RU2791610C2 - Method for production of hydrocarbon base of drilling muds with improved operational properties - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the production of a hydrocarbon base for the production of drilling muds (hereinafter – HBDM). A method for the production of HBDM includes preparation of a mixture of weighted medium distillate fractions of atmospheric-vacuum distillation of oil, catalytic cracking, and delayed coking, catalytic hydrogenation of the specified mixture, alkalization of the resulting hydrogenation hydrogenate to achieve a sulfur content in the final product to a level of not more than 0.001 wt.%, rectification of the resulting hydrogenate, catalytic hydrocracking of vacuum gas oil obtained during distillation of fuel oil, rectification of the resulting hydrogenate of catalytic hydrocracking. Catalytic hydrogenation of the mixture of weighted medium distillate fractions of atmospheric-vacuum distillation of oil, catalytic cracking, and delayed coking is carried out at pressure of 20.0-32.0 MPa, temperature of 300-420°C, and multiplicity of hydrogen-containing gas circulation of 1500-4300 nm³ of hydrogen : 1 m³ of raw materials. During rectification of the resulting hydrogenate, an intermediate fraction is isolated, boiling off within 200-320°C. Catalytic hydrocracking of vacuum gas oil obtained during distillation of fuel oil is carried out at pressure of 20.0-32.0 MPa, temperature of 320-420°C, and multiplicity of hydrogen-containing gas circulation of 500-1500 nm³ of hydrogen : 1 m³ of raw materials. During rectification of the resulting hydrogenate of catalytic hydrocracking, gasoline, diesel fractions and a target product – a heavy residue are isolated. The heavy residue is sent for catalytic dewaxing with partial isomerization and hydrogenation. Catalytic dewaxing is carried out at pressure of 3.3-4.2 MPa and temperature of 280-380°C. Rectification of the resulting dewaxing agent is carried out to remove light hydrocarbons with release of a heavy fraction boiling at a temperature above 240°C, with a flash point above 130°C. The resulting heavy fraction boiling at a temperature above 240°C, with a flash point above 130°C is mixed with a fraction boiling within 200-320°C, obtained from hydrogenate of hydrogenation of weighted medium distillate fractions of atmospheric-vacuum oil distillation, catalytic cracking, and delayed coking, at the ratio of 10-90:90-10 wt.% to obtain HBDM with a flash point of more than 85°C, a solidification temperature below minus 50°C, a content of aromatic hydrocarbons below 2 wt.%, and capability of adjusting kinematic viscosity at 40°C in the range from 2 to 8 mm²/s.

EFFECT: expansion of a raw material base and technological solutions for the production of HBDM, improvement of operational properties of HBDM.

1 cl, 1 dwg, 1 tbl

Description

The field of technology to which the invention belongs

The invention relates to the field of refining oil and heavy fractions of the processes of primary and secondary refining of oil (fuel oil components) and obtaining special oil products, in particular, to the production of a hydrocarbon base for obtaining drilling fluids used in the oil and gas industry in the technological process of drilling gas and oil wells .

State of the art

In most cases, drilling fluids are complex colloidal systems that perform many different functions during well drilling, from the removal of cuttings from the bottom of the well and cooling the bit to maintaining the stability of the borehole walls and protecting drilling equipment from corrosion and abrasive destruction.

Depending on the geological conditions and requirements of the drilling process, various agents can be used as the basis for creating a continuous phase of drilling fluids. Most often, water or aqueous brines, as well as hydrocarbon liquids, are used for these purposes.

Hydrocarbon base for drilling fluids (hereinafter referred to as RBM), as a rule, is used when drilling easily swelling and caving-prone clayey rocks, salt-bearing deposits, as well as productive formations with low reservoir properties. In this case, RBBR can be used either in pure form, or in a mixture with water or with an aqueous solution in the composition of emulsions, where the hydrocarbon liquid forms a continuous phase.

Oil, gas condensate, base oils, oils of vegetable origin, diesel fuel, poly- and alpha-olefins are traditionally used as a hydrocarbon medium for the preparation of drilling fluids. At the same time, these RBWs have both positive and negative operational characteristics.

At present, the requirements for the quality of RBBR are being tightened in terms of ensuring operational, environmental and fire safety properties. WWRP should have a low content of sulfur and aromatic hydrocarbons, a high flash point, and a low pour point.

At the same time, at present, additional requirements are imposed on RBW to improve such indicators as flash point, pour point and total aromatic hydrocarbon content. Also, additional requirements appear from oil production enterprises for the creation of RBBR with an increased kinematic viscosity at 40 ° C - 4.0-6.0 mm ² / s, while on an industrial scale RBBR are produced with a kinematic viscosity at 40 °C below 4, 0 mm ² /s.

Ensuring these characteristics of RRW is possible only through the use of special technologies, taking into account the selection of certain raw materials, the use of catalytic processing processes and the use of highly efficient rectification to isolate target products. At the same time, it is especially important in the conditions of the Russian Federation to develop new technical solutions for obtaining RBF from typical common raw materials for oil production enterprises of the Russian Federation, which will solve the problem of import substitution, because. a significant part of the RBBR is purchased from foreign manufacturers.

There are a number of products and methods for their production, which allow the production of RBW.

In drilling practice, synthetic liquid paraffins can be used. Thus, the invention [patent RU 2547653] describes a method for producing a component of environmentally friendly oil-based drilling fluids having a boiling range in the range of 188-304°C according to ASTM D 86, including co-oligomerization of ethylene with α-olefin at a temperature of 180-200°C and an ethylene pressure of 4.0-5.0 MPa in the presence of a catalyst, adding to the mixture of cocatalyst in the form of a Lewis base - isopropyl alcohol in an amount of from 0.2 to 1% wt. based on the initial comonomer of ethylene, fractionation of the resulting liquid product and the selection of the target fraction with a boiling range in the range of 188-304°C.

Received by this method RBW due to the absence of aromatic and sulfur-containing compounds in it is non-toxic to the environment. At the same time, WWBR has a fairly low pour point of minus 55°C and below minus 60°C. However, a significant disadvantage of this method for producing RBM is the technological complexity of its production, the scarcity and high cost of raw materials, and, as a result, the high cost of the resulting product relative to other analogues, which may limit its use in drilling practice. In addition, this RBF has insufficient high flash point - below 60°C and reduced kinematic viscosity at 40°C - 1.53-1.65 mm ² /s.

From the patent of the Russian Federation No. 2699419, a method is known for obtaining a component for drilling fluids from oil, which includes the distillation of oil with the release of a diesel fuel fraction, fuel oil, catalytic hydrotreatment of the diesel fuel fraction, and the hydrotreated diesel fuel fraction is sent to isodewaxing, carried out at a pressure of 41-43 atm, the resulting technological product is sent for fractionation and a fraction is taken, boiling in the range of 160-360°C.

Common features of this method and the present invention are:

- Use of oil and raw materials obtained during its processing as a raw material for the production of RBW;

- Increased yield of the target product on the feedstock 43.6% (table 2 from the description of the patent of the Russian Federation No. 2699419 - 96 m ³ /h RBF at the feedstock consumption for the hydrogenation unit 220 m ³ /h);

- Obtaining as a result of RBW with a high flash point of 88-90°C, a low pour point of less than minus 70°C and a low sulfur content.

The disadvantages of this method are:

- The use of high-value raw materials - straight-run diesel fuel obtained by atmospheric distillation of oil (typical boiling ranges are 160-360 ° C), the cost of which is much higher than that of heavy middle distillate fractions obtained by atmospheric-vacuum distillation of oil and fuel oil and in secondary processing processes oil (coking and catalytic cracking), vacuum gas oil. At the same time, the use of straight-run diesel fuel as a raw material for the production of RBF will lead to a decrease in the production of highly valuable Euro 5 diesel fuel that is in demand on the Russian market.

- The high cost of the resulting RBW due to the high costs in the implementation of the catalytic process using an isomerization catalyst containing precious metals.

- WWBR has low kinematic viscosity at 40°C 1.8-2.2 mm ² /s;

- Problems with ensuring the requirements for the content of aromatic hydrocarbons (no more than 3 wt.%) in the resulting component for drilling fluids, because at a given pressure of the hydrotreatment process, specified in the patent of the Russian Federation No. 2699419, there is no complete saturation of the aromatic hydrocarbons contained in the feedstock. This aspect is not covered in this patent.

A known method of obtaining a component for drilling fluids from oil, for example, distillate fractions or products of secondary oil processing [RF patent No. 2668612]. The method for obtaining a component for drilling fluids from oil includes the distillation of oil with the release of fuel oil. The resulting fuel oil is sent to vacuum distillation to obtain a vacuum gas oil. The obtained vacuum gas oil is subjected to hydrocracking. The unconverted residue formed during the hydrocracking process is sent to isodeparaffinization, then to hydrofinishing. The resulting technological product is sent for fractionation. As a component of drilling fluids, a fraction is taken that boils away in the range of 195-305°C.

Common features of this method and the present invention are:

- Use of oil and raw materials obtained during its processing as a raw material for the production of RBW;

- Obtaining as a result of WWBR with a high flash point of 88-90°C, a low pour point of less than minus 75°C.

The disadvantages of the prototype are:

- Low yield of the product on the feedstock of the hydrocracking process vacuum gas oil - less than 0.5% (information taken from the description of the patent of the Russian Federation No. 2699419, table 2 - 1.05 m ³ / h RBF at a feedstock consumption for the hydrocracking unit of 300 m3 / h) . What allows to produce a product per year - ROBR 6.0 thousand tons (information taken from an article in the journal "Oil refining and petrochemistry", 2018, No. 11, pp. 3-6).

- Non-optimal quality indicators of the obtained RBW, which has limitations of the kinematic viscosity index at 40°C not more than 1.8-2.0 mm ² /s. At the same time, consumers are currently declaring additional requirements to improve the quality indicators of RBW in terms of kinematic viscosity at 40°C more than 4.0 mm ² /s.

- The high cost of the obtained hydrocarbon base for drilling fluids due to the low yield of the target product and high costs when implementing a three-stage catalytic process at high pressures and temperatures, including the use of an isomerization catalyst containing precious metals.

The closest, the prototype of the present invention, is a method for obtaining RBF by processing oil and oil products [application for invention of the Russian Federation No. 2018136548 dated 10/16/2018, abstract]. The proposed RRSP can be obtained on the basis of individual diesel fractions of primary and secondary oil refining processes or mixtures thereof by carrying out a deep hydrogenation process, followed by separation of the intermediate hydrocarbon fraction from the hydrogenation product using a rectification process. In addition to diesel fractions, light gas oils from primary and secondary oil refining processes can be used as feedstock components for obtaining the present invention. At the same time, the resulting RBW contains aromatic substances in an amount of not more than 3 wt. %, total sulfur is not more than 0.001 wt. %, has a flash point in a closed crucible is not lower than 70°C, a pour point is not higher than minus 45°C and the value of the kinematic viscosity index at 40°C is not more than 4 mm ² /s.

The common features of the prototype and the proposed invention are that raw material weighted components obtained during oil refining are used as raw materials for the production of WWBR, and also that for the processing of these components the hydrogenation process of this raw material is used at high pressure up to 31.0 MPa and temperature up to 420°C on similar catalysts containing d-metals (groups VI and VIII of the periodic table) in the sulfide form with modifying additives. The result is a RBW with a low content of sulfur and aromatic hydrocarbons.

The disadvantages of the prototype are:

- Limited capacity at the refinery using high pressure hydrogenation technologies, which does not allow to increase the production of RRW. Sufficiently low yield of RRSP during the rectification of the hydrogenate obtained by hydrogenation of vacuum gas oil - no more than 22%.

- Non-optimal quality indicators of the obtained RBW, which has a low flash point in a closed crucible not lower than 70°C, an insufficient pour point not higher than minus 45°C and limits on the kinematic viscosity index at 40°C not more than 4 mm ² /s. At the same time, consumers are currently declaring additional requirements to improve the quality indicators of RBM in terms of flash point not lower than 85-90°C, pour point from minus 50°C to minus 60°C and kinematic viscosity at 40°C 4.0-6, 0 mm ² /s.

The objective of the invention is to expand raw materials and technological solutions for the production of RBF, increase the volume of its production in the Russian Federation as part of import substitution, obtain RBBR with improved quality indicators for flash and pour points, aromatic hydrocarbon content, and the ability to control kinematic viscosity in a wide range.

Disclosure of the essence of the invention

The solution of the problem and the achievement of the technical result is carried out by using a method for obtaining RBF with improved performance properties by processing fractions obtained from oil, including the preparation of a mixture of weighted middle distillate fractions of atmospheric vacuum distillation of oil, catalytic cracking and delayed coking, catalytic hydrogenation of the specified mixture, alkalization the resulting hydrogenation hydrogenation product to achieve the sulfur content in the final product to a level of not more than 0.001 wt. %, distillation of the obtained hydrogenate, catalytic hydrocracking of vacuum gas oil obtained by distillation of fuel oil, rectification of the obtained hydrogenate of catalytic hydrocracking, catalytic hydrogenation of a mixture of heavy middle distillate fractions of atmospheric vacuum distillation of oil, catalytic cracking and delayed coking are carried out at a pressure of 20.0-32.0 MPa , temperature 300-420 ° C and the frequency of circulation of hydrogen-containing gas 1500-4300 nm ³ hydrogen: 1 m ³ raw materials on a nickel-tungsten-sulfide catalyst with the addition of aluminum oxide or on a catalyst containing hydrogenating components nickel, molybdenum in oxide form, during rectification of the obtained hydrogenate, an intermediate fraction is isolated, boiling away in the range of 200-320 ° C, catalytic hydrocracking of vacuum gas oil obtained during the distillation of fuel oil is carried out at a pressure of 20.0-32.0 MPa, a temperature of 320-420 ° C and a circulation rate of hydrogen-containing gas of 500- 1500 nm ³ hydrogen: 1 m ³ cheese on a catalyst containing active components nickel, molybdenum in oxide form on an alumina carrier, during the rectification of the resulting catalytic hydrocracking hydrogenate, gasoline, diesel fractions and the target product - a heavy residue are isolated, the heavy residue is sent to catalytic dewaxing with partial isomerization and hydrogenation, catalytic dewaxing is carried out at a pressure of 3.3-4.2 MPa and a temperature of 280-380 ° C on a nickel-molybdenum catalyst, and hydrogenation on an aluminum-cobalt-molybdenum catalyst, the obtained dewaxing product is rectified to remove light hydrocarbons with the release of a heavy fraction that boils away at a temperature above 240 ° C, with a flash point above 130°C, mixing of the obtained heavy fraction, boiling over at a temperature above 240°C, with a flash point above 130°C, with a fraction boiling over in the range of 200-320°C fractions of the atmosphere rno-vacuum distillation of oil, catalytic cracking and delayed coking, in a ratio of 10-90:90-10 wt. % to obtain a hydrocarbon base for drilling fluids with a flash point of more than 85°C, a pour point below minus 50°C, an aromatic hydrocarbon content of less than 2 wt. % and the ability to control the kinematic viscosity at 40°C in the range from 2 to 8 mm ² /s.

Due to the production and compounding of the two components, the production of RBW is increased by 70-85% compared to the prototype.

In this case, the invention may be characterized by the following essential features:

- RBBR is obtained by processing oil and petroleum hydrocarbon fractions, which makes it possible to use a wide range of large-tonnage refined products as a raw material base for its production.

- The raw material for the production of RBF involves weighted fractions obtained during oil refining, which are components of heating oil and have a low cost, which makes it possible to obtain a more profitable product with lower production costs.

- The technological processes that are used to implement the invention are standard for the industry in question, and expensive catalysts containing precious metals are not used. This leads to an additional reduction in the cost of RBF according to the claimed invention in comparison with the prototype and analogues.

- An increase in the output of the target product for the total raw material due to the production of two large-tonnage components and their mixing.

At the same time, the resulting RBBR has high operational, environmental and fire-fighting characteristics:

- contains in its composition of aromatic compounds less than 2 wt. %, sulfur below 0.001 wt. %, (ensures environmental safety);

- has a pour point below minus 50°С (allows storage and operation in cold climatic zones), a flash point in a closed cup above 85°С (provides the required level of fire safety during storage of the liquid and its operation during drilling);

- depending on the ratio of components, the kinematic viscosity at 40°C can be adjusted from 2 to 8 mm ² /s (according to consumer requirements).

This makes it possible to conclude that the criterion of inventive step is met.

Implementation of the invention

To confirm the possibility of implementing the claimed invention, JSC Angarsk Petrochemical Company (JSC ANHK) carried out pilot runs for the production of two components according to various technological schemes, followed by compounding of these components in various ratios in laboratory conditions and subsequent testing of the obtained samples on quality indicators of RRR. The schematic flow diagram for obtaining RBW is shown in Fig. 1.

The present invention was obtained as a result of the following technological operations:

1. Getting the first component:

Mixtures of heavy middle-distillate fractions of primary (atmospheric-vacuum distillation of oil) and secondary (catalytic cracking and delayed coking) oil refining processes, boiling up in the range of 155 to 455°C, are fed from the block for preparing mixed raw materials 1 to the block for deep hydrogenation and alkalization 2, where are subjected to hydrogenation at a feed space velocity of 0.3-1.0 h ^-1 (8-25 m ³ /h), high pressure of 20.0-32.0 MPa, temperature of 300-420°C and the frequency of circulation of hydrogen-containing gas 1500 -4300 nm ³ hydrogen: 1 m ³ raw materials on special catalysts (on a nickel-tungsten-sulfide catalyst with the addition of aluminum oxide or on a catalyst containing hydrogenating components (nickel, molybdenum) in oxide form) to a level that ensures the content of aromatic compounds in the final product, not more than 3 wt. %. To achieve the required sulfur content in the product to a level of not more than 0.001 wt. % (not more than 10 ppm) the resulting hydrogenate is additionally subjected to alkalization. The resulting hydrogenate is divided into fractions in the distillation unit 3 with the release of an intermediate fraction, boiling in the range from 200 to 320°C (according to the prototype), which is a component 1 of the RBF. Qualitative characteristics of the obtained component 1 are presented in the table, column 2. The yield of the RBBR component obtained according to this scheme is at least 60% of the feedstock.

As weighted middle distillate fractions of the processes of primary and secondary oil refining at unit 1, heavy straight-run diesel fuel (HDF), light catalytic cracking gas oil (LGKK), diesel fraction (DFZK) and light gas oil (LGZK) of delayed coking of oil residues are used.

2. Getting the second component:

Obtained during oil refining at the AVT unit at the vacuum distillation unit of straight-run fuel oil 4, the vacuum distillate with boiling points of 250-460°C is sent to the hydrocracking unit 5 (Fig. 1). The hydrocracking process is carried out at a feed space velocity of 0.4-1.0 h ^-1 (8-21 m ³ /h), a high hydrogen pressure of 20.0-32.0 MPa, a temperature of 320-420 gas 500-1500 nm ³ hydrogen: 1 m ³ raw materials in three successively installed reactors on a typical cracking catalyst containing active components (nickel, molybdenum) in oxide form on an alumina carrier. Before using the catalyst, it is sulfided. As a result of the hydrocracking process, a hydrogenate is obtained containing a minimum amount of aromatic and heteroatomic hydrocarbons. The resulting hydrocracking hydrogenate is sent for atmospheric distillation to a distillation unit 6 with the separation of gasoline and diesel fractions and obtaining the target product - a heavy residue (fraction 270°C-KK). Next, the heavy residue is sent to the block of catalytic dewaxing 7 with partial isomerization and hydrogenation and subsequent stabilization (rectification) of the dewaxing product to ensure the required flash point (removal of light hydrocarbons) to obtain component 2 of the RWBR, boiling over 240 ° C and characterized by a flash point of more than 130 ° C and high viscosity. The dewaxing process proceeds on the active sites of the catalyst in the presence of hydrogen at a feed space velocity of 0.4-1.0 h ^-1 (5.0-12.5 m ³ /h), a pressure of 3.3-4.2 MPa and a temperature 280-380°C. A nickel-molybdenum catalyst is used as a dewaxing catalyst, and an aluminum-cobalt-molybdenum catalyst is used as a hydrogenation catalyst. The output of the RBBR component obtained according to this scheme is at least 44% for the initial vacuum gas oil. RBBR component 2 obtained according to this production scheme has, in comparison with component 1 obtained according to the previous paragraph (columns 12 and 2 of the table), a higher kinematic viscosity at a temperature of 40 ° C, a low pour point, a high flash point in a closed crucible, a reduced content aromatic hydrocarbons, at the same low sulfur content.

3. Mixing two components.

The obtained two components are mixed in various ratios on the block for the preparation of a mixed RBF 8 (Fig. 1) to improve the performance properties and obtain the required kinematic viscosity, which is determined by the requirements of consumers. At the same time, the introduction of component 2 at the level of 10-90% into the mixed product allows to improve the quality indicators of RBW (table):

- lower the pour point to a level below minus 50°C;

- raise the flash point to more than 85°C;

- Reduce the content of aromatic hydrocarbons below 2 wt. %;

- Get the ability to control the kinematic viscosity at 40°C in the range from 2 to 8 mm ² /s.

Due to the compounding of the two components, the production of WBR is increased by 70-85% compared to the prototype.

To increase the chemical stability of RBBR, an antioxidant additive Agidol-1 (4-methyl-2,6-diteric butylphenol) or its analogue can be added, in an amount of up to 0.4 wt. %.

The presented data indicate that the obtained samples of RBBR have improved rheological, low-temperature and environmental quality indicators, while the production of RBBR increases due to compounding of two large-tonnage components. This, in turn, confirms the possibility of achieving the claimed technical result, subject to the use of the proposed invention.

Claims (1)

A method for producing a hydrocarbon base for drilling fluids with improved performance properties by processing fractions obtained from oil, including preparing a mixture of heavy middle distillate fractions of atmospheric vacuum distillation of oil, catalytic cracking and delayed coking, catalytic hydrogenation of the said mixture, alkalization of the resulting hydrogenation hydrogenation product to achieve a sulfur content of final product to a level of not more than 0.001 wt.%, rectification of the obtained hydrogenate, catalytic hydrocracking of vacuum gas oil obtained by distillation of fuel oil, rectification of the obtained hydrogenate of catalytic hydrocracking, characterized in that the catalytic hydrogenation of a mixture of heavy middle distillate fractions of atmospheric-vacuum distillation of oil, catalytic cracking and delayed coking is carried out at a pressure of 20.0-32.0 MPa, a temperature of 300-420°C and a circulation rate of hydrogen-containing gas of 1500-4300 nm ³ hydrogen a: 1 m ³ of raw material on a nickel-tungsten-sulfide catalyst with the addition of aluminum oxide or on a catalyst containing hydrogenating components nickel, molybdenum in oxide form, during the rectification of the obtained hydrogenate, an intermediate fraction is isolated, boiling in the range of 200-320 ° C, catalytic hydrocracking vacuum gas oil obtained during the distillation of fuel oil is carried out at a pressure of 20.0-32.0 MPa, a temperature of 320-420 ° C and a circulation rate of hydrogen-containing gas of 500-1500 nm ³ hydrogen: 1 m ³ of raw material on a catalyst containing active components nickel, molybdenum in the oxide form on an alumina carrier, during the distillation of the resulting catalytic hydrocracking hydrogenate, gasoline, diesel fractions and the target product - a heavy residue are isolated, the heavy residue is sent to catalytic dewaxing with partial isomerization and hydrogenation, catalytic dewaxing is carried out at a pressure of 3.3-4.2 MPa and temperature 280-380°C on nickel-molybdenum rolled mash, and hydrogenation on an aluminum-cobalt-molybdenum catalyst, the resulting dewaxing product is distilled to remove light hydrocarbons with the release of a heavy fraction boiling over at a temperature above 240 ° C, with a flash point above 130 ° C, mixing the resulting heavy fraction boiling off at a temperature above 240°C, with a flash point above 130°C, with a fraction boiling away in the range of 200-320°C, obtained from the hydrogenation product of the hydrogenation of heavy middle distillate fractions of atmospheric-vacuum distillation of oil, catalytic cracking and delayed coking, in the ratio 10-90: 90-10 wt.% to obtain a hydrocarbon base for drilling fluids with a flash point of more than 85°C, a pour point below minus 50°C, an aromatic hydrocarbon content of less than 2 wt.% and the ability to control the kinematic viscosity at 40°C in the range from 2 up to 8 mm ² / s.

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