FI128142B - Process and apparatus for producing hydrocarbons - Google Patents

Description

20105094 prh 25 -09-20199

Method and apparatus for producing hydrocarbons

Field of the Invention

The invention relates to a method and apparatus for the production of hydrocarbons. In particular, the invention relates to the conversion of terpenes into hydrocarbon compounds useful as gasoline components or as gasoline fuel as such.

Background of the Invention

The use of renewable hydrocarbon components in fuels instead of fossil feedstocks is of increasing interest. Their use is highly desirable for environmental reasons. There is a great deal of literature related to the production of fuel compositions from biological raw materials such as vegetable oils such as tall oil.

US 2004/0230085 A1 discloses a process for the production of hydrocarbon components from wood-based tall oil by a two-step process in which hydrogen from oxygen in the tall oil fatty acid fraction (TOFA) is used to hydrogenate TOFA in the presence of a catalyst followed by isomerization to hydrocarbons. The products obtained from the isomerisation are mainly i-paraffins suitable for use as components in diesel fuels. Suitable hydrocarbon chain lengths for diesel components are typically in the range C9-C20.

US 2009/0020089 A1 describes a fuel composition comprising at least tetramethylcyclohexane and optionally an aromatic isoprenoid compound and a monocyclic and acyclic hydrocarbon component. The fuel composition may be, for example, gasoline fuel grade. Tetramethylcyclohexane is produced by hydrogenation of pinene in the presence of a hydrogenation catalyst. The pinene and the raw materials for the optional components included in the fuel composition are produced by microbiological methods using a host cell.

In addition, US 5959167 A describes the preparation of gasoline components from lignin-based material by a multi-step process. US 5186722 A describes palladium-catalyzed hydrotreating of a starting material containing vegetable oils or extracts. US 2009/0200204 relates to a hydroprocessing catalyst that can be used to process hydrocarbon feedstocks. GB 252787 relates specifically to the manufacture of light oil suitable for diesel engines from organic material. US 2009/012260 A1 describes the conversion of terpene to fuel with an acidic zeolite-type cracking catalyst and US 4922048 describes the refining of a gasoline olefin with a zeolite catalyst.

Tall oil is a by-product of the coniferous sulphate process.

By-product of the same process is also obtained from crude turpentine. The chemical compositions of these 5 substances differ significantly.

Tall oil is composed mainly of fatty acids and resin acids of varying chain lengths in the range C12 to C18 and fused ring systems in the form of abietic acids and sitosterols, whereas crude turpentine comprises a mixture of terpenes derived from pitch. Terpenes are a wide range of volatile hydrocarbons having the chemical formula C10H16, including typically unsaturated monocyclic and bicyclic hydrocarbons. Terpene-containing crude turpentine is formed in the sulfate process and is commonly referred to as crude sulfate turpentine (CST). The major terpene components in CST are α-pinene, B-pinene and Δ-3-carene. The major component is typically α-pinene.

α-pinene B-pinene Δ-3-carene

20105094 prh 25 -09-20199

The unsaturated two-ring terpenes in the turpentine of the formulas given above are too reactive to be used as such as fuel components. In addition, the high sulfur content of turpentine prevents its use as a fuel.

Methods for converting terpenes into cymenes are known in the art. In these processes, different types of catalysts are used for the conversion. They use, for example, alkali metal carbonate catalysts, catalysts comprising noble metals or rare earths on a zeolite support, and a palladium catalyst on activated carbon or alumina.

CST, which contains a large number of terpene isomers, also contains a relatively large amount of sulfur, about 1 to 3%, as an impurity. In order to further exploit the CST, sulfur removal will be required. In EP 0267833 A1, sulfur is removed from the terpenes in the crude turpentine by hydrogenation in the presence of a cobalt and molybdenum oxide catalyst on an inorganic support. Chemical conversion of terpenes is avoided during the hydrogen desulphurisation process.

20105094 prh 25 -09-20199

Today, crude sulfate turpentine is processed for use as a solvent or fragrance in the pharmaceutical and cosmetic industries. However, wider utilization of turpentine is limited by the high sulfur content and there are no cost effective methods for sulfur removal and processing. Therefore, a large amount of crude sulfate turpentine is incinerated without further treatment.

Brief Description of the Invention

It has now been found that unsaturated Cs-C10 cyclic and acyclic hydrocarbons can be converted into suitable gasoline components by a one-step process using a conventional dewaxing catalyst. The components obtained by the process of the invention can be used as fuel components as such or as fuel additives in gasoline fuel compositions. Some of the components produced can also be used in other products such as cosmetics or pharmaceuticals. The hydrocarbon components obtainable by the process have a typical carbon 15 number for gasoline fuel components ranging from C4 to C10.

In a particular embodiment of the invention, crude sulfate turpentine is used as the starting material. The crude sulfate turpentine may also comprise distillate residues of turpentine. As mentioned above, the high sulfur content of turpentine prevents its use as a fuel. Surprisingly, it was found that crude sulfate turpentine can be produced as fuel components by using only one catalyst capable of both cleaving hydrocarbons and sulfur removal from the CST in a one-step process. The process has the advantage that no pre-treatment is required to remove the sulfur from the CST prior to further treatment. Thus, one embodiment of the invention provides a simple, efficient, and economical process for treating crude sulfate turpentine to provide a product useful in fuels.

The invention provides a simple, efficient, and economical method for converting unsaturated Cs-C10 hydrocarbons into gasoline components that can be used either directly or as a blend in gasoline to provide a gasoline composition conforming to gasoline standard EN 228: 2008. In particular, the relative proportions of the components in the product can be controlled by further converting the aromatics to toluene as needed.

It is therefore an object of the invention to provide a method and apparatus for producing gasoline components. The object of the invention is achieved as described in the independent claims.

20105094 prh 25 -09-20199

It is also an object of the invention to use the gasoline components obtained by the process of the invention as an additive in gasoline fuel compositions or as a gasoline fuel as such.

Brief Description of the Drawings

Figure 1 illustrates an embodiment of an apparatus according to the invention comprising a single reactor packed in a single layer of a catalyst system.

Figure 2 shows another embodiment of the apparatus of the invention comprising a single reactor packed in two separate layers in a reactor.

Figure 3 illustrates an embodiment of the apparatus of the invention comprising two reactors each packed in a single layer of catalyst systems.

Figure 4 shows an embodiment of an apparatus according to the invention comprising a reactor and a hydrogen sulphide separator.

Detailed Description of the Invention

It is an object of the invention to provide a process and apparatus for the production of gasoline components which comprises introducing a feed of unsaturated C 5 -C 10 cyclic and acyclic hydrocarbons into a one-step hydrogen treatment and wax removal catalyst in the presence of a catalyst system containing the catalyst component.

The unsaturated C 8 -C 10 cyclic and acyclic hydrocarbons which form the starting material of the process of the present invention can be obtained from any suitable source. Hydrocarbons may contain heteroatoms and trace amounts of heavier hydrocarbons as impurities. In one embodiment of the invention, the hydrocarbon feed consists of C 10 Hie terpenes. In one embodiment of the invention, the terpene feed consists essentially of crude turpentine. In the present invention, the raw turmeric is to be understood to be of wood origin. In a particular embodiment of the invention, the crude turpentine is obtained from the softwood sulfate process as a crude sulfate turpentine, which consists primarily of the resinous unsaturated C 10 Hie terpene isomers obtained from pitch. This type of crude turpentine of this origin is also called crude sulfate turpentine (CST). Due to the process chemicals used in the sulfate 35 process, sulfur is present in the crude turpentine

20105094 prh 25 -09-20199 as an impurity and is typically present at 0.5 to 3% by weight. Turpentine distillation residues can also be used as a terpene feed.

In another embodiment of the invention, the crude turpentine is obtained from a mechanical pulp of wood, for example abrasive and pressure abrasion, a thermomechanical pulp or a chemimechanical pulp. From these processes, turpentine may be recovered in gaseous form provided that the process includes gas recovery means. Turpentine can also be recovered in gaseous form from wood chips or sawmills.

In yet another embodiment of the invention, a mixture of 10 different raw fly insects can also be used as a raw fly feed. In yet another embodiment of the invention, the terpene feed may consist of one or more terpene compounds, such as α-pinene, isolated from the terpene mixture, for example, crude sulfate turpentine.

In another embodiment of the invention, sulfur-containing C5-C10 hydrocarbon streams or side streams from the wood processing industry can be used as the raw fly ash feed 15.

In one embodiment of the invention, the fuel components are produced by a one-step hydrogen treatment using a conventional dewaxing catalyst known in the art (hereinafter also referred to as the HW20 catalyst). In one embodiment of the invention, the wax removal catalyst is used with NiW on a carrier selected from Al2O3, zeolite, zeolite Al2O3 and Al2O3-S1O2. In a particular embodiment, NiW is used on an AkOs carrier.

In the following, the invention will be further illustrated by the use of raw sulfate sulfate (CST) as a starting material, but it is to be understood that the invention is not limited to this embodiment.

The dewaxing catalyst used in the present invention is capable of hydrogenating the olefinic bonds of the terpene compounds in the CST, opening at least one of the bicyclic rings, and cleaving the propene30 side chains and other hydrocarbon chains in one step. Splitting can also be called wax removal. In particular, 1-isopropyl-4-methylbenzene, also called cymene, can be degraded to toluene. In addition, the dewaxing catalyst is preferably capable of simultaneously removing unwanted sulfur compounds in the CST, such as dimethyl sulfide, dimethyl disulfide and methyl 35 mercaptan, by converting the organic sulfur compounds to gaseous hydrogen sulfide. Sulfur removal is commonly referred to as hydrodesulfurization (HDS). At issue

In the invention of 20105094 prh 25 -09-20199, CST thus undergoes one step in which the aforementioned chemical transformation reactions take place simultaneously.

Light gaseous hydrocarbons such as methane are also formed at this stage. In general, gaseous compounds, including hydrogen sulphide, methane and H2 formed in reactions 5, can be readily removed from the process and separated if necessary.

It is characteristic of a dewaxing catalyst that sulfur must be present in order to maintain the catalytic activity of the catalyst. Preferably, when the hydrocarbon feed comprises CST, the sulfur hydrogen required for the catalytic activity of the dewaxing catalyst is simultaneously obtained from the sulfur compounds naturally present in the CST. Gaseous hydrogen sulphide can be readily removed from the gasoline blend if necessary.

The process may require additional sulfur to maintain the catalytic activity of the catalyst. The additional sulfur may be supplied in gaseous form, such as hydrogen sulphide, or it may be any material which produces hydrogen sulphide in the process, for example organic sulfur compounds such as dimethyl disulfide. In one embodiment of the invention, additional sulfur is obtained by recycling H2S-containing gas recovered from the gasoline component blend produced by the process of the invention. The amount of additive depends on the amount of sulfur present in the CST. In general, the ratio of H2 input to H2S must be kept above about 0.0001. This means that the amount of sulfur added is about 100 to 200 ppm. Sulfur may be fed, for example, to the first feedstock feedstock or to the hydrotreating step.

In one embodiment of the invention, the catalyst system further comprises a hydrodesulfurization (HDS) catalyst. The catalyst may be any conventional HDS catalyst known in the art. It should be noted that any conventional catalyst for the removal of heteroatoms from organic compounds can be used in the process of the invention. Heteroatoms are typically sulfur, oxygen and nitrogen. Particularly in the art, catalysts known as hydrodeoxygenation (HDO) catalysts can be used in the process. HDO catalysts are specifically designed for deoxygenation, but can also be used for desulfurization and nitrogen removal. In a preferred embodiment of the invention, the HDS catalyst is provided upstream of the dewaxing catalyst. In this embodiment, the HDS catalyst acts as a prehydrogenation catalyst which produces aromatic hydrocarbons which are further converted to toluene in the presence of a dewaxing catalyst as required.

In the present invention, the HDS catalyst is selected from the group consisting of N1O / M0O3, C0O / M0O3 and a mixture thereof with a carrier selected from Al2O3 and AbOs-SiCte. In a particular embodiment of the invention, NiO / MoOs are used with the AbOs carrier.

Like the dewaxing catalyst, the HDS catalyst must contain sulfur in order to maintain the catalytic activity of the catalyst. The HDS catalyst has no cleavage properties but is capable of hydrogenating the olefinic bonds of the terpene compounds, opening at least one of the bicyclic rings, and converting the organic sulfur compounds to hydrogen sulphide.

The amount of hydrogen gas required to hydrogenate the olefinic bonds of the terpene structure is determined by the amount of the turpentine feed. The appropriate amount of hydrogen may be determined by one skilled in the art. Typically, the ratio of H 2 to turpentine feed is from about 200 to 1500 Nl / L, preferably from about 250 to 550 (Nl = normal liter).

If necessary, any gasoline component may be isolated from the blend obtained by the process of the invention.

In one embodiment of the invention, the mixture of hydrodesulfurized gasoline components is subjected to a hydrogen sulphide removal step to remove any residual sulfur hydrogen from the mixture.

The terpene compounds in CST undergo a variety of chemical reactions including hydrogenation, isomerization, dehydrogenation, hydrogenolysis, and C-bond cleavage and cleavage. The various reactions are affected by reaction conditions, particularly temperature and CST feed rate (WHSV) for the reaction. The different reactions of the initial components of CST, i.e. α-pinene and Δ-3-carene, can be described, for example, as follows:

20105094 prh 25 -09-20199

The compounds obtained in the process of the invention can be classified as unsaturated non-terpenic hydrocarbons, terpenes, and acyclic, polycyclic, monocyclic and aromatic hydrocarbons. In addition, when the 5 propyl group is removed from the aromatic substances (o-, m- and p-cymene), toluene is formed as follows:

20105094 prh 25 -09-20199

This reaction is particularly advantageous when used in combination with the HDS + HW catalyst system.

If the ring opening does not occur completely during the hydrotreatment step, C10 bicyclic compounds may also be formed which have the same structure as the starting components, except that there are fewer olefinic bonds.

20105094 prh 25 -09-20199 p.m. It has been recognized that when low temperatures are used, the ring opening of the parent components is reduced and the relative amount of bicyclic compounds increased. Thus, the relative proportions of the components of the product can be influenced by controlling the temperature through the catalyst bed. The temperature of the hydrogenation / cleavage step 5 may range from about 200 to 450 ° C, preferably from about 275 to 375 ° C.

At temperatures above about 330 ° C, the amount of toluene tends to increase. This is due to the increasing content of aromatic hydrocarbons, especially cymenes such as 1-propyl-4-methylbenzene. In the process of the invention, p-cymene is further converted to toluene.

The conversion of p-cymene to toluene can be accomplished in whole or in part, depending on the properties desired for the gasoline product to be produced, and controlled by adjusting temperature and / or WHSV.

The composition of the gasoline component mixture can be influenced by controlling the temperature and / or WHVS. The type of catalyst also affects the relative proportions of the components. For example, if only one catalyst bed comprising the HW catalyst is used, the amount of toluene may be increased by keeping the temperature high, e.g., above about 330 ° C, and the WHVS low, e.g., below about 5. If WHVS is added and the temperature is kept high, the amount of toluene will be reduced and the product will contain more cymene. If 20 dual-catalyst systems are used, with the first layer downstream of the tungsten inlet inlet being the HDS catalyst and the second layer being the HW catalyst, keeping the temperature high and the WHVS low may result in the HDS layer producing cymene and converting the HW layer to toluene. .

The octane number of toluene is preferably high (RON = 121, MON = 107). In addition, the vapor pressure of toluene is favorable to provide the base gasoline fuel. If desired, an octane enhancer such as ethanol may be added to the product obtained by the process of the invention.

The production of p-cymene and / or toluene can also be increased by recycling, whereby the gasoline component blend obtained in the process is recycled to the styrene feed and / or the hydrotreating and digestion step. In particular, if only HW catalyst is used, it is possible to obtain a high yield of toluene at lower process temperatures by recycling the mixture. On the other hand, in one embodiment where the HDS catalyst is used for prehydrogenation, the mixture is recycled to obtain a high yield of the parasymene at lower temperatures. The p-cymene is then cleaved to toluene by HW catalyst.

The reaction with the dewaxing and hydrodesulfurization catalyst is

20105094 prh 25 -09-20199 extremely exothermic and the temperature therein may be raised to a level which is detrimental to the catalytic activity of the catalyst and / or the quality of the product. In some cases, it may be necessary to adjust the temperature variations. Product recycling provides an effective way to control the exothermic reaction, whereby the recycled product stream acts as an inert medium that lowers the temperature of the bed in a controlled manner. In one embodiment of the invention, the gasoline components obtained in the process are recycled to the original turpentine feed and / or to the on-going hydrotreating step.

The pressure in the process may range from about 10 to about 150 bar, preferably about 20 to about 70 bar. More preferably, the process of the invention is carried out at a pressure of about 25 to about 50 bar.

The hydrogen treatment step may be carried out either in one catalyst bed of the catalyst system or in two or more catalyst beds. One or more catalyst layers may be provided in a single reactor or in several reactors, as further described below. When two or more catalyst layers are used, the catalyst system containing HDS and HW catalysts may be divided such that the first catalyst layer upstream of the following layers contains HDS catalyst material but not dewaxing catalyst material, and the next layer (s) only i sto catalyti m ate ri aal i a.

After the hydrogen treatment step, the sulfur is removed in the form of gaseous hydrogen sulfide, which is easily removed from the product, i.e. the gasoline component blend. In addition, light gaseous hydrocarbons, such as methane, are formed which are easily removed from the process if desired. The sulfur content of the product blend may be reduced to a level not exceeding 10 ppm, which is the limit for petrol fuels. However, in some cases, it may be necessary to remove traces of hydrogen sulphide from the product to achieve the above sulfur level. This can be accomplished in many ways, such as stripping, flash separation, or bubbling with an inert gas such as nitrogen gas. If desired, the resulting hydrogen sulphide may be introduced into the reactor to maintain the catalytic activity of the catalyst.

In addition, if necessary, a pretreatment step may be carried out prior to the hydrotreating step. The pretreatment step may include one or more of the following procedures: distillation, filtration and purification of CST.

The process according to the invention provides as a product a high-quality hydrocarbon component useful as a gasoline component. In addition, the product can be used as a fuel additive in conventional gasoline formulations. The invention thus further provides a method according to the invention

20105094 prh 25 -09-20199 use of petrol components as additives in petrol compositions or in petrol as such.

It is also an object of the invention to provide an apparatus for producing gasoline components. The apparatus according to the invention is suitable for carrying out an embodiment of the method according to the invention. The hardware comprises

- at least one reactor 1, T comprising at least one catalyst bed 3, 3 '

terpene inlet pipe 9

- hydrogen supply pipe 5, 50, 50 '

a product outlet tube 10, 15 for recovering the gasoline component mixture.

Referring to Fig. 1, the crude sulfate turpentine and hh are fed to a reactor 1 containing a catalyst bed 3 catalyst system comprising a dewaxing catalyst for hydrodesulfurization and cleavage of CST. The reactor is, for example, a separate vessel or a tubular reactor. CST and H2 are fed through the terpene supply line 4 and the hydrogen supply line 5, respectively. In Figure 1, CST and H 2 are combined and fed together through a terpene inlet 9 to reactor 1. In one embodiment of the invention, the inlet 9 is omitted and the feed pipe Ha 4 and 5 are separate inlets to reactor 1.

The catalyst layer comprising the catalyst system may be packed in one or more layers 3, 3 '. In addition, one or more catalyst layers may be diluted with a suitable medium. The diluent may be, for example, a passive material used in the passive layers described below or another catalyst suitable for hydrogen treatment. It is also possible to form a dilute catalyst by mixing the HW catalyst material and the HDS catalyst material. In one embodiment where multiple catalyst layers are used in the reactor, the first layer downstream of the turpentine feed is diluted while the other layers are not. If the first layer downstream of the turpentine feed is diluted, it acts as a prehydrogenation catalyst. In the case of Ku30, the catalyst system is packaged in a single layer 3. Preferably, the catalyst layer is undiluted in the embodiment shown in Figure 1.

20105094 prh 25 -09-20199

The H2 feed can be fed to reactor 1 downstream of the turpentine feed. The H 2 feed may also be fed to the reactor 1 from the H 2 feed tube 50, which may be at one or more locations between the terpene inlet 9 and the product outlet 10, preferably at one or more locations on the lithium layer 3, to control the reaction conditions. These H2 input inputs are designated by reference numerals 6, 7, and 8.

H2 can also be fed upstream of the tufted feed, i.e., the H2 and tuft feeds are upstream of each other (not shown in Figure 1).

Catalytic hydrodesulfurization and other reactions, i.e. ring opening and olefinic bond saturation and cleavage reaction, take place in catalyst bed 3 packed in reactor 1. The product is recovered from reactor 1 via the product outlet 10. At least a portion of the product, i.e., the gasoline component blend, can be recycled to reactor 1 via a recycling tube 100 according to the dotted line shown in the figure. In recycling, the product can be combined with the original CST and H2 inputs into a single feed stream and fed to reactor 1 via a terpene inlet 9 as shown in the figure. Recycle tube 100 may also be provided in the reactor 1 apart from the terpene inlet pipe 9. The product may also be fed to the reactor 20 at one or more locations between the terpene inlet pipe 9 and the product outlet pipe 10, preferably one or more catalyst beds 3 through inlets 6, 7.

In addition, at least a portion of the product may be fed through conduit 101 to separation reactor 17 to separate some component from the gasoline component mixture. One or more separated components may be recovered via conduit 18.

The reactor 1 may also be provided with passive layers 11 and 12 comprising a suitable passive or inert material such as AbC, SiC or glass beads. They serve as protective layers against harmful substances in the feed. When the passive layer is arranged in the reactor 1 as the first layer to receive the feed from the inlet pipe 9, the catalyst upstream, it also acts as a feed preheat layer. It also improves the uniform distribution of the feed to the catalyst. In Figure 1, the first passive layer 11 is arranged upstream of the catalyst layer 35 and the second passive layer 12 is arranged downstream of the catalyst layer 3.

20105094 prh 25 -09-20199

In one embodiment of the invention, the catalyst system comprising the dewaxing catalyst and the HDS catalyst are mixed and packed in a single layer 3.

If necessary, additional sulfur is fed to reactor 1 via inlets 6, 7, 8 and / or 9 from an external source via a sulfur feed tube 16. Additional sulfur can also be fed to the turpentine feed. The additional sulfur fed through the tube 16 can be any compound that produces hydrogen sulphide in the process, for example an organic sulfur compound such as dimethyl disulfide.

The crude turpentine is pumped into reactor 1 at the desired rate. The feed hourly spatial velocity (WHSV) of Turpentine 10 feed is proportional to the amount of catalyst and is calculated by the following equation:

WHSV [/? *] = ^V ^ ^{fe [g //,]} m catalyst [g] where V _input [g / h] is the pumping speed of the crude sheaf feed and mc catalyst [g] is the amount of catalyst.

In an embodiment where only one catalyst layer comprising the HW catalyst is used, WHSV is typically in the range of about 2 to about 8, preferably at most about 5. In one embodiment with at least two catalysts in 20 layers, WHSV is typically in the range of about 0.5 to about 6. , preferably between about 1 and about 4. In one embodiment of the invention, WHSV is between about 1 and about 1.5. In one embodiment with two catalyst layers, multiple combinations of catalyst types are possible. Both catalyst layers may comprise an HW catalyst in which the first catalyst layer is diluted and the second catalyst layer is undiluted. It is also possible that the first catalyst layer comprises an HDS catalyst and the second catalyst layer comprises an HW catalyst.

In one embodiment of the invention, when there are multiple catalyst layers, the operating parameters must be adjusted accordingly to achieve an optimal product composition. For example, if the first catalyst layer 3 'is an HDS catalyst and the second catalyst layer 3 is an HW catalyst, such as in the embodiment illustrated in Figure 2, the amount of H2 feed to the catalyst layers is adjusted according to the layer with higher H2 or HW catalyst demand. Another way is to introduce more recycled hydrogen into the 35 HW catalyst bed.

20105094 prh 25 -09-20199

The ratio of gasoline components in the product blend can be influenced by adjusting the WHVS. The optimal VVHVS values for HDS and HW catalysts are different. HDS catalyst WHVS and _S nights _e ratio is lower than between the HW catalyst. Since there are no means for controlling the catalyst feed rate between layers 5, the only possibility is to control the amount of catalyst material packed in the bed. In practice, this means that the amount of HW catalyst must be less than that of the HDS catalyst.

The amount of hydrogen feed is proportional to the amount of turpentine feed and the composition of the catalyst system. For example, in a catalyst system comprising both HDS and HW catalysts in separate layers, the ratio of H 2 feed to tannin feed is higher than in a system comprising only HW catalyst. Typically, the ratio of H 2 feed to turpentine feed is about 200-1500 Nl / L, for example about 250-550 (Nl = normal liter).

Figure 2 shows another embodiment of the apparatus according to the invention wherein the catalyst system in reactor 1 is packaged in two separate layers, a first catalyst layer 3 'and a second catalyst layer 3. The first catalyst layer 3' is arranged upstream of the second catalyst layer 3. In one embodiment, the HDS catalyst is packaged in the first catalyst layer 3 'and the HW catalyst in the second catalyst layer 3. The HDS catalyst layer 3' is preferably diluted. In this embodiment, the HDS catalyst acts as a prehydrogenation catalyst. In addition, an insulating intermediate layer 13 is disposed between the two catalyst layers to prevent mixing of the layers and to facilitate operation of the first and second catalysts at different temperatures. The same material as the pas25 wing layers can be used as the intermediate layer. The passive layer 11 is disposed upstream of the first catalyst layer 3 '.

The H2 feed may be fed to reactor 1 either downstream of the ferruginous feed, or the H2 feed may be fed to the reactor 1 via the H2 feed pipe 50 at one or more positions designated 6, 7 30 and 8. If necessary, the H2 feed may be divided so that part of it is fed to the first catalyst layer 3 'and part to the second catalyst layer 3 as shown in Figure 2.

20105094 prh 25 -09-20199

As in the embodiment shown in Fig. 1, external sulfur can be fed to reactor 1 via sulfur feed pipe 16 if necessary. Further, the external sulfur feed can be divided so that a portion of the external sulfur feed is fed to the first catalyst layer 3 'and part to the second catalyst layer 3.

The catalyst materials used in the catalyst layers 3 'and 3 must be activated before they can be effective. The activation comprises several steps, one of which is the treatment of the catalyst with an activating sulfur compound, for example dimethyl disulfide. Catalyst activation is generally known in the art and is not discussed in further detail herein.

The product recovered through the product outlet 10 may be further introduced into the separation reactor 17 in the same manner as shown in Figure 1 (not shown in Figure 2).

Fig. 3 shows an embodiment of the invention in which the catalyst system is packaged in two separate catalyst layers, a first catalyst layer 3 'and a second catalyst layer 3, which layers 3' and 3 are disposed in different reactors, first reactor T and second reactor 1, respectively. is provided upstream of the second catalyst layer 1. In one embodiment of the invention, the first catalyst layer 3 'contains a diluted HDS catalyst, while the second catalyst 20 layer 3 contains an undiluted HW catalyst. The reactors T and 1 are provided with passive layers 1T and 12 'and 11 and 12 respectively.

The crude sulfate turpentine is fed to the first reactor T. The product from the first reactor T is recovered via the tube 10 'and further fed to the second reactor 1. The product is recovered from the product outlet 25 via the second reactor.

The H2 feed is fed to both reactors T and 1. The H2 feed can be fed either downstream of the prime feed or the H2 feed can be fed to the reactors T and 1 via H2 feed pipes 50 'and 50, designated at one or more positions 6', 7 'and 8' and left, 6, 7 and 8 respectively.

In another embodiment of the invention, both the first and second catalyst layers 3 'and 3 comprise diluted catalyst material. The catalyst layers may be arranged in the same reactor as in the embodiment of Figure 2, or may be arranged in different reactors, as illustrated in the embodiment of Figure 3.

20105094 prh 25 -09-20199

At least a portion of the product, i.e., the gasoline component blend, can be recycled to the first reactor 1 'via a recycle tube 100, as shown by the dashed line in Figure 3. In recycle, the product can be combined with the original CST and H2 inputs into a single feed stream as shown.

Recycle tube 100 may also be arranged in the first reactor 1 'apart from the terpene inlet tube 9. The product may also be fed to reactor 1' at one or more locations between the terpene inlet tube 9 and the product outlet tube 10 ', preferably one or more positions 7' and 8 '.

If necessary, additional sulfur is supplied to reactor 1 'via inlets 6', 7 ', 8' and / or 9 and / or to reactor 1 via inlets 6, 7, and / or 8. Additional sulfur may be fed to the turpentine feed and / or to the H2 feed.

The product recovered through the product outlet 10 may be further introduced into the separation reactor 17 in the same manner as shown in Figure 1 (not shown in Figure 3).

Figure 4 illustrates an embodiment of the apparatus of the invention in which the product recovered from the catalytic hydrodesulfurization and digestion of CST in liquid form is fed from reactor 1 through tube 10 to H2S effluent reactor 2. In the HteS effluent reactor 2, 14 through. This can be accomplished, for example, by stripping, flashing, or bubbling with an inert gas such as nitrogen.

When additional sulfur is desired, at least a portion of the gaseous compounds recovered from reactor 2 may be recycled to reactor 1 via a HteS recycling tube 140 as shown in the dotted line of Figure 4. Additional sulfur can also be fed to the reactor 1 from an external source via a sulfur feed pipe 16 via inlets 6, 7, 8 and / or 9. Extra sulfur can also be fed into the tannins30. The additional sulfur fed through the tube 16 can be any compound that produces hydrogen sulphide in the process, for example an organic sulfur compound such as dimethyl disulfide.

In the H2S effluent reactor 2, the treated petrol-grade product is recovered via the product tube 15. As with the embodiment35 shown in Figure 1, at least a portion of the product can be fed to the separation reactor 17 to separate any component from the gasoline component blend. Further, the recycling of the product obtained by the process of the invention via the recycle tube 100 may be carried out in the same manner as in the embodiment shown in Figure 4 (not shown).

The gaseous compounds may also be introduced into a gas treatment system (not shown in Figure 4). The gas treatment system deals with gaseous compounds recovered from the H2S reactor. Unreacted hydrogen is purged from hydrogen sulphide and methane by, for example, membrane technology. Purified hydrogen is pressurized and can be recycled to reactor 1 (not shown). The recovered hydrogen sulphide can also be recycled to chemical recovery at pulp mills and converted to elemental sulfur by the Claus method.

The following examples are provided to illustrate the invention without, however, limiting it.

Example 1

The crude turpentine obtained by the sulphate process, i.e. CST, was used as a feed for crude peat. The crude turpentine comprised 50-60% α-pinene, 20-30% Δ-carene and the rest other terpenes. The sulfur content was about 1.5%.

The catalyst system contained NiW as a dewaxing catalyst. The hydrodesulfurization catalyst was not present.

20105094 prh 25 -09-20199

table 1

Feed Pumping (Vseed) (g / h) 48 Catalyst NiW (10g) Reaction pressure (bar) 48 H ₂ (l / h) 25 WHSV (h ' ¹ ) 4.9 Bed temperature (° C) 365 H2 Feed / Fermented Feed (Nl / I) 440

The composition of the product is shown in Table 2.

Table 2

Liquid yield (%) 93 Heterocycles (%) 8.4 Monocycles (%) 27.9 Acyclicals (%) 5.1 Aromatic substances (cymenes) (%) 26.9 Toluene (%) 4.5 Other (Ce, C7, C10) (%) 27.2

Example 2

The same turpentine feed as in Example 1 was used. The process parameters and product composition are summarized in Tables 3 and 4, respectively.

20105094 prh 25 -09-20199

Table 3

Feed Pumping (Vseed) (g / h) 28 Catalyst NiW (1 Og) Reaction pressure (bar) 47 H ₂ (l / h) 20 WHSV (h ' ¹ ) 2.8 Bed temperature (° C) 330 H2 Feed / Fermented Feed (Nl / I) 607

The composition of the product is shown in Table 4.

Table 4

Liquid yield (%) 84 Heterocycles (%) 11.5 Monocycles (%) 37.4 Acyclicals (%) 4.0 Aromatic substances (cymenes) (%) 12.5 Toluene (%) 9.3 Other (Ce, C7, C10) (%) 25.3

Examples 1 and 2 show the importance of WHSV in the composition of the product.

Example 3

In this example, the same turpentine feed was used as in Example 1. The catalyst system comprised NiW and NiMo / Al 2 O 3 as a hydrodesulfurization catalyst. The two catalysts were packaged in different layers of a single reactor with the NiW layer placed downstream of the HDS catalyst layer 10, i.e. the layer comprising NiMo / Al 2 O 3. Upstream of the HDS catalyst layer was deposited an AkOs protective layer, whereby the CST feed first entered the protective layer prior to the HDS layer. An AbOs intermediate was placed between the catalyst layers. The SiC layer was placed downstream of the NiW layer, i.e., the bottom of the reactor, toward the product recovery outlet.

The process parameters are summarized in Table 3 below.

20105094 prh 25 -09-20199

Table 5

Feed Pumping (Vseed) (g / h) 59 Catalyst N1MO / AI2O3 (21g) + NiW (6g) Reaction pressure (bar) 47 H ₂ (l / h) 20 WHSV (h ' ¹ ) (N1M0 / AI2O3) 5.9 Bed Temperature (N1MO / AI2O3) (° C) 390 Bed temperature (NiW) (° C) 380 H2 Feed / Fermented Feed (Nl / I) 290

The composition of the product is shown in Table 6.

Table 6

Liquid yield (%) 78-81 Heterocycles (%) 17.1 Monocycles (%) 22.1 Acyclicals (%) 8.8 Aromatic substances (cymenes) (%) 2.0 Toluene (%) 25.6 Other (Ce, C7, C10) (%) 24.2

20105094 prh 25 -09-20199

Claims (17)

A process for producing gasoline components, the process comprising: - taking an inflow of C5-C10 cyclic and acyclic saturated hydrocarbons, comprising crude sulfur turpentine, the conduction of the inflow together with hydrogen to a one-step hydrogen treatment in a catalytic system comprising dewaxing catalyst and hydrodesulfurization catalytic, to form a waxed benzate and benzene benzate. A method according to claim 1, wherein the inflow, which comprises hydrocarbons, mainly consists of crude sulfur turpentine, which originates from wood sulphate boiling. 15 A process according to claim 1 or 2, wherein the dewaxing catalyst is NiW on a carrier selected from the following: AI2O3, zeolite, zeolite-AbOa and AI2O3-S1O2, advantageously the dewaxing catalyst is NiW on AbOa support. A process according to any preceding claim, wherein the hydrodesulfuration catalyst is selected from the following: N1O / MOO3, COO / MOO3 and a A mixture of them on a carrier selected from the following: Al2O3, Al2O3-S1O2, advantageously the hydrodesulfuration catalyst is N1O / MOO3 on AbOa support. A method according to any preceding claim, wherein sulfur inflow is measured into the hydrogen treatment stage. A method according to any preceding claim, wherein at least a portion of the gasoline component mixture is circulated back into the hydrocarbon stream and / or hydrogen treatment stage. A method according to any preceding claim, wherein the gasoline component mixture is led to the sulfur hydrogen removal stage to remove any sulfur hydrogen residues from the mixture. 30 A method according to claim 7, wherein hydrogen sulphide residues are removed by stripping, flash separation or by bubbling with inert gas. A process according to any preceding claim, wherein the hydrogen treatment stage is carried out at about 200 - 450 ° C temperature, advantageously at about 275 - 375 ° C temperature. 20105094 prh 25 -09- 2019 A method according to any preceding claim, wherein the pressure during the hydrogen treatment stage is about 10 - 150 bar, advantageously about 20 - 70 bar, most advantageously about 25 - 50 bar. A method according to any preceding claim, wherein The H2 inflow relative to the sulfur inflow is poured over about 0.0001. A method according to any preceding claim, wherein the H 2 inflow relative to the hydrocarbon influx is about 100 - 1500 Nl / I, advantageously about 100 - 350 Nl / I, most preferably about 100 - 300 Nl / I. A method according to any preceding claim, wherein The hydrocarbon inflow pumping velocity WHSV, measured according to the following formula ™ catalytic [5] where Vinfeed [g / h] means the hydrocarbon inflow pumping speed and mcatai [g] means the amount of catalytic acid; is about 2 - 8, preferably at most 5, where the catalytic system is arranged in a catalytic layer, or is about 0.5 - 6, advantageously about 1 - 4, most advantageously about 1 - 1.5, where the catalytic system is arranged in at least two katalytlager. A process according to any preceding claim, wherein a gasoline component mixture comprising toluene is obtained. 20 A method as claimed in claim 1, wherein said component as a heist component is separated from the gasoline component mixture. Use of gasoline component blend prepared as claimed in claims 1-15, as gasoline or additive in gasoline compositions. Use of gasoline component blend prepared as claimed in claims 1-15, in cosmetic or pharmaceutical products.