The method of obtaining of raw materials of high-sulphur crude oil

 

(57) Abstract:

We propose a method of obtaining of raw materials of high-sulphur crude oil by contacting desalted and dehydrated oil from Ecumenical and/or aluminoborosilicate catalysts in the environment of hydrogen at elevated temperature and pressure, characterized in that as an additive to the desalted and dehydrated sour crude oil on the catalyst is fed in an amount of 1-20%. a mixture of one of the organic alcohols with long hydrocarbon chain C1-C4 with water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume 70-120A at a temperature of 370-400oAnd pressure 35-70 MPa and subsequent processing in the usual way at the refinery. table 1.

The invention relates to the refining and petrochemical industries, in particular, to a method of refining.

Known methods of refining [1-2] which includes a preliminary fractionation desalted and dewatered oil and subsequent processing of the narrow oil fractions leads to the formation of significant quantities of residual oil with a high content of sulfur, heavy metals and hard PNA processing. These oils are high-sulphur oil Canada, Venezuela, Egypt and others.

One of the ways of solving the tasks involved in the processing of so-called "off-grade" oils and production of crude oil in the processing of high-sulfur heavy oil is advance preparation by Hydrotreating.

Currently, the methods of separate hydrofining of petroleum fractions: gasoline, kerosene, diesel fraction. There are publications on the Hydrotreating of the heavy oil feedstock [3-6]

However, currently known approaches to separate hydrofining petroleum fractions not applicable for hydrobromide oil in General.

The closest solution to the technical essence and the achieved result is a method of Hydrotreating a hydrocarbon feedstock, in particular vacuum gasoil or deasphalting residual oil [7] However, this method also does not allow for hydrofining oil at the stage of preliminary processing, i.e. before fractionation, when composed of a wax substance.

The purpose of the proposed invention is the floor of the refinery.

This goal is achieved by contacting desalted to dehydrated oil from Ecumenical and/or aluminoborosilicate catalysts in the environment of hydrogen at elevated temperature and pressure, provided that desalted and dehydrated oil is pre-mixed with 1-20% about. mixtures of one of the aliphatic saturated C1-C4 alcohols and water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume 70-120A at a temperature of 370-400oC and a pressure of 3.5 to 7.0 MPa.

A distinctive feature of the proposed method is that the catalyst is supplied desalted and dehydrated oil is pre-mixed with 1-20% about. mixtures of one of the aliphatic saturated C1-C4 alcohols and water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume 70-120A at a temperature of 370-400oC and a pressure of 35-70 MPa.

The basis of the proposed method of refining is the process of hydrofining oil c and subsequent processing of the received sweet crude oil according to the usual scheme refinery. During hydrofining oil flow processes Hydrotreating light the metals.

An important advantage of the proposed method is the possibility of profitable processing of heavy and sour crude oils, the processing of which by the usual options is difficult and requires dilution other varieties with high levels of light and lower sulfur content.

The process hydrofining oil in a mixture with the additive which is a mixture of the alcohol with the specified length of the hydrocarbon chains and water in a certain ratio under given technological parameters allows the hydrofining process dehydrated and desalted oil prior to its division into individual fractions, which can significantly reduce the sulphur content in refined oil and then process it in the usual way.

In the known methods of refining the application of the described technology is unknown. Therefore, this solution meets the criteria of "novelty" and "significant difference".

The proposed method is illustrated by the following examples.

Example 1. The raw material used oil with the following physical-chemical characteristics:

density, 8960 kg/cubic m

the viscosity at 20oWith, 18,6 KVM is Shemot, 6,3;

99 ml of oil specified composition was mixed with 1ml of additives consisting of 0.95 ml of methanol and 0.05 ml of water.

The resulting mixture was subjected to hydrofining at a temperature of 370oC, hydrogen pressure of 35 MPa at lookbetteronline.com catalyst with a predominant pore 70A.

Conducted fractionation of the feedstock and the resulting hydrogenated feed is cut showed that the amount of light distillates (gasoline and kerosene, gas oil fractions) when such processing is increased by 5%vol.

As can be seen from the data in table 1, the proposed method at the first stage of refining to get from high-sulphur raw material raw material reforming and Hydrotreating diesel fractions with relatively low sulfur content. In addition, at the same time, sweet crude oil.

The same table lists the parameters of the process, the raw materials used catalyst, as well as the quality of the obtained hydrogenated feed is separated in examples 2-6. The sequence of operations used to test a sample of oil when running examples 2 to 6 is similar to example 1.

The method of obtaining of raw materials of high-sulphur crude oil by kami in the environment of hydrogen at elevated temperature and pressure, wherein the desalted and dehydrated oil is pre-mixed with about 1-20. mixtures of one of the aliphatic saturated alcohols WITH1-C4and water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume at a temperature of 370-400oC and a pressure of 3.5 to 7.0 MPa.

 

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FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

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FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

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40 cl, 2 tbl, 19 ex

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SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.

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3 cl, 4 tbl, 13 ex

FIELD: petroleum refining industry.

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EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.

7 cl, 2 tbl, 2 ex

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EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: petroleum processing and petrochemistry.

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4 tbl, 3 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.

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5 cl, 6 tbl, 12 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.

EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.

2 ex

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

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29 cl, 8 ex

FIELD: petroleum processing.

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EFFECT: simplified process.

2 cl, 1 tbl, 3 ex

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