sulfide is supplied to the reactor system, and the high-purity sulfide is S(C) x H (2x+1) )2, including any of the methods in embodiments 21 to 23.

[0115] Appearance 25: R 1 SH is supplied to the reactor system, and the high-purity sulfide is converted into S(C) x H (2x+1) )(R 1 Any method of embodiment 21 to 24, including ).

[0116] Appearance 26: R 1 -SH thiol R 1 The method according to any of embodiments 21 to 25, wherein is methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexyldecyl, n-heptadecyl, or n-octadecyl.

[0117] Embodiment 27: Formula C x H (2x) A method in any of embodiments 21 to 26, wherein x is an integer from 2 to 18, for the olefin.

[0118] Embodiment 28: Hydrogen sulfide or R 1 SH and formula C x H (2x) An apparatus for producing high-purity sulfide products from olefins, wherein the apparatus is: A reactor system, wherein the reactor system is: The hydrogen sulfide or the R 1 SH, and the aforementioned formula C x H (2x) Accepting the olefin, The product sulfide, the unreacted hydrogen sulfide, or the unreacted C x H (2x) R 1 Forms a reactor effluent containing SH and other components; A reactor system configured to recirculate a first portion of the reactor outflow into the reactor system; A sulfide separation system, wherein the sulfide separation system is in communication with the reactor system, and the sulfide separation system is: The second portion of the reactor outflow from the reactor system is received; Unreacted hydrogen sulfide, unreacted C x H (2x) The olefin, the unreacted R 1A sulfide separation system configured to produce at least one recirculation stream containing SH and at least a portion of other components, and a product stream containing the high-purity product sulfide, A device including a device.

[0119] Embodiment 29: The sulfide separation system includes a first separation unit communicating with the reactor system and a product sulfide purification system communicating with the first separation unit, The first separation unit is: The reactor outflow from the reactor system is received; Unreacted hydrogen sulfide and unreacted R 1 SH or the unreacted C of the above formula x H (2x) The olefin and at least one first portion of the recirculation flow comprising at least a portion of the other components, and the product sulfide and the unreacted R 1 SH or the unreacted C of the above formula x H (2x) A crude sulfurized logistics product containing the other olefin is produced; The crude sulfide flow containing the product sulfide is configured to be supplied to the product sulfide purification system; The aforementioned sulfide purification system is: Unreacted R 1 SH or the unreacted C of the above formula x H (2x) Apparatus according to embodiment 28, configured to produce at least one second portion of the recirculation flow containing at least a portion of the other olefin, and a sulfide product flow containing the purified product sulfide.

[0120] Embodiment 30: comprising a flash vaporizer in communication with the reactor system and the sulfide separation system, wherein the flash vaporizer is: The second portion of the reactor effluent is received; Unreacted hydrogen sulfide or unreacted R 1 SH or the unreacted C of the above formula x H (2x)A light recirculating flow containing at least a portion of the olefin, and the product sulfide and the unreacted R 1 SH or the unreacted C of the above formula x H (2x) A crude sulfurized liquid is produced containing the other olefin and the aforementioned other components; An apparatus according to embodiment 28 or 29, configured to supply the crude sulfide transport to the sulfide separation system.

[0121] While embodiments described herein are intended to provide a clear and concise description, it will be understood that embodiments can be combined and separated in various ways without departing from the present invention. For example, it should be understood that all preferred features described herein are applicable to all embodiments of the present invention described herein.

[0122] In some embodiments, the inventions herein can be interpreted as excluding elements or process steps that do not substantially affect the basic and novel properties of the curable compositions, materials, products, and articles prepared therefrom, as well as the methods for producing and using such curable compositions as described herein. Furthermore, in some embodiments, the inventions can be interpreted as excluding elements or process steps of methods not specified herein.

[0123] While the present invention is illustrated and described herein with reference to specific embodiments, it is not intended to be limited to the details shown. Rather, various modifications to the details can be made within the equivalent scope and range of the claims and without departing from the present invention. [Examples]

[0124] Example 1: A 1:10 molar mixture of dodecene-1 and liquid H2S is fed into the reactor tubes until a stable flow is established. Next, UV light is turned on and the mixture is recirculated until 20-60% conversion to NDM is reached. Then, a portion of the mixture is fed into a vaporizer to remove most, if not all, of the H2S overhead and return it to the reactor loop. Next, the liquid is pushed into an olefin tower, where unreacted olefins are removed from the overhead and returned to the reactor for recirculation. The bottom of the olefin tower is pushed into a secondary tower, where secondary mercaptans and residual hydrocarbons are removed from the overhead, and the crude product flow is removed from the bottom of the secondary tower and pushed into the product tower. Here, the product NDM is removed from the overhead, and sulfide byproducts containing residual NDM are removed from the bottom of the product tower and pushed into the residue stripper. The residue stripper strips most, if not all, of the NDM present, partially breaking down the sulfides into olefins and NDM, which are then returned to the olefin tower for recycling. The product NDM is analyzed for purity by gas chromatography and for sulfur content by mercaptan sulfur titration, and the product tower conditions are modified to obtain the specified NDM product purity.

[0125] Table 1 below shows how the method of the present invention results in the preparation of high-purity mercaptans. In the case of n-dodecyl mercaptan, the levels of undesirable tetradecyl mercaptan and sulfide impurities were well below 0.1%.

[0126] [Table 1]

[0127] Example 2: Hydrogen sulfide at 360 psig and 37°C, and olefin at 360 psig and ambient temperature are introduced into an absorber recirculation tank and sent to a photochemical reactor operating at 40°C and 450 psig. In the photoreactor, catalytic addition of hydrogen sulfide to the terminal olefin occurs via a UV photocatalyst. The majority of the reactor effluent (65–90%) is returned to the absorber recirculation tank via the reactor recirculation line and recycled. The remainder of the reactor effluent is sent to a flash vaporizer operating at 150°C and 370 psig. The remaining liquid, which is essentially H2S-free, is then introduced into an olefin distillation tower (OT) operating at a pressure of 100 mmHga, a bottom temperature of 204–230°C, and a reflux ratio of 0.2–0.5. The olefin tower separates unreacted olefin from mercaptans and product sulfides. The olefin taken from the top of this tower is returned to the absorber recirculation tank via a new olefin supply line. The effluent from the bottom of the olefin tower is introduced into a secondary mercaptan distillation tower operating at a pressure of 50 mmHga, a bottom temperature of 221–232°C, and a reflux ratio of 15–60. The secondary tower removes secondary mercaptans produced as byproducts of the UV-catalyzed reaction. The effluent from the bottom of this tower is introduced into a product distillation tower (PT). The product distillation tower is equipped with structured packing as internal material and operates at a pressure of 25 mmHga, a bottom temperature of 182–232°C, and a reflux ratio of 0.2–1. The final product, n-dodecyl mercaptan, is removed as an overhead product.

[0128] In this example, hydrogen sulfide and 1-dodecene as an olefin were supplied to the reactor system shown in Figure 1. The product thiol was n-dodecylthiol, also known as n-dodecyl mercaptan (NDM). Various flows were analyzed by gas chromatography. The flow composition was monitored by gas chromatography (GC) with a flame ionization detector (FID) and was found to have the compositions shown in Table 2.

[0129] [Table 2]

Claims

1. A method for producing a high-purity thiol product from hydrogen sulfide and an olefin, wherein the method is: A step of supplying the hydrogen sulfide and the olefin to a reactor system, wherein the reactor system is: A step configured to form a reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components; A step of separating the reactor effluent into a first portion and a second portion, wherein the first portion and the second portion have the same chemical composition; A step of recirculating a first portion of the reactor outflow into the reactor system; A step of supplying a second portion of the reactor outflow to a flash vaporizer, wherein the flash vaporizer is: A process configured to produce a hydrogen sulfide recirculation stream containing at least a portion of the unreacted hydrogen sulfide and a crude thiol stream containing the product thiol, the unreacted olefin and the other components; The process of supplying the hydrogen sulfide recirculation flow to the reactor system; The process involves supplying the crude thiol stream to a crude thiol separation system, wherein the crude thiol separation system is: Separate at least a portion of the unreacted olefin from the crude thiol stream: A process configured to produce an olefin recirculation stream containing the unreacted olefin, a first byproduct stream containing a first portion of the other components, and a crude thiol product stream containing the product thiol and a second portion of the other components; The steps include supplying the olefin recirculation flow to the reactor system; The process involves supplying the crude thiol product stream to a product thiol purification unit, wherein the product thiol purification unit comprises: A process configured to produce a thiol product stream containing purified product thiol containing at least 90 weight percent of the product thiol, and a second byproduct stream containing the second portion of the other components, A method that includes this.

2. The method according to claim 1, wherein the olefin comprises a linear hydrocarbon of a C4 to C18 linear alphaolefin.

3. The method according to claim 1 or 2, wherein the olefin comprises a linear hydrocarbon of a C12 linear alpha-olefin, and the product thiol comprises n-dodecyl mercaptan, tetradecyl mercaptan in a weight of less than 1000 ppm, and a sulfide in a weight of less than 1000 ppm.

4. The method according to any one of claims 1 to 3, wherein the amount of the first portion of the reactor effluent that is recirculated to the reactor system maintains an amount of 20% to 60% by weight of the product thiol in the reactor system.

5. The crude thiol separation system includes an olefin separation unit and a secondary separation unit. The crude thiol stream is supplied to the olefin separation unit. The olefin separation unit is: The aforementioned olefin recirculation flow and secondary flow are generated; The system is configured to supply the secondary flow to the secondary separation unit. The aforementioned secondary separation unit is: The method according to any one of claims 1 to 4, wherein the secondary flow is separated to generate the first byproduct flow and the crude thiol product flow.

6. The second byproduct stream, which includes the second portion of the other components, contains sulfides, and the second byproduct stream is supplied to a sulfide cracking and stripping unit, the sulfide cracking and stripping unit: The aforementioned sulfide is converted into an olefin and a thiol; A third byproduct stream containing the aforementioned sulfide is generated; The method according to any one of claims 1 to 5, configured to supply the olefin and thiol to the crude thiol separation system.

7. The crude thiol separation system includes an olefin separation unit and a crude thiol separation unit, The crude thiol stream is supplied to the crude thiol separation unit, which then: The crude thiol product stream and the olefin stream are generated; The olefin stream is configured to supply the olefin separation unit; The olefin separation unit is: The method according to any one of claims 1 to 6, configured to separate the olefin flow and generate the first byproduct flow and the olefin recirculation flow.

8. The reactor system includes an absorption unit that communicates with the reactor bank, and the absorption unit is: The hydrogen sulfide, the olefin, and the first recirculation portion of the reactor outflow are received. A liquid reactor bank supply flow containing at least a portion of the hydrogen sulfide dissolved in the olefin and the first recirculation portion of the reactor outlet flow are formed. The liquid reactor bank supply flow is configured to supply the reactor bank; The reactor bank is: The first recirculation portion of the reactor outflow and the liquid reactor bank supply flow are received. The method according to any one of claims 1 to 7, configured to form the reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components.

9. The method according to any one of claims 1 to 8, wherein the reactor effluent contains 20% to 70% by weight of the product thiol.

10. The method according to any one of claims 1 to 9, wherein the first portion of the reactor effluent constitutes at least 70 weight percent of the total reactor effluent.

11. The method according to any one of claims 1 to 10, wherein the conversion of linear alphaolefins to the product thiols in the reactor system is 50% by weight or less, and the amount of sulfides in the reactor is less than 10% by weight.

12. The method according to any one of claims 1 to 11, wherein the reactor system is further configured to use electromagnetic radiation having a wavelength of 100 nm to 600 nm to form the product thiol from the hydrogen sulfide and the olefin, and the reactor effluent contains less than 5 weight percent of an accelerator compound and / or less than 5 weight percent of an initiator compound selected from the group consisting of alkylboranes, phosphites, azobisisobutyronitriles, benzophenones, thiobenzophenones, xanthene compounds, and mixtures thereof.

13. The method according to any one of claims 1 to 12, wherein the purified product thiol contains phosphorus in an amount of less than 5 ppm by weight.

14. The method according to any one of claims 1 to 13, wherein the product thiol purification unit includes at least one distillation column containing structured packing.

15. An apparatus for producing high-purity thiol products from hydrogen sulfide and olefins, wherein the apparatus is: A reactor system configured to receive the hydrogen sulfide and the olefin and generate a reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin and other components, further configured to separate the reactor effluent into a first and second portion, and to recirculate the first portion of the reactor effluent back into the reactor system, wherein the first and second portions have the same chemical composition; A flash vaporizer in communication with the reactor system, the flash vaporizer being configured to receive a second portion of the reactor outflow and generate a hydrogen sulfide recirculation flow containing at least a portion of the unreacted hydrogen sulfide and a crude thiol flow containing the product thiol, the unreacted olefin and the other components, and the flash vaporizer being configured to supply the hydrogen sulfide recirculation flow to the reactor system; A crude thiol separation system comprising an olefin separation unit communicating with a secondary separation unit, wherein, The olefin separation unit is in communication with the flash vaporizer and the reactor system, and Accepting the aforementioned crude thiol flow; Generates olefin recirculation flow and secondary flow; The olefin recirculation flow is supplied to the reactor system; The secondary flow is configured to be supplied to the secondary separation unit; The secondary separation unit is in communication with the product thiol purification unit, and: The aforementioned secondary flow acceptance; A crude thiol separation system configured to separate the secondary flow and generate a first byproduct flow and a crude thiol product flow; A product thiol purification unit that communicates with the crude thiol separation system, wherein the product thiol purification unit comprises: The crude thiol product stream is accepted; A product thiol purification unit configured to produce a product thiol stream containing purified product thiol with at least 98.5 weight percent of the product thiol, and a second byproduct stream containing a second portion of the other components, A device including a device.

16. The apparatus according to claim 15, wherein the product thiol purification unit includes at least one distillation column containing structured packing.

17. An apparatus for producing high-purity thiol products from hydrogen sulfide and olefins, wherein the apparatus is: A reactor system including an absorption unit communicating with a reactor bank, wherein the absorption unit is: The hydrogen sulfide and the olefin are received, A liquid reactor bank supply flow containing at least a portion of the hydrogen sulfide dissolved in the olefin and a first recirculation portion of the reactor outlet flow are formed. The liquid reactor bank supply flow is configured to supply the reactor bank; The reactor bank is: The first recirculation portion of the reactor outflow and the liquid reactor bank supply flow are received. A reactor system configured to form the reactor effluent containing the product thiol, unreacted hydrogen sulfide, unreacted olefin, and other components; A means for separating the reactor effluent into a first portion and a second portion, and for returning the first portion of the reactor effluent to the reactor system and recirculating it, wherein the first portion and the second portion have the same chemical composition. A flash vaporizer in communication with the reactor system, the flash vaporizer being configured to receive a second portion of the reactor outflow and generate a hydrogen sulfide recirculation flow containing at least a portion of the unreacted hydrogen sulfide and a crude thiol flow containing the product thiol, the unreacted olefin and the other components, and the flash vaporizer being configured to supply the hydrogen sulfide recirculation flow to the reactor system; A crude thiol separation system communicating with the flash vaporizer and the reactor system, wherein the crude thiol separation system is configured to receive the crude thiol stream, and the crude thiol separation system is: At least a portion of the unreacted olefin is separated from the crude thiol stream to produce an olefin recirculation stream containing the unreacted olefin, a first byproduct stream containing a first portion of the other components, and a crude thiol product stream containing the product thiol and a second portion of the other components; A crude thiol separation system configured to supply the aforementioned olefin recirculation flow to the reactor system; A product thiol purification unit that communicates with the crude thiol separation system, wherein the product thiol purification unit comprises: The crude thiol product stream is accepted; A product thiol purification unit is configured to produce a product thiol stream containing purified product thiol, which contains at least 98.5 weight percent of the product thiol, and a second byproduct stream containing the second portion of the other components. A device including a device.

Images