Treatment process

FIELD: petroleum processing.

SUBSTANCE: invention relates to process of treating hydrocarbon stock, in particular to reducing nitrogen level in liquid hydrocarbon stock. Process is characterized by that (a) liquid hydrocarbon stock containing alkylation agent and organonitrogen compounds is brought into contact with acid catalyst at elevated temperature in a first reaction zone to form liquid hydrocarbon stock with reduced content of alkylation agent and organonitrogen compounds having elevated boiling temperatures; and (b) liquid hydrocarbon stock with reduced content of alkylation agent and containing organonitrogen compounds with elevated boiling temperatures is fractioned to remove said organonitrogen compounds.

EFFECT: enabled production of liquid hydrocarbon stock with reduced content of alkylation agent and reduced nitrogen level.

14 cl, 3 dwg

 

The invention relates to a cleaning method, in particular to a method for removal of nitrogen compounds from hydrocarbons.

Nitrogen compounds it is desirable to remove from hydrocarbons, for reasons of environmental protection. In addition, hydrocarbons are often recycled with the aim of obtaining products of high quality. These processes recycling can include catalytic reforming, catalytic Hydrotreating, catalytic desulfurization and adsorption. Such catalysts and adsorbents usually are deactivated due to the presence of nitrogen compounds, and therefore nitrogen compounds it is desirable to remove from hydrocarbon raw materials to refining raw materials, in order to avoid deactivation of the catalyst or adsorbent.

Thus, the present invention provides a method of raising the temperature of boiling nitrogen-containing organic compounds present in the liquid hydrocarbon feedstock, in which the said method is that the liquid hydrocarbon feedstock containing nitrogen-containing organic compounds in contact with an acid catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon feedstock containing nitrogen-containing organic compounds with high boiling point.

Nitrogen-containing organic compounds with the appreciation is authorized boiling point can be formed as a result of the condensation process between the nitrogen-containing organic compounds or can be formed by the interaction of nitrogen-containing organic compounds with aromatic compounds present in liquid hydrocarbon raw materials.

Preferably, nitrogen-containing organic compounds with high boiling points are formed by the interaction of nitrogen-containing organic compounds with an alkylating agent.

Thus, the present invention also provides a method of raising the temperature of boiling nitrogen-containing organic compounds present in the liquid hydrocarbon feedstock, wherein said method is that the liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds in contact with an acid catalyst at elevated temperature in the first reaction zone, in order to obtain liquid hydrocarbons having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling point.

In addition, the present invention provides a method of reducing the nitrogen content in the liquid hydrocarbon feedstock, wherein said method consists in the fact that:

a) a liquid hydrocarbon feedstock containing nitrogen-containing organic compounds in contact with an acid catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon feedstock containing nitrogen-containing organic compounds with high boiling point,

b) dilaut nitrogen-containing organic compounds with high boiling point, in order to obtain liquid hydrocarbons having a reduced nitrogen content.

In relation to liquid hydrocarbons, which contains an alkylating agent and a nitrogen-containing organic compounds, the present invention provides a method of reducing the content of nitrogen in liquid hydrocarbons, with this method is that:

a) a liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds in contact with an acid catalyst at elevated temperature in the first reaction zone, to form a liquid hydrocarbon having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling point,

b) remove the nitrogen-containing organic compounds with high boiling point, in order to obtain liquid hydrocarbons having a low content of an alkylating agent and a low nitrogen content.

Nitrogen-containing organic compounds with a high boiling point can be removed with the use of traps for nitrogen compounds, which may contain an adsorbent or molecular sieve for nitrogen compounds. Preferably, nitrogen-containing organic compounds with high boiling point are removed by fractionation.

Thus, preferred is a recreational embodiment, the present invention provides a method of reducing the content of nitrogen in liquid hydrocarbons, moreover, this method lies in the fact that:

a) a liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds in contact with an acid catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon, which has a low content of alkylating agent and contains a nitrogen-containing organic compounds with high boiling point,

b) liquid hydrocarbons having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling point, fractionary, in order to remove nitrogen-containing organic compounds with high boiling point, receiving liquid hydrocarbons having a low content of an alkylating agent and a low nitrogen content.

In addition, the methods of the present invention can be used in combination with the method of sulfur removal. In many countries legislation for hydrocarbon fuels, such as gasoline and middle distillates, such as diesel fuel and gasoline, restricts the upper limit of the content of sulfur compounds in the fuel to protect the environment. There is a continuous need for improved methods of desulfurization with the aim of obtaining hydrocarbon fuels with low with what uranium sulfur.

Thus, the present invention also provides a method of reducing the sulfur content and nitrogen in liquid hydrocarbons, and the above-mentioned method is that:

a) a liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic and organic sulfur compounds in contact with an acid catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon having a low content of alkylating agent includes organic sulfur and nitrogen-containing organic compounds with high boiling point,

b) a liquid hydrocarbon cheese having reduced contents of an alkylating agent, and includes organic sulfur and nitrogen-containing organic compounds with high boiling point, in contact with an acid catalyst at elevated temperature in the second reaction zone, to form a liquid hydrocarbon having a low content of an alkylating agent, and comprising organic sulfur compounds with high boiling temperature and nitrogen-containing organic compounds with high boiling point,

b) liquid hydrocarbons having a low content of alkylating agent comprising organic sulfur compounds with a high temperature of Kipen who I am and nitrogen-containing organic compounds with high boiling point, fractionary, in order to remove nitrogen-containing organic compounds with high boiling point and organic sulfur compounds with high boiling point and to obtain liquid hydrocarbons having a low content of an alkylating agent and a low content of nitrogen and sulphur.

Alternatively, the liquid hydrocarbon feedstock having a reduced content of an alkylating agent comprising organic sulfur compounds and nitrogen-containing organic compounds with high boiling point, formed in stage (a)may be subjected to fractionation to bring it into contact with the acidic catalyst in the second reaction zone.

Thus, the present invention additionally provides a method of reducing the sulfur content and nitrogen in liquid hydrocarbons, and the above-mentioned method is that:

a) a liquid hydrocarbon feedstock containing an alkylating agent and organic nitrogen compounds and sulfur in contact with the acidic catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon with a low content of an alkylating agent, and containing organic sulfur compounds and nitrogen-containing organic compounds with high boiling point.

b) liquid hydrocarbons having lower is the amount of content alkylating agent, includes organic sulfur compounds and nitrogen-containing organic compounds with high boiling point, fractionary to remove nitrogen-containing organic compounds with high boiling point, and obtaining a liquid hydrocarbon having a low content of an alkylating agent, organic sulfur compounds and low nitrogen content.

b) liquid hydrocarbons having a low content of an alkylating agent, organic sulfur compounds and reduce the content of nitrogen in contact with the acidic catalyst at elevated temperature in the second reaction zone to form a liquid hydrocarbon having a low content of an alkylating agent, organic sulfur compounds with high boiling point and low nitrogen content.

d) liquid hydrocarbons having a low content of an alkylating agent, organic sulfur compounds with high boiling point and low nitrogen content, fractionary to remove organic sulfur compounds with high boiling temperature, to form a liquid hydrocarbon having a low content of an alkylating agent and a low content of nitrogen and sulphur.

Liquid hydrocarbon raw material is typically a liquid at tempera is ur 25° C and a pressure of 102 kPa (wt.), and mostly it is obtained with the direct or indirect distillation of crude oil. Normally liquid hydrocarbon feedstock contains unsaturated hydrocarbons, for example, branched and unbranched alkanes and alicyclic hydrocarbons and varying quantities of aromatic and/or unsaturated compounds such as olefins.

Liquid hydrocarbons can be easy or middle distillate, which may represent one or more oil fractions with a boiling range 10-450°C, preferably 190-390°C. Appropriate, the flow of the middle distillate is a combination of these oil fractions. Examples of suitable petroleum fractions include naphtha catalytic cracking (NCC), naphtha process of coking (NC), naphtha visbreaking (UXO), light gas oil (LHA), heavy gas oil (TGO), a light recycle oil (LRM), oil coking (GOK) and the oil of the visbreaking process (gowb). Preferably, the liquid hydrocarbon feedstock is a diesel fuel, gasoline, kerosene or jet fuel and appropriate is a diesel or jet fuel.

Liquid hydrocarbon raw material contains a nitrogen-containing organic compounds. Usually nitrogen-containing organic compounds include alkylamines followed, anilines, pyrrole and pyridine. Usually the liquid is hydrocarbon, containing nitrogen-containing organic compound has a total nitrogen content (calculated as elemental nitrogen (N) 5-3000 ppm (by weight) N, preferably 10-500 ppm N, for example, 100 ppm N. When a liquid hydrocarbon containing a nitrogen-containing organic compounds, is a diesel fuel, it may contain pollutants sulfur substances in amounts of 10-100 ppm (calculated as elemental sulfur S). Usually nitrogen compounds have a boiling point between 50 and 450°C.

When the method of the present invention is used in combination with a method of removing sulfur liquid hydrocarbon feedstock typically contains organic sulfur compounds.

Typically, these organic sulfur compounds include mercaptans, tifany and benzothiophene (BT), for example dibenzothiophene (DBT) and spatial difficult alkyl substituted dibenzothiophene (employed DBT). Normally liquid hydrocarbons which comprises alkylating agent and organic nitrogen compounds and sulfur, has a total sulfur content (calculated as elemental S) 10-50000 ppm S, preferably 50-20000 ppm S, for example 500 ppm S.

In addition, the liquid hydrocarbon feedstock may contain alkylating agent.

The alkylating agent may be an alcohol and/or olefin, and usually it is present in the liquid hydrocarbon feedstock containing nitrogen, the content of inorganic fillers connection. Alternatively, the alkylating agent can be added to the liquid hydrocarbon feedstock containing nitrogen-containing organic compound, prior to contacting with the acidic catalyst.

Usually alkylating agent is an olefin, and suitable olefins include cyclic olefins, substituted cyclic olefins, and olefins of the formula (I)in which R1means hydrocarbon group, and each radical R2independently selected from the group consisting of hydrogen and hydrocarbon groups. Preferably, R1represents an alkyl group, and each radical R2independently selected from the group consisting of hydrogen and alkyl groups.

Examples of suitable cyclic olefins and substituted cyclic olefins include cyclopentene, 1 methylcyclopentene, cyclohexene, 1-methylcyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, cycloheptene, cyclooctene and 4-methylcyclohexane. Examples of suitable olefins of the type of formula (I) include propylene, 2-methylpropene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-1-butene, 3,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 2-ethyl-1-butene, 2-ethyl-3-methyl-1-butene, 2,3,3-trimethyl-1-butene, 1-penten, 2-penten, 2-methyl-1-penten, 3-methyl-1-penten, 3-methyl-1-penten, 2,4-dimethyl-1-penten, 1-hexene, 2-hexene, 3-hexene, 1,3-hexadiene, 1,4-hexadiene, 1,5-GE is Sadie, 2,4-hexadiene, 1-hepten, 2-hepten, 3-hepten, 1-octene, 2-octene, 3-octene, 4-octene. Secondary and tertiary alcohols are preferred in comparison with primary alcohols, because they usually have a higher reactivity than primary alcohols, and they can be used in milder reaction conditions.

Preferred alkylating agents can contain between 3 and 20 carbon atoms, suitable between 5 and 10 carbon atoms. The optimal number of carbon atoms in the alkylating agent typically will be determined by the desired value of the boiling point.

Liquid hydrocarbon feedstock typically contains at least 1 wt.% alkylating agent, preferably at least 3 wt.% alkylating agent, and most preferably at least 5 wt.% alkylating agent.

When a liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds in contact with an acid catalyst at elevated temperature in the first reaction zone, is obtained liquid hydrocarbons having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling point.

Can be used with any suitable acid catalyst, which is able to accelerate the alkylation of astrogenic the ski compounds with olefins or alcohols in the first reaction zone. This acid catalyst may be a liquid, such as sulfuric acid, however, the preferred acid catalyst is a solid.

Solid acid materials may include acidic polymeric resins caused acid, and acidic inorganic oxides. Suitable acid polymer resin include polymer sulfoxylate resin. Caused acids are usually acids Branstad, for example phosphoric acid, sulfuric acid, boric acid, hydrogen fluoride, persulfonic acid, triftormetilfullerenov acid, and dihydroxypregna acid, but they can also be Lewis acids, for example, BF3, BCl3, AlCl3, AlBr3, FeCl2, FeCl3, ZnCl2, SbF5, SbCl5and composition AlCl3and HCl, which are deposited on a solid substance, such as silicon dioxide, aluminum oxide, aluminosilicates, zirconium oxide or clay.

In addition, acidic inorganic oxides include aluminum oxide, aluminosilicates, natural and synthetic layered clays, both natural and synthetic zeolites, such as faujasite, mordenite, L-zeolite, omega-, X-, Y-, beta, and ZSM-zeolite. Very suitable zeolites include beta-zeolite, Y, ZSM-3, ZSM-4, ZSM-5, ZSM-18 and ZSM-20. It is advisable that the zeolites were included in the inorganic matrix oxide the first material, such as aluminosilicate.

The acid catalyst may include a mixture of different materials, such as Lewis acid, for example, BF3, BCl3, SbF5and AlCl3, neoreality solid inorganic oxides, such as silicon dioxide, aluminium oxide and silicates, porous crystalline molecular sieves, such as zeolites, layered clay and alumophosphate.

Preferably, the acid catalyst is at least partially deactivated in relation to the formation of organic sulfur compounds with high boiling point, and useful in the first reaction zone is used an acid catalyst, which was previously used in the second reaction zone, as described below.

Preferably, the liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds in contact with the acid catalyst in the first reaction zone at a temperature between 50 and 300°C, preferably between 100 and 200°With, for example, at 150°and under a pressure between 0.1 and 10.2 MPa, preferably between 1,02 and 4,08 MPa, for example 2.05 MPa.

Usually the first reaction zone is a fixed bed of the catalyst.

In the first reaction zone is formed of liquid hydrocarbons having a low content of an alkylating agent containing nitrogen is organic compounds with high boiling points. The content of the alkylating agent in the liquid hydrocarbon feedstock is reduced, since this agent reacts with the nitrogen-containing organic compounds, with the formation of alkyl nitrogen-containing organic compounds, which typically have a boiling point higher than 200°C. Typically, the temperature of boiling nitrogen-containing organic compounds is shifted up at least 50°C, preferably at least 100°and appropriate, at least at 150°C.

Usually alkiliruyutza at least 50 wt.% nitrogen-containing organic compounds present in the hydrocarbon feedstock, preferably at least 60 wt.% and appropriate alkiliruyutza at least 70 wt.% these compounds.

In the first reaction zone is formed of liquid hydrocarbons having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling point, and appropriate, these raw materials are fed to the first installation fractionation in order to obtain liquid hydrocarbons having a low content of an alkylating agent and a low nitrogen content.

Usually when fractionation is formed of at least two streams of hydrocarbons, whereby a stream of hydrocarbon feedstock has a higher boiling range and high content of nitrogen and the other thread angle is hydrogen raw material has a lower boiling range and low nitrogen content.

Fractionation is usually carried out by distillation, to separate the hydrocarbon and nitrogen compounds with high boiling point, and usually they are removed at temperatures above 150°C, preferably above 180°C.

The first installation of the fractionation may be a distillation column, designed for special purposes, such as column fractionated distillation, however, preferably, the fractionation is carried out in an existing installation distillation of crude oil (UDN) or in the main distillation column of fluid catalytic cracking (FCC).

Expediently, the first reaction zone can be located in the first installation fractionation.

The method of the present invention provides a liquid hydrocarbon feedstock having a boiling range between 10 and 450°With, for example, 10-200°or 200-350°With a nitrogen content less than 50 ppm N, for example 20-40 ppm N, preferably less than 10 ppm N, for example 5-10 ppm N, and expediently less than 5 ppm N, for example, 2-4 ppm N or less than 1 ppm of N, for example, 0.01 to to 0.5 ppm by weight, based on elemental nitrogen).

When a liquid hydrocarbon feedstock contains an alkylating agent and organic nitrogen compounds and sulfur, this liquid hydrocarbons can be brought into contact with the acid cat is a lyst at elevated temperature in the first reaction zone, as described above, with the formation of liquid hydrocarbons with a reduced content of an alkylating agent, which includes organic sulfur compounds and nitrogen-containing organic compounds with high boiling points. Then it received the hydrocarbon feedstock can be contacted with the acid catalyst in the second reaction zone to obtain liquid hydrocarbons with a reduced content of an alkylating agent, and containing organic sulfur compounds with high boiling temperature and nitrogen-containing organic compounds with high boiling point.

In the second reaction zone is usually maintained temperature between 100°300°C, preferably between 160 and 220°With, for example 190°and a pressure between 0.1 and 10.2 MPa, preferably between 1,0 and 6.1 MPa, for example a 2.0 to 4.1 MPa, and usually it includes a fixed layer of an acid catalyst.

The acid catalyst in the second reaction zone may be acidic catalyst, which is already described above.

In the second reaction zone is produced liquid hydrocarbons having an even lower content of alkylating agent, and containing a nitrogen-containing organic compounds with high boiling point and organic sulfur compounds with high boiling points. The content of the alkylating agent vidcom hydrocarbon raw material is additionally reduced, as the agent interacts with organic sulfur compounds, with the formation of alkyl of organic sulfur compounds, which typically have a boiling point between 100 and 250°C.

Usually the boiling point of the organic sulfur compounds is shifted up at least 50°C, preferably at least 100°and appropriate, at least at 150°C.

Usually alkiliruyutza at least 50 wt.% organic sulfur compounds contained in the liquid hydrocarbon feedstock, preferably, alkiliruyutza at least 60 wt.% and appropriate alkiliruyutza at least 70 wt.%.

In the first and second reaction zones is formed of liquid hydrocarbons having a low content of an alkylating agent containing organic sulfur compounds with high boiling temperature and nitrogen-containing organic compounds with high boiling point, and these raw materials are sent to the appropriate installation fractionation to remove nitrogen-containing organic compounds with high boiling points, and organic sulfur compounds with high boiling point and to obtain a liquid hydrocarbon feedstock with a reduced content of an alkylating agent and a low content of nitrogen and sulphur.

Usually when fractionation is formed, at least, zapoteca hydrocarbons, one stream of hydrocarbon feedstock has a higher boiling range and high content of nitrogen and sulfur, and the other stream of hydrocarbon material has a lower boiling range and low content of nitrogen and sulphur.

Fractionation is usually carried out by distillation, as described above, in order to separate the hydrocarbons, sulfur and nitrogen compounds with high boiling point, and usually they are removed at temperatures above 150°C, preferably above 180°C.

Expediently, the first and second reaction zones may be located in the first installation fractionation.

Alternatively, the liquid hydrocarbon feedstock with a reduced content of an alkylating agent, and containing organic sulfur compounds and nitrogen-containing organic compounds with high boiling point, may be subjected to fractionation in the first installation fractionation, to contact with the acidic catalyst in the second reaction zone. Usually fractionation (described above) are formed at least two streams of hydrocarbons, whereby a stream of hydrocarbon feedstock has a higher boiling range and high content of nitrogen, and the other stream of hydrocarbon material has a lower boiling range and low nitrogen content. Then thread Ugledar the underwater raw materials with a lower boiling range and low nitrogen content (which, in addition, it contains an alkylating agent and organic sulfur compounds) served in the second reaction zone in which is formed a liquid hydrocarbon feedstock containing organic sulfur compounds with high boiling points, which are subsequently removed in the second installation fractionation.

Expediently, the second reaction zone can be located in the second installation fractionation.

Furthermore, the method of the present invention provides a liquid hydrocarbon feedstock having a boiling range between 10 and 450°With, for example, 10-200°or 200-350°containing less than 50 ppm nitrogen, for example 20-40 ppm N, preferably less than 10 ppm N, for example 5-10 ppm N, and expediently less than 5 ppm N, for example 2-4 ppm N or less than 1 ppm N, for example, from 0.01 to 0.5 ppm N (by weight, based on elemental nitrogen and sulfur content less than 500 ppm S, for example, 200-400 ppm S, preferably less than 200 ppm S, for example, 50-100 ppm S, and expediently less than 50 ppm S, for example 20-40 ppm S or less than 10 ppm S, for example, 0.1 to 5 ppm by weight, based on elemental sulfur).

The methods of the present invention can be appropriate to provide raw materials for any process stage at which it is undesirable in the presence of nitrogen and optionally sulfur. In particular, the methods of the present izobreteny which can be appropriate to provide raw materials for catalytic reforming, catalytic Hydrotreating and catalytic hydrodesulphurization unit.

Expediently, the method of reducing the content of nitrogen in liquid hydrocarbons, which are described above, can provide raw materials for sulfur removal processes, which are disclosed in the documents US 6024865, US 6048451, US 6059962, WO 01/53432A1 and WO 01/53433, the description of which is entered in this invention as a reference.

Appropriate, this method can be used for the removal of nitrogen to the process of adsorption of sulfur to prevent the preferred adsorption of nitrogen compounds on the adsorbent as compared with the sulfur compounds.

Now, this invention will be described with reference to the following drawings.

Figure 1 shows the first reaction zone (1) and the fractionation unit (2). A liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds, is passed to the first reaction zone (1) through line (3), in which it is in contact with the acidic catalyst, and a nitrogen-containing organic compounds alkiliruyutza with the formation of nitrogen-containing organic compounds with high boiling point.

Then liquid hydrocarbons in line (4) is fed to the fractionation unit (2), in which it is shared with the formation of a stream of hydrocarbons with lower boiling range and low nitrogen content, which leaves the unit fraction the simulation (2) line (5), and flow of hydrocarbons with higher boiling range and a high content of nitrogen, which leaves the fractionation unit (2) through line (6).

Figure 2 shows the first reaction zone (1), the second reaction zone (2) and the fractionation unit (3). A liquid hydrocarbon feedstock containing an alkylating agent and organic nitrogen compounds and organic sulfur compounds, is fed through line (4) in the first reaction zone (1), in which it is in contact with the acidic catalyst, and a nitrogen-containing organic compounds alkiliruyutza with the formation of nitrogen-containing organic compounds with high boiling point.

Then the flow of hydrocarbons through line (5) is fed to the second reaction zone (2), in which it is in contact with the acid catalyst, and organic sulfur compounds alkiliruyutza with the formation of organic sulfur compounds with high boiling point.

Then liquid hydrocarbons in line (6) is fed to the fractionation unit (3), in which it is shared with the formation of a stream of hydrocarbons with lower boiling range and low content of nitrogen and sulfur, which leaves the fractionation unit (3) line (7), and the flow of hydrocarbons with higher boiling range and a high content of nitrogen and sulfur, which leaves the block practionier the project (3) line (8).

Figure 3 shows the first reaction zone (1), the second reaction zone (2), the first block fractionation (3) and the second block fractionation (4). A liquid hydrocarbon feedstock containing an alkylating agent and organic nitrogen compounds and organic sulfur compounds, is fed through line (5) in the first reaction zone (1), in which it is in contact with the acidic catalyst, and a nitrogen-containing organic compounds alkiliruyutza with the formation of nitrogen-containing organic compounds with high boiling point.

Then liquid hydrocarbons in line (6) into the first fractionation unit (3), in which it is shared with the formation of a stream of hydrocarbons with lower boiling range and low nitrogen content, which leaves the first block fractionation (3) line (7), and the flow of hydrocarbons with higher boiling range and a high content of nitrogen, which leaves the fractionation unit (3) line (8).

Then the flow of hydrocarbons coming out of the first block fractionation (3) line (7) is fed to the second reaction zone (2), in which it is in contact with the acid catalyst, and organic sulfur compounds alkiliruyutza with the formation of organic sulfur compounds with high boiling point.

Then liquid hydrocarbons on the line is (9) into the second fractionation unit (4), in which it is shared with the formation of a stream of hydrocarbons with lower boiling range and low sulfur content, which leaves the second block fractionation (4) line (10), and the flow of hydrocarbons with higher boiling range and a high sulfur content, which leaves the second block fractionation (4) line (11).

1. The method of raising the temperature of boiling nitrogen-containing organic compounds present in the liquid hydrocarbon feedstock, wherein said method is that the liquid hydrocarbon feedstock containing an alkylating agent and a nitrogen-containing organic compounds, with the specified liquid hydrocarbon feedstock is one or more oil fractions with a boiling range 10-450°selected from naphtha catalytic cracking, coking naphtha and naphtha visbreaking, contact with contributing to the alkylation acid catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling points.

2. The method of reducing the nitrogen content in the liquid hydrocarbon feedstock, wherein said method consists in the fact that

a) liquid hydrocarbons, sod is rashee alkylating agent nitrogen-containing organic compounds, with the specified liquid hydrocarbon feedstock is one or more oil fractions with a boiling range 10-450°selected from naphtha catalytic cracking, coking naphtha and naphtha visbreaking, contact with contributing to the alkylation acid catalyst at elevated temperature in the first reaction zone to form a liquid hydrocarbon having a low content of an alkylating agent containing a nitrogen-containing organic compounds with high boiling point,

b) remove the nitrogen-containing organic compounds with high boiling point, in order to obtain liquid hydrocarbons having a low content of an alkylating agent and a low nitrogen content.

3. The method according to claim 2, in which the nitrogen-containing organic compounds with high boiling point are removed by fractionation.

4. The method according to claim 2, in which

at the stage of (a) the use of liquid hydrocarbons, optionally containing organic sulfur compounds, and form liquid hydrocarbons, optionally containing organic sulfur compounds with a high boiling point;

at the stage (b) in addition carry out the contacting liquid hydrocarbons having a low content of alkylating agent and sod rasego of organic sulfur and nitrogen-containing organic compounds with high boiling point, with an acid catalyst at elevated temperature in the second reaction zone, to form a liquid hydrocarbon having a low content of an alkylating agent containing organic sulfur compounds with high boiling temperature and nitrogen-containing organic compounds with high boiling point;

followed by fractionation of liquid hydrocarbons having a low content of an alkylating agent containing organic sulfur compounds with high boiling temperature and nitrogen-containing organic compounds with high boiling point, in order to remove nitrogen-containing organic compounds with high boiling point and organic sulfur compounds with high boiling point and to obtain liquid hydrocarbons having a low content of an alkylating agent and a low content of nitrogen and sulphur.

5. The method according to claim 2, in which

at the stage of (a) the use of liquid hydrocarbons, optionally containing organic sulfur compounds, and form liquid hydrocarbons, optionally containing organic sulfur compounds with a high boiling point;

at the stage (b) first additionally carry out the fractionation of liquid hydrocarbons having a reduced content is of an alkylating agent containing organic sulfur and nitrogen-containing organic compounds with high boiling point, in order to remove nitrogen-containing organic compounds with high boiling point and to obtain liquid hydrocarbons having a low content of an alkylating agent, the low content of nitrogen and organic sulfur compounds;

then carry out the contacting liquid hydrocarbons having a low content of an alkylating agent containing organic sulfur compounds and the low content of nitrogen, with an acid catalyst at elevated temperature in the second reaction zone to form a liquid hydrocarbon having a low content of an alkylating agent, organic sulfur compounds with high boiling point and low nitrogen content;

followed by fractionation of liquid hydrocarbons having a low content of an alkylating agent, organic sulfur compounds with high boiling point and low nitrogen content, in order to remove organic sulfur compounds with high boiling temperature, to form a liquid hydrocarbon having a low content of an alkylating agent and a low content of nitrogen and sulphur.

6. The method according to any one of the preceding paragraphs, in which liquid hydrocarbons are selected from gasoline, kerosene, diz is high or jet fuel.

7. The method according to claims 1 to 5, in which the nitrogen-containing organic compounds selected from alkylamines followed, anilines, pyrrole and/or pyridines.

8. The method according to claims 1 to 5, in which the liquid hydrocarbon feedstock containing nitrogen-containing organic compounds, usually has a total nitrogen content (calculated as elemental nitrogen) between 5 and 3000 hours/million n

9. The method according to claims 1 to 5, in which the nitrogen-containing organic compounds have a boiling point between 50 and 450°C.

10. The method according to claims 4 and 5, in which organic sulfur compounds selected from mercaptans, teofanov and benzothiophenes, dibenzothiophenes and/or spatial difficult alkyl substituted dibenzothiophenes.

11. The method according to claims 4 and 5, in which liquid hydrocarbons which comprises alkylating agent and organic nitrogen compounds and sulfur, has a total sulfur content (calculated as elemental sulfur) 10-50000 hours/million S.

12. The method according to claims 1 to 5, in which the acid catalyst is a solid.

13. The method according to any one of claims 1 to 5, in which in a first reaction zone to maintain the temperature between 50 and 300°and a pressure between 0.1 and 10.2 MPa.

14. The method according to claims 4 and 5, in which the second reaction zone to maintain the temperature between 100 and 300°and a pressure between 0.1 and 10.2 MPa.



 

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19 cl, 1 ex

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1 dwg, 3 tbl

FIELD: oil production, oil refinery and petrochemical industries, particularly for hydrogen sulfide and mercaptan neutralization in hydrocarbon medium with the use of chemical neutralization agents.

SUBSTANCE: hydrogen sulfide and mercaptan neutralizing agent comprises 30-58% by weight of formalin, alkali metal, preferably sodium, hydroxide or carbonate in amount of 0.1-3% by weight, hexamethylenetetramine in amount of 15-25% by weight, remainder is tertiary alkamine, preferably triethanolamine and/or methyldethanolamine. Neutralizing agent in accordance with the second embodiment additionally includes bactericide composition.

EFFECT: increased neutralizing agent efficiency, enhanced manufacturability (low solidification temperature) and reactivity, provision of high hydrocarbon medium (oil, oil product and gaseous hydrocarbon) cleaning of hydrogen sulfide and light-weight mercaptans at room and increased temperatures (of 10-90°C and higher), improved bactericidal activity and corrosion inhibiting effect in hydrogen sulfide mediums, possibility of neutralizing agent usage as bactericide and corrosion inhibitor in oil-field media.

7 cl, 15 ex, 1 tbl

FIELD: crude oil treatment.

SUBSTANCE: to remove hydrogen sulfide and mercaptans, 3-30% solution of urotropin in technical-grade formalin or in formalin/aqueous ammonia is added to crude material in amounts corresponding to 0.8-3.5 mole formaldehyde and 0.009-0.3 mole urotropin per 1 mole hydrogen sulfide and mercaptan sulfur. Reaction is carried out at 15 to 70°C. Method is applicable for oil and gas production and petroleum processing industries.

EFFECT: reduced consumption of reagents at high degree of purification of raw material.

5 cl, 3 tbl

The invention relates to petrochemistry, in particular to methods of refining oil, gas condensate and their fractions from mercaptans and hydrogen sulfide

The invention relates to the refining, in particular to methods of cleaning condensate and its fractions from mercaptans

The invention relates to methods for cleaning hydrocarbons from sulfur compounds and can be used in gas - and oil-refining industry

The invention relates to means for neutralization of hydrogen sulfide and light mercaptans, inhibit the growth of sulfate reducing bacteria (SRBs) and inhibition of hydrogen sulfide corrosion in oilfield environments

The invention relates to the purification of petroleum products from sulfur compounds and can be used in industry gazoneftepererabatyvayuschy

The invention relates to methods of oil for transport and can be used in the oil and gas industry in the preparation of sulfur crude oil, condensates with high content of hydrogen sulfide and mercaptans

FIELD: crude oil treatment.

SUBSTANCE: to remove hydrogen sulfide and mercaptans, 3-30% solution of urotropin in technical-grade formalin or in formalin/aqueous ammonia is added to crude material in amounts corresponding to 0.8-3.5 mole formaldehyde and 0.009-0.3 mole urotropin per 1 mole hydrogen sulfide and mercaptan sulfur. Reaction is carried out at 15 to 70°C. Method is applicable for oil and gas production and petroleum processing industries.

EFFECT: reduced consumption of reagents at high degree of purification of raw material.

5 cl, 3 tbl

FIELD: oil production, oil refinery and petrochemical industries, particularly for hydrogen sulfide and mercaptan neutralization in hydrocarbon medium with the use of chemical neutralization agents.

SUBSTANCE: hydrogen sulfide and mercaptan neutralizing agent comprises 30-58% by weight of formalin, alkali metal, preferably sodium, hydroxide or carbonate in amount of 0.1-3% by weight, hexamethylenetetramine in amount of 15-25% by weight, remainder is tertiary alkamine, preferably triethanolamine and/or methyldethanolamine. Neutralizing agent in accordance with the second embodiment additionally includes bactericide composition.

EFFECT: increased neutralizing agent efficiency, enhanced manufacturability (low solidification temperature) and reactivity, provision of high hydrocarbon medium (oil, oil product and gaseous hydrocarbon) cleaning of hydrogen sulfide and light-weight mercaptans at room and increased temperatures (of 10-90°C and higher), improved bactericidal activity and corrosion inhibiting effect in hydrogen sulfide mediums, possibility of neutralizing agent usage as bactericide and corrosion inhibitor in oil-field media.

7 cl, 15 ex, 1 tbl

FIELD: crude oil treatment.

SUBSTANCE: treatment of hydrogen sulfide-containing crude oil before transportation and separation comprises multistep separation of original crude oil followed by dehydration and desalting, flushing with hydrocarbon gas in desorption column, and addition of monomethanolethanolamine (obtained by reaction of monomethanolamine with formaldehyde), and stirring. Flushing is accomplished with hydrogen sulfide-containing gas ensuring weight percentage of hydrogen sulfide in post-flushing oil no higher than 200 ppm. After addition of monomethanolethanolamine, according to invention, up to 10% of fresh washing water is additionally charged. All aforesaid operations are carried out before desalting step.

EFFECT: reduced contents of hydrogen sulfide and water in commercial oil.

1 dwg, 3 tbl

FIELD: petrochemical industry; other industries; methods of production of the hydrogen for the fuel composition.

SUBSTANCE: the invention is pertaining to the method of production of hydrogen for the fuel composition. The method of production of hydrogen for the fuel composition from the hydrocarbon fuel composition includes the following stages: preparation of the hydrocarbon fuel composition, which is produced: i) injection of the liquid hydrocarbon raw including the alkylating agent, in contact with the acid catalyst in the conditions, which are effective for alkylation, at least, of the parts of the hydrocarbon raw, where the liquid hydrocarbon raw additionally includes the aromatic compounds, which are alkylated at the stage of the alkylation; and ii) separation from the stage of the alkylation of the low-boiling fraction containing the hydrocarbons and the aromatic hydrocarbons with the lowered concentration in the capacity of the hydrocarbon fuel composition, transformation of the hydrocarbon fuel composition into the hydrogen and optional injection of the produced hydrogen into the fuel composition. The invention makes it possible to raise efficiency of the production process.

EFFECT: the invention ensures the increased efficiency of the production process.

10 cl, 3 tbl, 3 ex

Treatment process // 2316577

FIELD: petroleum processing.

SUBSTANCE: invention relates to process of treating hydrocarbon stock, in particular to reducing nitrogen level in liquid hydrocarbon stock. Process is characterized by that (a) liquid hydrocarbon stock containing alkylation agent and organonitrogen compounds is brought into contact with acid catalyst at elevated temperature in a first reaction zone to form liquid hydrocarbon stock with reduced content of alkylation agent and organonitrogen compounds having elevated boiling temperatures; and (b) liquid hydrocarbon stock with reduced content of alkylation agent and containing organonitrogen compounds with elevated boiling temperatures is fractioned to remove said organonitrogen compounds.

EFFECT: enabled production of liquid hydrocarbon stock with reduced content of alkylation agent and reduced nitrogen level.

14 cl, 3 dwg

FIELD: oil and gas processing.

SUBSTANCE: neutralizer contains 30-60% formalin, 0.1-3% alkali metal (sodium) hydroxide and/or carbonate, 5-35% bactericidal agent, preferably Baktsid, Sontsid, or Sulfan, and tertiary aminoalcohol (triethanolamine and/or methyldiethanolamine) to 100%. Neutralizer may further contain urotropin in amount from 5 to 22%. With such composition, effective neutralizer is characterized by high processability (low freezing temperature) and reactivity, which favors high degree of purification of crude oil, petroleum products, and hydrocarbon gases polluted by hydrogen sulfide and light mercaptans.

EFFECT: enhanced neutralization activity accompanied by bactericidal activity and anticorrosion effect in hydrogen sulfide-containing media.

4 cl, 1 tbl, 15 ex

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

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