The method of reducing the content of the bromine-reactive contaminants in aromatic materials
Usage: petrochemistry. Essence: bromine-reactive hydrocarbon impurities are removed from aromatic materials by preparing aromatic starting material, which is characterized by low concentration of dienes. The source material is introduced into contact with an acid active catalyst composition under conditions sufficient to remove monoolefins. Aromatic material may be pre-treated to remove dienes by contacting this material with clay as a catalyst, hydrogenation or Hydrotreating conditions sufficient to remove a substantial part of dienes, but not monoolefins. The technical result is an increase in cycle times. 9 C.p. f-crystals, 2 tab., 2 Il. The invention relates to removing bromine-reactive hydrocarbon contaminants from aromatic materials through contact of these products with acid active catalyst. Aromatic materials are characterized by low content of dienes to contact and reduced content of monoolefins dienes and after contact. In accordance with the invention, the ical materials produced by such processes, as the reforming of gasoline, ligroin fraction and thermal cracking (pyrolysis). These aromatic materials also contain undesirable hydrocarbon impurities, including monoolefinic, dieny, sterols and heavy aromatic compounds such as anthracene.Such aromatic materials are used as starting materials when carrying out various subsequent processes of petrochemical synthesis. During some of these processes, such as obtaining para-xylene, for example, from aromatic material containing benzene, toluene and xylene (BTX), or disproportionation of toluene, hydrocarbon impurities cause undesirable side reactions. Thus, hydrocarbon impurities must be removed before further processing of aromatic materials.Moreover, advanced techniques for aromatic materials, such as described in Handbook of Petroleum Processing, McGrow-Hill, new York, 1997, page 4.3-4.26, allow to increase the yield of aromatic materials, but with the formation of increased amounts of bromine-reactive hydrocarbon contaminants. In the transition from preregistration risoluto reforming significantly increases the proportion of bromine-reactive contaminants. This in turn involves an even greater need to develop more effective and less costly to implement ways to remove hydrocarbon contaminants from aromatic materials.The concentration of undesirable hydrocarbon contaminants containing olefinic communication, quantitatively expressed using bromine index (BI). Undesirable olefins, including both diene and monoolefinic, usually removed from an aromatic materials, such as containing BTK, in parallel, by contacting the aromatic material with the acid-treated clay. For this purpose, use other materials, such as zeolites. Clay is a naturally occurring amorphous material, whereas zeolites used for this purpose usually synthesize, so they are more expensive. As clay and zeolites are characterized by a very limited lifespan in the processing of aromatic materials. The lifetime associated with the concentration of bromine-reactive contaminants in the source material. BI-reactive impurities quickly age as clay, and zeolites. Although virtually of these two materials clay and is less than a million dollars a year. In addition, since zeolites are much more expensive clay, their use in the removal of hydrocarbon contaminants can be justified only in the event of a sharp increase stability in the processing of aromatic materials, whereby the length of the operating cycle would be of practical value.The objective of the invention is to develop methods for removing bromine-reactive hydrocarbon contaminants from aromatic materials with longer practical work cycle.Another object of the invention is the development of approaches associated with removing bromine-reactive hydrocarbon contaminants from aromatic materials with the use of catalysts based on crystalline molecular sieve under conditions conducive to the stability of the catalyst to the extent which is sufficient for economic viability replacement used for this purpose clay.Another object of the invention is to develop a method of pre-processing of aromatic materials to remove dienes to remove monoolefins.Method of removing bromine-reactive hydrocarbon contaminants in the specified minor concentration of dienes, and contacting this material with an acid active catalyst composition under conditions sufficient to remove monoolefinic bromodomain reactive hydrocarbon contaminants.The preferred acid active catalyst is a crystalline molecular sieve comprising oxygen-containing ring with ten or more members, more preferably layered material.Aromatic hydrocarbon material, which is intended for contact with acid active catalyst, is an essentially free of dienes and aromatic hydrocarbon material. This material can be obtained free of dienes form from another oil refining process or containing diene material may be pre-treated for the selective removal of dienes. The material may be pre-treated by contact with clay or Hydrotreating catalyst under conditions sufficient to remove substantial amounts of dienes, but not monoolefins.Attached to the description of the drawings shown in Fig.1 is a graph illustrating obtained in example 4, the results, and Fig.2 - Graveline bromine-reactive hydrocarbon contaminants from aromatic materials.Aromatic materials can be obtained from the processes of reforming and cracking. These materials include, for example, monocyclic aromatic hydrocarbons and unsaturated olefins including styrene, and are characterized by a bromine index (BI) 100-3000. The bromine index is an indicator of the presence of olefinic linkages. Bromine index was determined in accordance with ASTM D 2710-92, and it reflects the number of milligrams of bromine consumed 100 g of the sample under these conditions.Aromatic materials include, for example, benzene, toluene, xylene, ethylbenzene, cumene and other aromatic compounds obtained, for example, from the product of the reformer. The product of reforming separated by distillation in an easy product reforming, which is mainly benzene and toluene, and the heavy product of the reformer, which includes toluene, ortho-, meta - and para-xylenes and other heavier aromatic compounds, which include9and more high-molecular compounds. Some aromatic materials, such as heavy reforming product obtained from preregistration processes when it comes from the recycling process includes minor amounts of dienes. Under a small concentration. Other aromatic materials, such as lightweight product reforming obtained from preregistration reforming units, and light and heavy products of the reforming process NKR (continuous catalyst regeneration) include more significant amounts of dienes that can be detected, for example more than 50 part./millionAromatic materials sent for processing in accordance with the invention, include bromine-reactive hydrocarbon compounds in the concentrations at which they interfere with subsequent processing of aromatic compounds. Unacceptable concentration of olefinic aromatic impurities is 0.05-1.5 mass percent (wt.%) or meets BI 100-3000.The method according to the invention allows to reduce the concentration of impurities in the aromatic material to the level where they do not hinder subsequent processing of these aromatic materials.Aromatic hydrocarbon material treated to remove monoolefins in accordance with the invention, practically free from dienes, i.e., contains diene in small quantities. If the concentration of dienes in the aromatic material exceeds ettiene. Dieny be more selective regarding the formation of coke and deactivation of the catalyst than monoolefinic. For this reason, those exhibiting high reactivity of diene materials almost completely removed above the first catalyst.In a preferred embodiment, the stage of pre-treatment is carried out at a temperature of 50 or 100 to 500oF, more preferably inlet 150 up to 450oF. the Preferred average hourly feed rate (SCSPS) is 0.1-10, and the preferred gauge pressure is 50-500 psig. Pre-processing performed in the absence of added hydrogen. Preferred catalysts for the preliminary processing stage include the acid-treated clay, such as bentonite, and traditional containing base metal catalysts for Hydrotreating or hydrogenation, such as Ni/Al2About3, CoMo/Al2O3, Ni/Al2About3and Ni/SiO2.Further pre-treated aromatic starting material is treated over a second catalyst to remove a substantial portion of monoolefins.Catalysts for the selective removal monoolefinic compounds include, for example, krupnoperistye as a product of M41S company SAPO, columnar and/or layered materials.Zeolites in accordance with their ERP systems/channels are divided into three main groups. These systems include 8-membered oxygen ring systems, 10-membered oxygen ring system, a 12-membered oxygen ring systems and double porous system, which includes 10 - and 12-membered oxygen ring openings. Usually they are called zeolites with pores small, medium or large size, which are caused 8-12-membered systems. These systems are more fully described in Atlas of Zeolite Structure Types, International Zeolite Asso., Polycrystal Book Service, Plattsburg, 1978.The chemical composition of zeolites can vary within wide limits, and they usually consist of SiO2in which some silicon atoms can be substituted tetravalent ions such as ions of Ti and Ge, or trivalent ions such as ions of Al, In, Ga, Fe, or divalent ions, such as ions Be, ions other representatives of group III of the Periodic table of elements or combinations of the above ions. When there is substitution of divalent or trivalent ions in the synthesized zeolite contains cations such as Na+, CA++, NH4-or H+; the same can be scatted using zeolite organic materials, as a rule, are removed by calcination. For ion exchange with residual cations, for example with NH4+usually followed by calcination to obtain the acid zeolite.Preferred catalysts include natural and synthetic crystalline molecular sieve with a ten-dvenadcatiletnie ring structures or with a large number of members. Crystalline molecular sieves which may be used as catalysts, as non-limiting examples include macroporous zeolites ZSM-4 (omega-zeolite) (US 3923639), mordenite, ZSM-18 (US 3950496), ZSM-20 (US 3972983), beta-zeolite (US 3308069 and replacement patent Re 28341), tasit X (US 2882244), tasit Y (US 3130007), USY (US 3293192 and US 3449070), REY and varieties X and Y, MCM-22 (US 4954325), MSM-36 (US 5229341), MCM-49 (US 5236575), MCM-56 (US 5362697) and crednerite materials such as M41S (US 5102643) and MCM-41 (US 5098684). Preferred molecular sieves include 12-membered oxygen ring structure ZSM-12, mordenite, beta-zeolite, USY and mixed 10-12-membered oxygen ring structure of the family of MCM-22, laminates and crednerite materials. Most preferred are molecular sieves family of MCM-22. This family, i.e., materials such as MCM-22 include, for example, MCM-22, MSM layer. This structural unit is described, for example, in US 5371310, US 5453554, US 5493065 and US 5557024.One criterion acid activity can be called the alpha value. The alpha value is an approximate indicator of the acid activity of the catalyst, which is characterized by constant relative speed (the speed of conversion of normal hexane to volume of catalyst per unit time). It is based on the activity of highly active kranidioti/aluminiumoxide of cracking catalyst taken as an alpha of 1 (rate constant = 0,16-1). Alpha test is described in US 3354078, Journal of Catalysis, volume 4, pages 527 (1965), volume 6, page 278 and volume 61, page 395 (1980). Experimental conditions used in this test include a constant temperature of 538oWith a variable flow rate as described in Journal of Catalysis, volume 61, page 395 (1980). Alpha values catalysts are 100-1000.The crystalline molecular sieve can be used in bound form, i.e. in the composition with a matrix material, including synthetic and naturally occurring substances, such as clay, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, kranidioti/aluminiumoxid and other metal oxides. Found in predate the actual matrix, which often, by nature, is acidic. Other porous matrix materials include kranidioti/maniaxe, kranidioti/zirconiated, kranidioti/trideoxy, kranidioti/brilliance, kranidioti/titanpoker, as well as ternary compositions, such as kranidioti/aluminiumoxid/trideoxy, kranidioti/aluminiumoxid/zirconiated and kranidioti/aluminiumoxid/maniaxe. Can also be used mixtures of these components. The relative amount of the crystalline molecular sieve material and the matrix can be varied in a wide range from 1 to 90 wt. %, typically from 20 to 80 wt.%. The catalyst can also be used in the absence of matrix or binder, i.e., in the unconjugated form. The catalyst may be used in the form of an extrudate, in a layered form (e.g., sandwich) or in powder form.Usually the way to remove monoolefins carried out under conditions including a moderately elevated temperature, preferably in the range from 200 or 250 to 500oF, more preferably from 250 to 450oF, average hourly feed rate (SCSPS) from 0.1 to 100, more preferably from 1 to 30, and a gauge pressure of from 50 to 1000 pounds per square is limiting its scope.The experiments were performed in the installation of the downdraft and a fixed layer in which there was a reactor of stainless steel with an external diameter of 18 1/2 inches with pocket thermocouple with an outer diameter of 1/8 inch and installed in the Central part inside the 10-inch one zone of the furnace. Source materials served With7and more high molecular weight aromatic products and crude toluene fraction derived from aromatic raw materials With7- and heavier products in beaumont (Beaumont). The initial bromine index (BI) of the source material was 850. The raw materials were introduced using two volumetric pumps of high pressure. The reaction gauge pressure was maintained at 200 psig using a bootable device. From the boot device the product was received in a collecting tank made of stainless steel, connected to a breathing valve. No gas is introduced, and was not received. Using capillary gas chromatography column liquid product was analyzed for conversion of olefins and the total concentration of bromine-reactive components with application of the test for bromine index in accordance with ASTM D 2710-92.To handle aromatizes the ow in the reactor was caliciviral at 250oC for at least one hour to remove water.EXAMPLE 1 processing of aromatic starting material used clay. The process conditions and the results are presented in table 1.To reduce the amount of time required initial stage of the experiment, presented in table 1, was carried out at increased SCSPS. As shown in table 1, the life of the clay when SCSPS 1,6 constituted, as defined, 24 days, and the performance of the clay at the required BI was equal to 2850 of barrella a pound of clay. This means that one pound of clay was able to handle 3.2 barrel of this source material with BI 850 until it reaches the end of the cycle according to the technical conditions with BI 70.EXAMPLE 2 In the second experiment on aging for the selective conversion of dienes within 96 days at temperatures below 291oF used clay F-24. The test conditions and the results are presented in table 2.Performance in relation to BI clay increased with 2850 in example 1 to 5200 in example 2. As in example 1 and in example 2, the lifetime of the clay at 390oF and SCSPS of 1.6 was 24 days, i.e. at a temperature below 250owhen clay accounted for 10% conversion with respect to the initial values of the underwater material. To identify GC-peaks associated with this decline in BEE product with MB-15 carefully analyzed by capillary GC-column and compared with the original material. Data GC was not possible to note any significant difference between raw material and product. Dieny able to interact with the bromine-reactive compounds, which are known, are the products of reforming in quantities sufficient to assess the observed decrease in BI, and contains many isomers in very low concentrations, which could be considered not allowed to observe their disappearance by GC. In the following example 3 used a different method of testing diene.EXAMPLE 3 For the dienes contained in the product of reforming With7and more high-molecular compounds at low concentrations, a simple analytical tests do not exist. To confirm the presence of significant amounts of dienes in raw materials was tasked with analyzing the incoming fraction. Aromatic With7- and heavier products, which were subjected to treatment with the use of clay was obtained by sampling the raw material flowing into the column at an oil C is, analyzed as follows: in a round bottom flask 300 g of the crude toluene fractions were added to 0.50 g of maleic anhydride. The flask was supplied with the refrigerator, put in the heater casing and the contents brought to the boil under reflux. After 20 h, the flask was again cooled to room temperature. All contents of the flask were concentrated using a rotary evaporator equipped with a vacuum pump for maintaining in the system a residual pressure of <5 mm RT.art., 50-ml tared round bottom flask. The temperature of the water bath was maintained at a level of 75oC. in This way received 104 mg of white crystalline material, which was analyzed by NMR spectroscopy according to the method described by L. B. Alemany and S. H. Brown, Energy and Fuels, 1995, 9: 257-268. These NMR spectroscopy showed that the material largely consisted of products of accession of maleic anhydride/dienes and presumably included 8 diene precursors. In addition, these data indicated that 70% of these products accession was obtained from cyclic dienes (presumably from dimethylcyclopentane) and 30% of acyclic dienes; 104 mg products attach corresponded to 170 ppm million dienes in ins in the boiling range C7- and heavier products cause, apparently, the decrease in BI 80, which is in good agreement with the content of dienes 170 part./million, which is installed in the light fraction. Because of the above analysis it is known that diene contained in the raw material in an amount which causes, apparently, the observed decrease in BI over the clay, you should find a convenient way to analyze obtained after treatment with clay product in the conversion of dienes. NMR spectroscopic analysis showed that the majority of dienes was cyclic compounds, whence we can conclude that the most visible danami in toluene boiling range are probably dimethylcyclopentane. The mass of the ion in the molecule of these compounds is 94, which cannot be explained any other hydrocarbons, which probably boil together with toluene. Raw materials and product with MB-15 was subjected to research on mass spectroscopy GC-analyzer equipped with means for selective monitoring of ions. Comparing responses to ion mass 94 in toluene range of raw materials and product. Four peak is clearly consistent with the raw materials and were absent during the study product, which was the m clay F-24.The results of the analysis confirm that the clay dieny much more reactive than olefins, and that you can define conditions in which diene raw materials usually undergo a full transformation, while contained in the raw material olefins largely remain neprevzaidennymi.EXAMPLE 4 Obtaining free of dienes source material for the second catalytic layer reduces the rate of aging of this second layer. To confirm that compared the results of an experiment carried out in two reactors, and the experiment conducted in the same reactor. In the first reactor, a twin installation was downloaded clay and within 7 days at 175oF and SCSPS of 1.6 was in the process using the product of reforming With7and more high-molecular compounds with BI 850. After 7 days B at the outlet of the reactor was 770. Then a continuous process performed in the second reactor samosatenus catalyst MCM-22 at SCSPS 10 and 290oF. the process of aging was monitored daily by defining BI product. In Fig.1 presents a graph of the rate of aging in two experiments, which shows that the rate of aging in a twin system is much lower than the speed with the C aromatic material, initial BI of which amounted to 850, felt the extrudate product MCM-22/aluminiumoxide, the extrudate samosatenus product MCM-22, zeolite extrudate in the hydrogen form USY/aluminiumoxide, the extrudate 65% beta zeolite/kremmidiotis and clay (product F-24 the company Engelhard).The conversion activity of the bromine-reactive contaminants in aromatic material was determined as a function of the length of the continuous process SCSPS 10, 390oF and under a gauge pressure of 200 pounds per square inch. Data on the aging of the catalyst is shown in Fig.2.The angle of slope of a plot of aging for samosatenus product MCM-22 was 6.5% B/day for MSM-22/aluminiumoxide was equal to 30% B/day for beta-zeolite/kremmidiotis was equal to 90% B/day for USY/aluminiumoxide was 140 units BI/day. Clay when SCSPS 10 were inactive.These results indicate that contrary to expectations when removing bromine-reactive contaminants from an aromatic materials product MCM-22 shows stability.
Claims1. Method of removing bromine-reactive contaminants from an aromatic hydrocarbon sustained fashion concentration of dienes, and contacting this material with an acid active catalyst composition under conditions sufficient to remove monoolefinic bromine-reactive contaminants.2. The method according to p. 1, characterized in that the concentration of dienes is less than 50 frequent. /million3. The method according to p. 1, characterized in that the aromatic hydrocarbon material is a product of reforming With7and more high-molecular compounds or light product of the reformer.4. The method according to p. 1, characterized in that the acid active catalyst composition is a crystalline molecular sieve with pores/channels having desyatiletnie oxygen ring openings or oxygen ring openings with a more significant number of members.5. The method according to p. 4, wherein the crystalline molecular sieve is a product MCM-22.6. The method according to p. 1, wherein the conditions include a temperature of 200-500oF, average hourly feed rate of 0.1-100 and manometrically pressure of 50-1000 pounds per square inch.7. The method according to p. 1, characterized in that the aromatic hydrocarbon material is characterized by the concentration of dienes that SN is I.8. The method according to p. 7, wherein pre-processing comprises contacting the aromatic hydrocarbon material containing diene, remove dieny catalytic composition under conditions sufficient to remove minor dienes, but not monoolefins.9. The method according to p. 8, wherein removing diene catalyst is a clay or containing a base metal catalyst Hydrotreating or hydrogenation.10. The method according to p. 8, wherein the conditions sufficient to remove a substantial part of dienes, but not monoolefins include temperature 50-500oF, average hourly feed rate of 0.1-10, gauge pressure ranges from 50 to 500 pounds per square inch and the absence of added hydrogen.
SUBSTANCE: present invention relates to removal of sulphur from hydrocarbon streams, to a composition which is suitable for use in desulphuration of streams of cracked petrol and diesel fuel, and a method of preparing the said composition. A method of preparing a composition for removing sulphur from hydrocarbon streams involving the following is described: (a) mixing: 1) a liquid, 2) first metal formate, 3) material containing silicon dioxide, 4) aluminium oxide and 5) second metal formate, to form a mixture of the said components; (b) drying the said mixture to form a dried mixture; (c) calcination of the dried mixture; and (d) reduction of the calcined mixture with a reducing agent under reduction conditions to form a composition which contains a low valency activator, (e) separation of the obtained composition, where the said calcined reduced mixture facilitates removal of sulphur from a stream of hydrocarbons under desulphuration conditions, and where the said liquid is ammonia, and the composition obtained using the method described above. A method of removing sulphur from a stream of hydrocarbons involving the following is described: (a) bringing the stream of hydrocarbons into contact with the composition obtained using the method described above in a desulphuration zone under conditions which facilitate formation of a desulphurated stream of hydrocarbons from the said sulphonated composition and formation of a separate desulphurated stream of hydrocarbons and a separate sulphonated composition; (c) regeneration of at least a portion of the said separate sulphonated composition in the regeneration zone to remove at least a portion of sulphur contained in it and/or on it and formation of a regenerated composition as a result, (d) reduction of the said regenerated composition in an activation zone to form a composition containing a low valency activator which facilitates removal of sulphur from the stream of hydrocarbons when it touches such a composition, and e) subsequent return of at least a portion of the said reduced composition to the said desulphuration zone. Cracked petrol and diesel fuel obtained using the method described above are described.
EFFECT: more stable removal of sulphur from streams of hydrocarbons during desulphuration.
26 cl, 8 tbl, 17 ex
FIELD: technological processes.
SUBSTANCE: invention relates to desulphurisation agents and use thereof. Described is a desulphurisation agent for liquid-phase adsorption desulphurisation, containing a metal oxide on which gold nanoparticles are deposited, having mean particle size of 50 nm or less. Described is a desulphurisation agent for liquid-phase adsorption desulphurisation, where said desulphurisation agent is fixed on a support element. Described is a desulphurisation method, which involves bringing said desulphurisation agent into contact with a liquid containing an organic compound which contains sulphur. Described is a method for reclamation of the desulphurisation agent, involving thermal treatment of the desulphurisation agent after desulphurisation in order to remove the sulphur-containing organic compound adsorbed on the desulphurisation agent. Described is a desulphurisation method, which involves bringing the desulphurisation agent, which is subjected to treatment and reclamation using the described method, into contact with a liquid containing an organic compound which contains sulphur.
EFFECT: described desulphurisation agent enables to remove sulphur compounds based on thiophenes to concentration lower than 10 ppm.
10 cl, 1 tbl, 7 dwg, 6 ex
FIELD: oil-and-gas industry.
SUBSTANCE: invention relates to the method for removal of organic sulphur compounds from liquid hydrocarbon fuel by passing through still absorber, which is γ- aluminium hydroxide modified by zinc oxide amounting wt % 0.1 - 10.0, or its combination with other adsorbers: γ- aluminium oxide and/or alumino-cobalt-molybdenum or alumino-nickel-molybdenum hydrotreating catalyst and/or synthetic zeolite of NaX or ZSM type and/or zinc and copper oxides. Fuel is passed through adsorbent at the temperature selected in the range from 0 to 100°C, atmospheric pressure with a relative volume flow rate falling within the range of values 0.1-10 hour -1.
EFFECT: removal of sulphur organic compounds formed by liquid hydrocarbon fuel using available adsorbents in soft conditions without using molecular hydrogen.
3 cl, 8 tbl, 11 ex
SUBSTANCE: invention relates to a method of producing a catalyst for intensification of extraction of heavy hydrocarbon raw material. Method comprises reaction of when heating from 80 to 180 °C variable-valence metal oxide and alkylbenzene sulphonic acid. Variable-valence metal used is molybdenum (VI) Mo, tungsten (VI) W or chromium (VI) Cr. Invention also relates to a method of using obtained catalyst, which comprises dissolving catalyst in a solvent and introducing into a formation.
EFFECT: technical result is reducing content of heavy fractions and increasing content of light fractions, in significant (up to 65 %) reduction of viscosity and high oil flow, helping to significantly increase efficiency of process of production and transportation of heavy hydrocarbon raw material.
9 cl, 3 ex
FIELD: oil and gas industry.
SUBSTANCE: salts obtained by saponification of carboxylic acids contained in vegetable oils are used as organic acid salts and inorganic salts of molybdenum, tungsten, chromium are used as water-soluble inorganic metal salts. The invention also relates to methods (alternatives) of catalyst use which is that the catalyst is dissolved in a solvent and injected into the reservoir layer, wherein in order to intensify the catalyst action it may be applied in combination with heating of the catalyst target object - heavy hydrocarbon raw material.
EFFECT: reduced viscosity and increased flow of oil-in-place, increased profitability of the process of oil production and handling, extended list of purpose catalysts.
15 cl, 1 tbl, 6 ex
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 production.
SUBSTANCE: invention related to a method of calcium content decrease in fluid hydrocarbon medium, which includes contacting of mentioned above fluid hydrocarbon medium with a sequestrant, represented with a carboxylic acid for calcium containing separating complex formation, b. contacting of mentioned above fluid hydrocarbon medium with water medium for emulsion formation, in which after the mentioned above emulsion separation, at least part of the mentioned separated calcium containing complex stays in the water medium, and contacting the mentioned water medium with water soluble or water dispersing polymer, with I formula for the calcium disposals inhibition on surfaces, contacting with the mentioned above water medium, where the polymer has: (I) formula, where E - is a repeating fragment, which remains after non-saturated ethylene type compound polymerization, R1 is a hydrogen atom or the lowest (C1-C6)- alkyl or carbonyl, Q - is O or NH, R2 - is the lowest (C1-C6)-alkyl, hydroxy - substituted the lowest (C1-C6)-alkyl, the lowest (C1-C6)-alkyl sulfonic acid -(Et-O)-n, -(iPr-O)-n or -(Pr-O-)n, where n - is a variable from around 1 up to 100, and R3 - is a hydrogen atom or XZ, where X - is anion radical, selected form a group, consisting from SO3, PO3 or COO, Z - is hydrogen atom or atoms or any other water soluble cationic fragment, which serves is a balance in X anion radical valence; F - when presented, is a repeating fragment with a II: formula, where X and Z are the sane as in I formula, R4 - is a hydrogen atom or (C1-C6) the lowest alkyl, R5 - is hydroxy - substituted alkyl or alkylene, which has from 1 to 6 atoms, and XZ can or can not to be presented, c and d - are positive whole numbers, e is not-negative number, and j is equal to 0 or 1.
EFFECT: calcium disposal decrease on a surfaces contacting with water phase water in oil separated emulsion.
21 cl, 7 ex, 7 tbl
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
FIELD: oil and gas production.
SUBSTANCE: invention relates to stabilisation of gas-saturated oil. Proposed method comprises two-stage separation at 20-80°C with separation of gas at 1st separation stage at 0.11-0.16 MPa. It comprises also separation of degassed oil at 2nd separation stage at 0.01-0.06 MPa to obtain separated oil and gas. Separated gas is sucked off by degassing device, for example, ejector operated on associated gas from oil field separation stage. Here, extracted gas is mixed with 1st separation stage gas. Produced gas mix is cut in stable condensate and dry gas. Then, stable condensate is mixed with separated oil to feed stabilised oil and dry gas to consuming equipment.
EFFECT: higher yield of separator oil.
3 ex, 1 tbl
FIELD: oil industry.
SUBSTANCE: present invention relates to a method of reducing content of organic chlorides in oil. Method includes preliminary dehydration and degassing of oil, heating oil with extraction of organic chlorides, discharge of purified oil. Preliminary dehydration is performed to oil water content of not more than 1 %, heating is carried out to temperature, which enables to distill a fraction from oil in a rectification column, said fraction containing organic chlorides and boiling at atmospheric pressure in temperature range from initial boiling point to 204 °C, and part of distilled fraction - reflux is used for irrigation of rectification column, volume of reflux is defined empirically depending on structural features of said column and oil volume, fed for distillation.
EFFECT: proposed method enables to obtain purified oil with content of organic chlorides of less than 10 ppm.
1 cl, 1 dwg, 1 ex
SUBSTANCE: invention relates to a method for treating a catalyst discharged from bubbling bed hydrogenation of residual oil. Method comprises following steps: (1) adjustment and control to reduce viscosity, wherein catalyst discharged intermittently from a bubbling bed hydrogenation reactor for residual oil, is adjusted for storage and then discharged continuously, subjected to temperature adjustment by adding water, such that viscosity of oil adsorbed on surfaces and inside pores of discharged catalyst particles is reduced, and flowability of adsorbed oil on surfaces and inside pores of the discharged catalyst particles is improved; (2) desorption and separation by rotational flow, wherein adsorbed oil is desorbed and separated from surfaces and inner pores of discharged catalyst particles by a flowing shear force from a rotational flow field; (3) separation and resource utilisation of three phase oil-water-catalyst, wherein oil/water/catalyst mixture produced from desorption and separation by rotational flow, is subjected to three-phase separation, achieving recovery of oil, recycling of water obtained by separation, and full recovery of solid particles obtained by separation. Invention also discloses a device for implementation of method.
EFFECT: technical result consists in reduction of cost of treatment, simplified process, higher oil recovery factor, reduced tendency to formation of secondary sources of contamination.
10 cl, 1 dwg, 1 ex
SUBSTANCE: method includes the following steps: a) conducting a demercaptization step by attaching, at least, a portion of the mercaptans to the olefins by contacting the gasoline with, at least, the first catalyst at a temperature of 50 to 250°C, a pressure of 0.4 to 5 MPa, and a liquid space velocity (LHSV) of 0.5 to 10 h-1. The first catalyst is presented in a sulfided form and comprises the first carrier, at least, one metal selected from group VIII, and, at least, one metal selected from group VIb of the Periodic Table of Elements, a weight percent expressed as the equivalent of metal oxide selected from group VIII, with respect to the total weight of the catalyst, is from 1 to 30%, and the weight percent expressed in the equivalent of metal oxide selected from group VIb is from 1 to 30% based on the total weight of the catalyst; b) carrying out the step of treating the gasoline from step a) with hydrogen in a distillation column comprising, at least, one reaction zone containing, at least, one second catalyst comprising the second carrier and, at least, one metal from group VIII. The conditions in step b) are selected such that the following operations are carried out simultaneously in the said distillation column: I) distillation with the separation of gasoline from step a) into a light gasoline fraction with a reduced content of sulfur-containing compounds and a heavy gasoline fraction having a higher boiling point, than light gasoline, and containing most of the sulfur-containing compounds, the light gasoline fraction being withdrawn at a point above the reaction zone, and the heavy gasoline fraction is withdrawn at a point located under the reaction zone; II) contacting the gasoline fraction from step a) with the second catalyst to carry out the following reactions: (i) thioetherification by attaching a portion of the mercaptans to a portion of the diolefins to produce thioethers, (ii) selective hydrogenating a portion of the diolefins to olefins and, optionally, (iii) isomerization of olefins.
EFFECT: method helps to produce a light gasoline fraction.
14 cl, 2 dwg