RU2450045C1 - Method of producing base oil having low content of sulphur and ecologically clean aromatic filler materials and caoutchouc and rubber plasticisers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing base oil with low content of sulphur, ecologically clean aromatic filler materials and caoutchouc and rubber plasticisers, involving selective purification of petroleum oil fractions with a selective solvent, separation of the first step extract and raffinate solutions, wherein the first step extract solution is cooled with subsequent separation a first step pseudo-raffinate solution in the settling tank, and after solvent regeneration, the first step raffinate solution is dewaxed and oxidised with subsequent extraction of the oxidised dewaxed oil to obtain second step raffinate and extract solutions; after solvent regeneration and subsequent adsorption or hydrofining, group II base oil with low sulphur content is obtained from the second step raffinate solution, wherein the second step extract solution is mixed with the first step pseudo-raffinate solution to obtain, after solvent regeneration, ecologically clean aromatic filler and a caoutchouc and rubber plasticiser with less than 2.9% content of polyaromatic hydrocarbons (PAH).

EFFECT: obtaining base oil with negligible sulphur content.

3 cl, 3 tbl, 3 dwg

Description

The invention relates to the field of chemical technology and can be used in oil refining, in particular for the production of base mineral oils of group II (by API) with a sulfur content of 0.03% and environmentally friendly petroleum fillers and plasticizers with a content of polyaromatic hydrocarbons (PAHs) of less than 2, 9% (according to IP 346) used in the production of rubber and rubber.

The prototype of the proposed method is a method for producing base oils, fillers and plasticizers of rubber and rubber according to the classical technology for the production of oils [1]. There are also various methods for producing fillers and plasticizers [2, 3]. As close analogues in technical essence and essential features to the proposed method for producing base oils, fillers and plasticizers of rubber and rubber, the following methods can be distinguished:

- Based on the procedure for the oxidation of oil distillate with hydrogen peroxide in the presence of a catalyst, extraction, dewaxing of raffinate and obtaining a base oil with a low sulfur content [2];

- Based on a two-stage extraction separation of oil distillate, in which, at the first extraction stage (extractor), the selective solvent interacts with the feed to obtain raffinate and extract solutions of the first stage and subsequent regeneration of the solvent from these solutions to obtain raffinate and extract of the first stage, which is in the second stage extraction interacts with a new portion of a selective solvent to obtain raffinate and extract solutions of the second stage and subsequent reg non-reaction of the solvent from these solutions to obtain the raffinate and extract of the second stage [3].

According to these sources [1, 2, 3], the base oil is obtained according to the classical one-stage purification scheme, including vacuum distillation of fuel oil, selective distillate purification, raffinate dewaxing, hydrotreating or adsorption purification of dewaxed oils to obtain the target base oil product, and a by-product extract of the first stage, which according to the method [3] is subjected to separation into the second stage of extraction to obtain a raffinate and extract of the second stage, the first of which is filler and plasticizer of rubber and rubber. The main disadvantage of the classical technology for producing base oils [1] is the inability to obtain a base oil of group II with a sulfur content of 0.03%. The main disadvantage of the method [2] is the need to use a “fresh” solvent at each extraction step, which leads to a high total solvent multiplicity for the raw materials to be separated, four solvent recovery units and, as a result, high specific energy consumption, which increases the cost of production. In addition, the second stage of extraction is characterized by poor separability of raffinate and extract solutions due to a slight difference in the densities of the interacting products, which is confirmed by numerous laboratory experiments during the purification of the extract with N-methylpyrrolidone.

The essence of the invention lies in the fact that in the production of oils the classic set of processes is supplemented by the stages: sludge of the extract solution to a temperature of 5 ÷ 45 ° C depending on the content of PAHs in the feed. If the PAH content is <7%, then the temperature of the phase sediment is carried out at a temperature of + 5 ° C and below. The separated phase of the pseudo-raffinate solution is directed to mixing with the extract solution of selective purification of dewaxed oil, and then to the regeneration of the solvent to obtain a filler and plasticizer of rubber and rubber containing less than 2.9% PAH; stage oxidation of dewaxed oil and its extraction to obtain a base oil with a sulfur content of 0.05-0.08%. Adsorption or hydrotreatment allows to increase the content of sulfur compounds in the base oil to 0.03%.

The main objective of the present invention is to obtain a base oil of group II with a sulfur content of 0.03%, as well as an environmentally friendly filler and plasticizer with a PAH content of less than 2.9%. At the same time, technical and economic indicators are improved, such as an increase in the selection of target products, a decrease in the ratio of solvent to raw materials during extraction, and a reduction in energy costs for obtaining modern base oils, fillers, and rubber and plasticizers. This goal is achieved by selective purification of oil distillates and deasphalting agent, settling at low temperatures of the extract solution, separating a pseudo-raffinate solution with a low PAH content, dewaxing of raffinate, oxidizing it with hydrogen peroxide and other oxidizing agents in the presence of a catalyst, one-stage extraction of oxidized dewaxing oil to obtain a second raffinate sulfur content of 0.05-0.08% and an extract solution, which is mixed with a pseudo-raffinate solution of the first stage of extraction, regeneration of the solvent to obtain a filler and plasticizer with a PAH content of less than 2.9%. The adsorption or hydrotreating of the second stage raffinate, the content of sulfur compounds in it is brought to 0.03%.

The addition of the classical technology for the production of oils by the stage of sedimentation of the extract of the first stage allows extracting valuable raw components of the extract solution in the form of a pseudo-raffinate solution up to 15%, which is mixed with the extract solution obtained by extraction of oxidized dewaxed oil. After regeneration of the solvent from them, an environmentally friendly filler and plasticizer with a PAH content of less than 2.9% is obtained. Mixing the pseudo-raffinate solution with the extract solution from the oxidized dewaxed oil allows loading the regeneration system of the (additional) solvent (15% pseudo-raffinate solution and 25% of the extract solution from the oxidized dewaxed oil). Dewaxed oil is oxidized with hydrogen peroxide or another oxidizing agent in the presence of a catalyst of acetone, vegetable oil, metals, etc. at a temperature of 20-80 ° C. Oxidation of dewaxed oil makes it possible to turn sulfide sulfur into more polar sulfoxides, which are completely extracted with solvent from dewaxed oil (its sulfur content decreases by 4 or more times). Adsorption or hydrotreating of raffinate of oxidized dewaxed oil allows to obtain base oils of group II with a sulfur content of 0.03%.

As a selective solvent, any selective solvent can be used, for example: phenol, furfural, N-methylpyrrolidone and others.

The set of distinctive features described above provides the technical advantages of the proposed method: increasing the selection of environmentally friendly petroleum plasticizer and filler, obtaining base oils of group II due to the implementation of:

- separation processes of the pseudo-raffinate solution by sludge at low temperatures;

- oxidation and extraction of dewaxed oil; adsorption and hydrotreatment of the second stage raffinate;

- mixing a pseudo-raffinate solution with an extract solution obtained by extraction of oxidized dewaxed oil, regeneration of a solvent from them to obtain an environmentally friendly filler and plasticizer of rubber and rubber.

Figure 1 presents a scheme for the separation of raw materials by a known method - a two-stage scheme for the separation of raw materials with selective solvent cleaning in a first-stage extractor to obtain raffinate and extract solutions and their regeneration (solvent separation) to obtain a raffinate and extract, which is then separated in a second extractor steps to obtain an extract solution of the second step. After regeneration of the solvent from it, an extract is obtained, and after regeneration of the solvent, a filler and plasticizer of rubber and rubber with a PAH content of less than 2.9% are obtained from the second-stage raffinate solution.

Figure 2 presents the scheme for obtaining oil with a low sulfur content. The oil distillate, deasphalting agent is oxidized in the pipeline, the separation of the raw materials into raffinate and extract solutions is carried out in the first stage extractor, after regeneration of the solvent, a raffinate with a low sulfur content is obtained and the extract is an oil plasticizer.

Figure 3 presents the proposed scheme for the production of base oils of group II with a sulfur content of 0.03%, as well as environmentally friendly filler and plasticizer of rubber and rubber with a PAH content of less than 2.9%.

The figures show: 1 - first stage extractor; 2 - block regeneration of the solvent from the raffinate solution; 3 - block regeneration of the solvent from the extract solution; 4 - second stage extractor; 5 - block regeneration of the solvent from the raffinate solution of the second stage of extraction of the extract of the first stage; 6 - block regeneration of the solvent from the extract solution of the second stage of extraction of the extract of the first stage; 7 - block dewaxing; 8 - sump, separation of the pseudo-raffinate solution; 9 - block regeneration of the solvent from a mixture of pseudo-raffinate and extract solution of the second stage; 10 - block regeneration of the solvent from the extract solution of the second stage; 11 - oxidation unit; 12 - block regeneration of the solvent from the raffinate solution of the second stage; 13 - block adsorption treatment; 14 - condenser-refrigerator; I - raw materials; II - oxidizing agent; III - solvent; IV - low sulfur raffinate; V is an extract; VI - raffinate of the first stage; VII - extract of the first stage; VIII - extract of the second stage; IX - second-stage raffinate, filler and plasticizer of rubber and rubber (PAHs less than 2.9%); X - raffinate solution of the second stage; XI - low sulfur dewaxed oil; XII - base oil of the II group; XIII - filler and plasticizer of rubber and rubber with a PAH content of less than 2.9%.

The crude oil distillate, deasphalting agent in the first-stage extractor is mixed with the solvent and removed in the form of raffinate and extract solutions, after regeneration of the solvent, the raffinate is obtained from the raffinate solution, and the extract solution is cooled to obtain a pseudo raffinate solution, which is sent to be mixed with the extract solution obtained after extraction dewaxed oil. After regeneration of the solvent, an oil plasticizer and a filler of rubber and rubber are obtained. And the raffinate after the first stage of extraction is dewaxed, oxidized with hydrogen peroxide or another oxidizing agent in the presence of a catalyst of acetone, vegetable oil, metals, etc. at a temperature of 20-80 ° C and is extracted in a second stage extractor, from which the raffinate and extract solutions of the second stage are removed . The solvent is regenerated from the second-stage raffinate solution. The low sulfur raffinate after adsorption treatment or hydrotreatment contains 0.03% sulfur.

Implementation of extraction equipment can be different, for example, extraction columns, settling mixers, rotary disk extractors, etc. Table 1, 2, and 3 present data confirming the achievement of the task - process indicators and the quality of the obtained base oil, environmentally friendly filler and plasticizer rubber and rubber according to known and proposed methods and test results of petroleum plasticizer obtained by the proposed method in rubber.

To verify the operability of the proposed method, laboratory studies were conducted on the selective purification of industrial raw materials of oil fraction V distillate or deasphalting agent to obtain raffinate, raffinate and second-stage extract by extraction of dewaxed oil. The conditions for the extraction, dewaxing and adsorption processes corresponded to the industrial parameters of the process. Atmospheric pressure. Selective purification of the oil fraction - the ratio of solvent to raw materials is 1.7: 1, the temperature in the first stage is 55 ° C, in the second stage 60 ° C, in the third 65 ° C. The oxidation of dep.oil is carried out at temperatures of 20-80 ° C, with the supply of 3% hydrogen peroxide to the feed. Deparaffinization - the ratio of the solvent to the raw material 4: 1. The temperature of the final cooling of the raw material minus 28 ° C. The adsorption purification unit is an adsorbent of aluminosilicate crumb, the adsorbent ratio to the feedstock is 0.3: 1, and the temperature is 40-60 ° C. Sump - the residence time of the extract of the first stage in the sump is 30-60 minutes.

The analysis of the quality of the obtained base oil, filler and plasticizer of rubber and rubber was carried out on certified equipment.

The results obtained (Tables 1, 2, 3) show that the proposed method allows to obtain a group II base oil and increase the selection of environmentally friendly filler and plasticizer of rubber and rubber.

Table 1 The name of the quality indicators of the base oil By a known method According to the proposed method (from deasphalting) 1. Kinematic viscosity, at 100 ° C, cSt 19.25 19.04 2. The sulfur content,% 0.4 0,03 3. The content of saturated hydrocarbons,% <90% 92%

table 2 The name of the quality indicators of oil plasticizer,% yield By a known method According to the proposed method (from deasphalting) 1. Density, kg / m ³ at 20 ° C - 0.967 2. Kinematic viscosity, at 1000С, cSt 19.8 20,2 3. The content of the PCA according to iP346 (DMSO), wt.% 2.5 0.74 4. The content of α-benzopyrene, ppm - 0.5 5. The output,% 90% of the extract 40%

Table 3 The name of indicators PN-6 29% Oil filler and plasticizer of rubber and rubber (experienced) 29% Mooney viscosity, conv. units fifty 47 Tensile strength, kg / cm ² 229 223 227 219 Elongation at break 667 655 607 606 Residual elongation,% 19.5 18.5 16,0 15,5 The time of vulcanization, min 60 60 80 80 Content,% wt .: - BC-1 0.30 0.28 - oils 29.3 29.0 - free organic acids 4.98 4.8 - organic acids 0.02 0.00 - volatile 0.04 0.09 Vulcanization parameters (rubber mixture according to TU 2294-0.08-73776139-2009), 60 min, 150 ° С, ± 1 arc - M1, N * m - The minimum torque corresponding to the minimum torque on the vulcanization curve, proportional to the viscoelastic properties of the rubber compound at the vulcanization temperature, characterizes its rigidity. 1,11 1.10 - Mn, N * m - The maximum torque corresponding to the maximum value of the torque from the vulcanization curve is proportional to the shear modulus of the rubber at the vulcanization temperature, characterizes the stiffness of the rubber at the end of the vulcanization process. 3.90 3.89 - T _s , min - The start time of vulcanization, determined by the increase in minimum torque by 0.1 N * m at an amplitude of 1 ^o and 0.2 N * m at an amplitude of 3 ^o and 5 ^o . 5,4 5.3 - t _op , min - The optimal vulcanization time, during which the optimum properties of the vulcanizer is achieved, it may differ from the actual optimal time required to achieve optimum properties 25,4 30,0 - R _y , min ^-1 - The rate of vulcanization proportional to the average steepness of the growing branch of the vulcanization curve. 5.00 4.04

Literature

1. Selective purification of oil raw materials / R. G. Nigmatullin, P. A. Zolotarev et al. - M.: Oil and gas, 1998. - 208 p., Pp. 133-144.

2. Patent No. 2243986 dated 02.10.2003 “Method for the purification of oil fractions” (C10G 53/04, C10G 53/14), authors Nigmatullin V. R., Sharipov V. A., Nigmatullin I. R.

3. Patent No. 2313562 dated December 27, 2007 (C10G 21/22, С08К 11/00), authors N.V. Khodov and etc.

Claims (3)

1. A method of obtaining base oils with a low sulfur content, environmentally friendly aromatic fillers and rubber and rubber plasticizers, including the selective purification of oil fractions of oil with a selective solvent, the separation of the extract and raffinate solutions of the first stage, characterized in that the extract solution of the first stage is cooled, followed by separation in the sump of the pseudo-raffinate solution of the first stage, and the raffinate solution of the first stage after regeneration of the solvent is dewaxed and oxidized followed by extraction of the oxidized dewaxed oil to obtain the second stage raffinate and extract solutions, from the second stage raffinate solution after solvent regeneration and subsequent adsorption or hydrotreating, a low sulfur group II base oil is obtained, while the second stage extract solution is mixed with the first stage pseudo raffinate solution with obtaining after regeneration of the solvent, environmentally friendly aromatic filler and plasticizer rubber and rubber with holding polyaromatic hydrocarbons (PAH) less than 2.9%. 2. The method according to claim 1, characterized in that the extract solution of the first stage is cooled to a temperature of 5-45 ° C. 3. The method according to claim 1, characterized in that the dewaxed oil is oxidized by hydrogen peroxide in the presence of a catalyst selected from the group: acetone, vegetable oil, metals, at a temperature of 20-80 ° C.

Images