Method of hydroprocessing of hydrocarbon raw stock

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

 

The present invention relates to hydroperiod hydrocarbons, in particular liquid oil flow in oil refineries.

Currently, the oil industry largely depends on relatively high-boiling material, produced from materials such as coal, tar Sands, oil shale, and heavy oil. Such raw material usually contains much more undesirable components, especially from the point of view of the environment. Such undesirable components include the halides, metals and heteroatoms such as sulfur, nitrogen and oxygen. In addition, the technical requirements for fuel, lubricants and chemical products in relation to such undesirable components all the time increasing. Accordingly, these types of raw materials and flows of products require a more significant quality improvement in order to reduce the content mentioned undesirable components. A more significant quality improvement, of course, greatly increases the cost of processing such oil flows.

Hydroperiod, which includes've got a hydro conversion, hydrocracking, hydrobromide, hydrogenation, Hydrotreating and hydroisomerization, plays an important role in improving the quality of oil flows and their compliance with more stringent quality requirements. For example, when there is an increasing need for improving the removal of heteroatoms, aromatic saturated compounds and reduce the boiling point. Currently conducting major works in the field of hydrobromide due to increased demands for the removal of heteroatoms, especially sulfur, transported and heated fuel flow. Hydrobromide well known in the art and typically involves the processing flow of oil with hydrogen in the presence deposited on the catalyst carrier in terms of hydrobromide.

Much work is being done in the development of more active catalysts and advanced reactors, designed to ensure compliance with the requirements of implementing more efficient processes hydrobromide.

It is known that metals of group VIII is very effective for hydrogenation. However, their use is limited due to their sensitivity to pollution impurities, especially in the above severe types of raw materials. The major polluting impurities that affect the catalysts based on metals of group VIII are nitrogen and sulphur.

Recently become available catalysts based on metals of group VIII, which is based on a strongly acidic media such as zeolites or containing zeolite media. Such catalysts based on noble metals have a high resistance to sulfur and nitrogen. E and the catalyst can withstand the mentioned contaminants in their content up to 1000 million hours or more in terms of hydroperiod. The disadvantage of these catalysts is that they show an increased tendency to cracking, which leads to reduced yield.

The aim of the present invention is to develop a method of the above type that provides increased resistance to contaminants such as sulfur and nitrogen. Another goal is to develop a method with preferred balance between yield and resistance to exposure to contaminants, in particular a good balance of life, activity and performance.

The invention is based on the surprising fact that these goals can be achieved by a combination of at least two layers of catalyst, and the first has better resistance to the effects of organic sulfur and nitrogen compounds, while the second layer has better properties in respect of cracking. It was established that in the case of the combination of these two layers is achieved by an optimal combination that allows you to process raw materials with high content of pollutants without a high level of cracking associated with the use of high acid media.

Accordingly, the invention relates to a method of hydroperiod hydrocarbons containing as impurities sulfur and/what does nitrogen; this method includes the first contact interaction of hydrocarbons with hydrogen in the presence of at least one of the first catalyst based on a metal of group VIII in the acidic medium, and then contact interaction of the feedstock with hydrogen in the presence of at least one of the second catalyst based on a metal of group VIII in the less acidic media.

Hydroperiod according to the present invention includes've got a hydro conversion, hydrocracking, hydrobromide, hydrogenation, Hydrotreating and hydroisomerization of petroleum raw materials such as solvents and middle distillates.

Found that the method according to the present invention is very suitable for reducing the content of aromatic compounds in raw materials with a high degree of selectivity. In particular, it was found that this can be achieved by essentially avoiding or at least reducing the formation of gaseous hydrocarbons, for example the formation of gaseous hydrocarbons when on the first hydrocracking catalyst. It was also found that the present invention permits the processing of raw materials in the product, boiling point which is changed (usually reduced) to a relatively low level in comparison with known methods.

In the present invention be hydroperiod the raw material is first subjected to a contact in the to aimogasta with hydrogen in one or more layers of catalyst. The catalyst in these one or more layers is a metal of group VIII in strongly acidic media (as defined below). In the case when there are several layers of catalyst mentioned first type strongly acidic media, the media of these layers may have the same or different acidity. If the acidity in any of these layers of catalysts in strongly acidic media are different, then it is preferable that the acidity was highest in the first catalyst layers and decreased with each subsequent layer of the catalyst. Metals of group VIII, intended for use in the context of the present invention include Pt, Pd, Ir, Rh, Ru, and combinations thereof (alloys)such as preferred PtPd alloy. Strongly acidic media designed for use in the first catalyst, preferably selected from zeolites containing zeolite media. Examples of suitable zeolites are molecular sieves with large pores, such as zeolite Y, an ultra-stable zeolite Y, zeolite beta, mordenite, materials like MCM or molecular sieve with a crystal size less than 2 microns. In addition, it is possible to use containing zeolite media, such as the combination of zeolite and iron oxides, metal/metalloid. The amount of metal of group VIII is a value between 0.01 and 2.5 wt. percent, based on the combined weight of catalyst and carrier.

The stream exiting the last-mentioned catalytic layer with a catalyst in an acid medium, optionally after steaming served on one or more second layers of a catalyst containing a catalyst based on a metal of group VIII, but less acidic media. When you use multiple second catalyst layers (i.e. layers containing the catalyst at a less acidic media), the media in these layers may have the same or different acidity. If the acidity in any second layers are different, then it is preferable that the acidity was relatively highest in the first catalytic layer and decreased with each subsequent layer of the catalyst. Metals of group VIII selected from the same group as described above. But it is not necessary to use the second catalyst metals of group VIII, are identical to those used in the first catalyst. The amount of metal of group VIII in the second catalyst may be in the same interval as in the case of the first catalyst. However, the number may not be the same. Media designed for use in the second catalyst is less acidic than the media in the first catalyst. Suitable materials media are the Xia silicon dioxide, alumina, silica-alumina, titanium oxide, zirconium dioxide, nizkochastotnye zeolites and mixtures thereof. The ratio of the volumes (and the residence time of the feedstock in the presence of catalysts) of the first catalyst layer and the second catalyst (layers) may vary within wide limits, depending on the nature of the feedstock and the desired type and amount of hydroperiod. It is generally preferable that the amount of the first catalyst, at most, equal to the volume of the second catalyst. Suitable volumetric relationships range from 1 to 10 and from 10 to 1, preferably 1 to 3 and 3 to 1, most preferably 1 to 1.

As indicated previously, the acidity of the media should be different. Typically, the acidity is defined as the acidity of the Given. According to a preferred variant implementation of the upper layers of the catalyst have the acidity to a Given, at least 5 mmol/g, as determined in the experimental part. In particular, the lower limit is preferably 25 μmol/g, more preferably 50 µm. The acidity of the medium in the lower layers of the catalyst is preferably the most 10 μmol/g, more preferably less than 4 µmol/g (both values are defined as indicated in the experimental part).

The present invention is that an optimal balance between the output of the m product and the catalyst can be achieved in hydroperiod, when the process is divided into two different catalyst, a difference primarily lies in the nature of solid media. In particular, the method of the present invention is less sensitive to impurities in the raw material than in the case when only used catalyst downward flow, which allows to increase service life of the catalyst without reducing output. In particular, reduced samaccount. Another advantage is that the total amount of the catalyst is reduced and therefore reduces the need for noble metal. Both advantages are of economic nature.

It is believed that over the first catalyst most of the organic sulfur - and nitrogen-containing compounds is converted, on the one hand, low molecular weight sulfur and nitrogen compounds and hydrocarbons, on the other hand. As the duration of contact with the first catalyst is low compared with the total duration of hydroperiod, samaccount is particularly low. These lower samaccount is the advantage of this method compared with the method, which provides for the exclusive use of high acid catalyst.

The process conditions of hydroperiod can be selected depending on the nature of the raw materials and the properties required from the product stream. Process conditions t is Auda known conditions, used for hydrogenation, hydroisomerization, hydrocracking and/or hydrodesulfurised used raw materials.

Pressure (partial) hydrogen used for hydrogenation, hydroisomerization, hydrocracking and/or hydrodesulfurised depends on the type of raw material and is preferably from 0.5 to 300 bar, more preferably from 0.9 to 250 bar.

It is usually best conditions for the method according to the invention additionally include a temperature in the range from 50 to 450°and flow rate of fluid per hour (LHSV) in the range from 0.1 to 25 h-1.

Depending on the type of substrate and the partial pressure of hydrogen, the temperature can be selected within the specified interval. In particular, it is noted that the hydrocracking requires interval very high temperatures, i.e. up to 450°whereas for hydrodesulfurised sufficient temperature to 400°C.

Hydrogenation and hydrazobenzene can be done using temperatures up to 350°C.

When you choose a higher temperature requires a higher pressure to prevent excessive formation of coke on the catalyst. This means that the process will not take place in conditions of reforming catalyst.

Technological scheme will depend largely on local conditions and the actual type of p is ocess. It is possible to use a single reactor or multiple reactors. You can also use one or more layers of catalyst for each catalyst either in a single reactor or in multiple reactors. You can also enable the two layers of catalyst in one reactor, one above the other or separate from each other by suitable devices.

In General, the flow coming from the first catalyst is in direct contact with the second catalyst. However, you can also include another working installation between them, for example stage steaming to remove the converted nitrogen and sulfur contaminants, which are converted on the first catalyst in volatile components.

The commodity flows to be processed by the method of the present invention, are typically the commodity flows based oil, such as solvents, middle distillates, diesel fuel, light cyclic oil, lubricating oil, white oil, food GTL plant, which are all preferably Gidropribor before use as raw material for the method. Can also be used mixtures of the mentioned commodity flows.

Typical raw materials for the hydrogenation, hydroisomerization, hydrocracking and/or getresultlist in the method of the present invention typically contains sulfur-containing contaminants in the number is the firmness of from 0.1 to 500 million hours, preferably from 0.1 to 300 million hours per sulfur by weight of the raw material. Examples of such materials are the benzene, white oil, gasoline, middle distillates, such as diesel fuel and kerosene, solvents and resins. In particular, the method is intended for use in the hydrogenation of aromatic compounds in such raw materials, such as dearomatization hydrocarbons, which may contain as pollutants thiophene sulfur and/or nitrogen-containing pollutants.

Suddenly it was further discovered that olefins to aromatic raw materials can be selectively gidrirovanny method according to the invention. If, when using a catalyst containing only palladium, similar to the hydrogenation of olefins to aromatic feedstock flows with high efficiency.

Further, the invention is illustrated by some examples which are not intended to limit the scope of the claims.

EXAMPLES

The acidity of the catalysts

Experiments on the adsorption of pyridine conducted in high-temperature diffusion-reflective camera, equipped with KBr Windows (Spectra-Tech). The camera is connected to the gas system, so that gases may flow through the camera and the camera can be vacuumed.

The samples are crushed into fine powder and placed in an aluminum Cup for samples. About azzy first heated to 450° With and support at 450°C for at least 1 h, while the flow of inert gas is blown through the chamber. After cooling to room temperature a mixture of pyridine and an inert gas is passed through the chamber for about 1 min. Then the flow of pyridine is stopped and the flow of inert gas continues to flow, the whole system of support in this state, at least within 1 h Finally, the sample is heated to 180°in a stream of inert gas and maintain at 180°at least for 1 h, then cooled to room temperature. The amount of adsorbed pyridine on plots acids Bronsted and Lewis is determined by the difference in the infrared spectrum after degassing at 450°and desorption of pyridine at 180°s With the corresponding absorption band of pyrimidine and the absorption band of the pyridine Lewis acid with a known extinction coefficients.

Dispersion

The degree of dispersion can be determined by measuring the amount of CO adsorbed on the sample in the reduced form of the catalyst at 25°and a pressure of 1 bar as follows. A known amount of the sample of catalyst introduced into the reaction mixture and recover hydrogen at 200°C. After cooling in hydrogen at 25°the reaction mixture is rinsed with helium for at least 30 mi the ut. Then the flow of helium alternating with six pulses of a known quantity of CO and the concentration measured at the outlet of the reactor heat-conducting detector. The amount of the catalyst and chosen so that the catalyst is saturated after the first pulse, second through sixth pulses are used to confirm this.

The upper limit of the degree of dispersion corresponds to theoretical number of atoms that can bind one atom of noble metal (Pt, Ir, Ru, Rh or Pd). For practical purposes, as the upper limit is usually advisable to size 1.

The results of the tests of the catalysts of the present invention are shown in the following table.

UnitThe catalyst AndThe catalyst InMixed catalyst
Δρkg/m3-8,7-19,5-14
HDS%548268
crackingwt.%0,23,01,0
Note: the Catalyst was obtained by impregnorium media containing 30 wt.% zeolite Y and synthesized from a powder of zeolite H and solutions of aluminum sulfate and silicon dioxide through aqueous Sol-gel method, an aqueous solution containing Pd and Pt, with subsequent drying and restoration.

The catalyst was obtained by impregnorium media not containing zeolite synthesized from solutions of aluminum sulfate and silica through Sol-gel method, an aqueous solution containing Pd and Pt, with subsequent drying and restoration.

Mixed catalyst contains in the first half of the catalyst A, and the second catalyst Century

1. How hydroperiod hydrocarbon feedstock containing sulfur and/or nitrogen-containing contaminants, the method includes the first contact interaction of hydrocarbons with hydrogen in the presence of at least one of the first catalysts based on metals of group VIII in the acidic media, and the media is chosen from the group of zeolites and zeolite-containing media, and then the flow coming from the first catalyst is in direct contact with hydrogen in the presence of at least one of the second catalyst based on a metal of group VIII in the less acidic solid carrier, and the specified solid carrier selected from the group of media based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites.

2. The method according to claim 1, in which the specified hydroperiod includes hydroco the version hydrocracking, hydrobromide, hydrogenation, Hydrotreating and hydroisomerization of petroleum types of raw materials such as solvents and middle distillate.

3. The method according to claim 1 or 2, in which the solid carrier, at least one first catalyst based on a metal of group VIII selected from the group of zeolites and zeolite-containing solid media.

4. The method according to claim 1, wherein the solid carrier, at least one second catalyst based on a metal of group VIII selected from the group of solid carriers include silica-alumina, and other media that are not related to the zeolites.

5. The method according to claim 1, wherein said strongly acidic solid support has an acidity of at least 5 μmol/g

6. The method according to claim 1, wherein said less acidic solid support has an acidity at most 10 μmol/g, provided that its acidity is lower than the acidity of the solid carrier, at least one first catalytic Converter.

7. The method according to claim 1, in which the metal of group VIII of both the first and second catalyst is chosen, independently of one another, from the group comprising Pt, Pd, Ir, Rh, Ru, and combinations of two or more of these elements.

8. The method according to claim 1, in which the number of metal of group VIII in the calculation on the total weight of the metal and solid media in the first and second catalysts, independently of one another represent a value between 0.001 and 2.5 wt.%.

9. The method according to claim 1, wherein the amount of at least one of the first catalyst is in the range between 10 and 50% of the total volume of the first and second catalysts.

10. The method according to claim 1, in which the temperature at the inlet of the first catalyst is in the range between 100 and 400°C.

11. The method according to claim 1, wherein the hydrogen pressure is a value in the range between 0.5 and 300 bar.

12. The method according to claim 1, in which the levels of organic sulfur in the raw materials supplied to the second catalytic layer is less than 500 mln, preferably less than 50 mlnc

13. The method according to item 12, in which the content of organic nitrogen in the raw material is supplied to the second catalyst is less than 100 mln, preferably less than 20 mlnc

14. The method according to claim 1 which includes the first and second layers of catalyst contained in a single reactor or in different reactors.



 

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18 cl, 2 dwg, 4 tbl, 3 ex

FIELD: petroleum processing.

SUBSTANCE: blend composed of vacuum distillate and distilled fraction of secondary destruction processes is subjected to hydrogenation processing at elevated temperature and pressure in presence of catalyst, said secondary destruction process fraction containing sulfur up to 1% and being taken in amount 2 to 25% based on total weight of feedstock, while vacuum distillate boils up to 560°C. More particularly, secondary destruction process fraction is catalytic cracking, visbreaking, or retarded coking gas oil fraction. Process is carried out at 340-415°C, pressure 4-10 MPa, and feedstock supply volume flow rate 0.5-2.0 h-1.

EFFECT: improved purification degree of residue and enabled involvement of heavy vacuum distillate.

2 cl, 3 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: to crude oil with 2-10% water content is added catalyst followed by activation of hydrogen donors and hydrogenation of crude oil. Catalyst is used in the form of water-soluble group VI and VIII element compounds, which dissolves in water contained in crude oil to form true solution. Hydrogen donors are own crude oil fractions and products obtained from own crude oil fractions.

EFFECT: simplified and deepened oil processing.

10 cl, 1 dwg, 1 tbl

The invention relates to the field of processing of crude oil to increase the output of light oil products
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