A method of processing technical hydrocarbons of c2-c5
(57) Abstract:Usage: petrochemistry. Hydrocarbon fraction C2-C5contact with a catalyst containing wt.%: zeolite type WHC, DCM, ZSM-5(8) 50 - 80, zinc 0,5 - 5 and a-alumina rest, activated with a mixture of inert gas and water vapor at 0.1 - 2.0 MPA, 230 - 560oC, space velocity of the raw material 1 to 6 h-1. Technical result: processing of various technical fractions of C2-C5in monoaromatics synthetic gasoline with an octane rating of 92 - 98 on the research method. 5 C.p. f-crystals, 9 PL. The invention relates to a method of processing industrial hydrocarbon fractions C2-C5containing paraffin and unsaturated hydrocarbons, heterogeneous catalyst, conditions of use, activation and regeneration of the catalyst.There is a method /Refining and petrochemicals - N 5, 1998. - C. 3 - 7/ processing registergui gas fractions C3-C4in high-octane gasoline - processes "Polinate and Dimersol", developed by the French Institute of petroleum. In the process it turns out monoaromatics a component of motor gasoline with an octane rating of 81-83 on m m catalyst, requiring careful handling and complex raw material preparation (deep Hydrotreating or amine purification; selective hydrogenation of acetylene and diene hydrocarbons; removing water at a molecular sieves), as well as complex procedures regeneration and neutralization of spent catalyst.Known methods /U.S. patent N 4490569. - 1994; U.S. patent N 5171912. - 1995/ to handle C3-C4-faction (propane-butane fraction) on heterogeneous zeolite catalyst in the aromatic concentrate is the process "Ziglar" firms "Wapi" and "British petroleum".The disadvantages of these methods are getting vysokoorganizovannoi hydrocarbon fraction, which in gasoline is hampered by a high content of benzene (>10%) and aromatic hydrocarbons (for a total of more than 90%), as well as the impossibility of processing olefinic hydrocarbons.There is a method /patent RF N 2117030. - 1998/ receive gasoline from the technical fraction C4. The process is performed on the butane-butylene fraction (containing butylenes 20-90%, divinyl not more than 3%) in contact with a heterogeneous catalyst containing a zeolite type WHC, DCM, ZSM-5(8), Zn - Al2 500-580oC; by reducing the activity of the catalyst in the process of conducting its reactivation recycle stream butane-butylene fraction at 510-530oC; regeneration of the catalyst is a nitrogen-air mixture with water vapor.In the process according to this method of butane-butylene fraction over zeolite catalyst in the temperature range of 250-550oC, a pressure of 0.1 to 1.5 MPa, the space velocity of the feedstock 1-6 h-1(in terms of liquid) turns motor gasoline with an octane rating 91-98 by I. M., contains, %: olefin - 28-64, aromatic hydrocarbons, 5-35, cycloalkanes - 9-21, alkanes - 5-26. Get gasoline inhibited when shipping the introduction of antioxidants - ionol or Agidol in quantities of not more than 0.2%.The disadvantage of this method is limited by the raw materials used - butane-butylene fraction, containing mainly hydrocarbons, C4in particular butylene - from 20 to 90%.The closest in technical essence is a method /Materials of the conference "Development and improvement of technologies for the production of catalysts, catalytic refining processes, organic and inorganic synthesis". - M. :high character, using a catalyst comprising a metal-containing heterogeneous catalyst based on zeolite ZSM-5 with pintasilgo structure. The optimal process parameters for this method are:
temperature - 530-580oC
pressure of 0.5-1.0 MPa
the volumetric rate of flow C2-C5- hydrocarbon - 500-800 h-1(gas)
The result of a process carried out in 4 consecutive reactors, from C2-C5-hydrocarbons we can produce containing 90-95% of monocyclic aromatic hydrocarbons, mainly 20-25% benzene, 42-48% toluene, 15-20% of xylenes, 3-5% of ethylbenzene, the rest is up to 10% of arenes C9-C10.A significant disadvantage of this method of processing C2-C5-hydrocarbon fractions is the inability to process under specified conditions C2-C5-hydrocarbon fraction containing both saturated hydrocarbon (alkanes) and unsaturated (alkenes), and high aromatizovani product.At the industrial enterprises of oil and gas processing, petrochemicals, organic synthesis and synthetic rubber are hydrocarbon fraction C2- the, processing of oil and gas resources: dehydrogenation, cracking, catalytic cracking, coking, and other thermal and catalytic processes.The purpose of the invention is catalytic treatment of various technical hydrocarbon fractions C2-C5containing olefins (alkenes) and paraffins (alkanes), monoaromatics synthesis of high-octane petrol.This goal is achieved by the proposed method hydrogen-free contact on the catalyst containing high-silica zeolite type WHC, DCM, ZSM-5(8) with silicate module 30-80 and 50-80% zinc and 0.5-5% and the aluminum oxide - the rest is up to 100%, and technical hydrocarbons of C2-C5containing alkenes C2-C418-95%, dienes C4-C5- no more than 1%, sulfur not more than 0.5%, of water is not more than 0.2%, of ester is not more than 0.05%, ethanol and methanol not more than 0.05% total amines not more than 0,01%, acetylene - traces of alkanes and hydrocarbons C5+- not more than 15% of total alkanes C3-C4- the rest is up to 100%.The catalyst shows high activity (the degree of conversion of alkenes C2-C4in the liquid - 70-100%) and stability (mainegenealogy mileage - 20-40 days) after it will prefix Django pair 50-500 h-1temperature 500-580oC, a pressure of 0.05 to 0.5 MPa. Such activation of the catalyst allows you to change the range of acidity of the catalyst and to regulate aromaticum (reduce) and oligomerizes (increase) the activity of the catalyst.One of the elements of novelty and distinctive feature of the proposed method is the use of raw materials - industrial hydrocarbon fractions C2-C5the following composition, wt.%:
alkenes C2-C5- 18-95
dienes C4-C5- no more than 1
sulfur compounds - not more than 0,5
water is not more than 0.2
ethers - not more than 0.05
ethanol and methanol are not more than 0.05 total
amines not more than 0,01
alkanes and hydrocarbons C5+- no more than 15 total
acetylene - tracks
alkanes C3-C4- the rest is up to 100
The process of technical hydrocarbon fractions C2-C5containing paraffin and unsaturated hydrocarbons is carried out on the catalyst of the above composition, which is in the process of reactivations (in the fall of the conversion of raw materials is not more than 30%) recycle C2-C4-hydrocarbon fraction with a content of alkenes is not more than 20 wt.% of the catalyst accumulates 10-15% of coke (for one cycle), that is a significant number of similar cyclic petrochemical processes of this kind are not known.The regeneration process zakoksovanie catalysts are nitrogen-air mixture with an oxygen content of 0.5-5 vol.%, at temperatures 250-595oC, with dilution steam at a mass ratio of nitrogen-air mixture: water vapor - 1:0,01-0,5.Industrial processing technology technical hydrocarbons of C2-C5via the described method is carried out at the facility, consisting of series-connected in the course of the raw materials of the site prior to the evaporation of the raw materials and/or furnace heating raw materials, sequential (series-parallel) reactors (1 to 3), loaded fixed bed of the catalyst of the proposed method, the system of heat exchangers and heat recovery (to generate steam or to heat raw materials), the system of separation and separation of the products of catalytic processing of raw materials (fuel gas and/or recycle stream and a liquid product is unstable synthesis gas), one or two columns (the first column stabilization of liquid product (oligomerizate) - used as a high-octane component of gasoline from surplus retained the K. in order to produce a marketable gasoline or qualitative synthesis of high-octane petrol).For the effective implementation of industrial catalytic technologies of processing of technical hydrocarbon fractions C2-C5the described method is performed a preliminary technical procedures:
- excessive levels of hydrocarbon, C5+contained in the raw material, before submitting to install pre-allocate the rectification (as a gasoline component) to a residual content of hydrocarbons, C5+in raw materials is not more than 0.1 wt.%;
- active sulfur compounds (hydrogen sulfide, light mercaptans are removed from the raw material pre-Hydrotreating or alkaline cleaning to the level of content in the raw material is not more than 0.01 wt.%
- when the contents in raw materials dienes C4-C50.25 wt.%, the feedstock is diluted hydrocarbon gas fraction (recycle stream or other technical gas C2-C4-hydrocarbon fractions containing dienes is not more than 0.01 wt.%) thus, to be fed into the processing of raw materials the content of dienes C4-C5did not exceed 0.25 wt.%;
- start the installation carried out for 5-10 hours on obzen avoid exothermic not managed a jump of temperature in the catalyst bed and the increased coke formation.As a result of implementation of the preliminary procedures and the process of catalytic conversion of technical hydrocarbon fractions C2-C5in the proposed method, the activation, reactivation and regeneration of the catalyst according to the described method, it turns out synthesis of high-octane petrol (gasoline), stabilized during shipment antioxidants Agidol, ionol, tributylphosphine or similar antioxidants, introduced in quantities of not more than 0.2 wt.% - to maintain the induction period of a commercial product on the level not lower than 450 minutesGet at least 15 wt.% stable synthesis gas has an octane number 92-98 by I. M., contains aromatic hydrocarbons of not more than 25 wt.%, is an environmentally friendly product and can be used as organic diluent, solvent and adsorbent, registertimer raw materials for the esterification of C1-C2-alcohols (methanol, ethanol), a component of motor fuel (high octane additives) and high-octane gasoline. Gas and gas-liquid flows, leaving the last reactor after the catalytic process, is or ethanol.To achieve the goal of the invention under the present method were selected:
- different types of raw materials - technical hydrocarbons of C2-C5source containing 0.02 to 0.5 wt.% sulfur compounds, and then hydrotreated and stable (see table. 1);
- the catalyst (see table. 2) prepared in JSC "VNIIS NC" described in method  technology;
- pilot plant, research and analytical base of JSC "VNIIS NC";
- results of pilot studies.Prior to testing on various types of raw material, the catalyst of the table. 2 proactivenet under the conditions listed in table. 3.Reactivation and regeneration has been on raw materials catalysts of table. 2, 3 carried out by the means indicated in the table. 4, N 1.The invention is illustrated by the following examples.Example 1.Tests are conducted on proektirovanii catalyst No. 1 of the table. 2, 3 different types of raw materials - technical hydrocarbon, C2-C5the fractions described in table. 1, and their mixtures.Reactivation and regeneration of the catalyst is performed according to the conditions table. 4, N 1.The results of the tests are presented in table. 5.In 5 according to the table. 5 found that the effective way of processing is carried out under the following conditions (when the total of the selected duration of test - 2000 hours):
the temperature is from 230 to 560oC;
the pressure is from 0.1 to 2.0 MPa;
the volumetric feed rate of raw material (liquid) from 1 to 6 h-1< / BR>- the main raw material composition, wt.%: alkenes C2-C4- 18-95 (with dilution in the implementation process up to 75 wt.% or less): dieny C4-C5- not more than 1 (with dilution to 0.25 wt.% or less);
the content of amines not more than 0.01 wt.%
Under these conditions, the implementation process and the selected duration of tests the number of reactivations of the catalyst does not exceed 5, regeneration - 4, and the resulting synthesis gas has an octane number of 92 to 98 by I. M. and contains not more than 25 wt.% aromatic hydrocarbons.Example 2.To establish the levels of catalytic poisons and technical impurities, which are present in industrial types of C2-C5-hydrocarbons, tests are carried out in this way.The experiment is carried out on proektirovanii catalyst No. 1 of the table. 2, 3 raw N from 1 table. 1 and are the conditions of table. 5, N 1.In mercaptan reactive (purity - 98,5%);
the sulphide technical (purity not less than 95%);
methanol reactive (degree of purity of 99.2%);
ethanol reactive (degree of purity of 98.5%);
methyl tertiary butyl ether (MTBE) technical (purity - 92,5%);
ethylcelluloses ether (ETBE) technical (purity of 96.2%);
diisopropyl ether (DIPE) technical (purity - 98,3%);
the pentane-hexane fraction (PGF) technical (content of hydrocarbon, C+- 98,5%).The results of the tests are presented in table. 6.From the data table. 6 it follows that for the effective implementation of the method of processing technical hydrocarbon fractions C2-C5the content of industrial impurities should be limited to the next level of content in raw materials, wt.%:
sulfur compounds is not more than 0.01;
water is not more than 0.2;
ethers - not more than 0.05;
ethanol and methanol are not more than 0.05 total;
alkanes and hydrocarbons C5+- no more than 15 total (with distillation fraction C5+to content in the raw material is not more than 0.1 wt.%).Example 3.To implement soft start process in an industrial environment, you must use the initial raw materials with materialitate table. 7. Tests were conducted on proektirovanii catalyst No. 1 of the table. 2, 3 different types of raw materials under the terms table. 4, N 1.Example 4.To establish the quality and stabilization of the products resulting from the processing of C2-C5-hydrocarbons (see the test results table. 5), were selected a representative sample of chemically unstable synthesis of gasoline - oligomerizate, which inhibited with BHT. Neighbourly oligomerized was subjected to rectification (perispomeni emitting residual fraction 180oC - K. K.) and Engibarov technical antioxidants - ionol, Agidol and tributylphosphine (TBPC) to produce gasoline AI-95 "Extra".Source oligomerized and products of its physical and chemical modifications were subjected to analysis and tests, the results of which are presented in table. 8.From the data table. 8 shows that after perispomeni (Department FR. 180oC - K. K.) and the inhibition by antioxidants of oligomerizate get gasoline AI-95 "Extra", which is better than oligomerized (in terms of "octane number", "content fact. resins"). However, to reach the target and the account level of 0.2 wt.% - to prevent the growth of the content of the fact. the resins.Example 5.In real industrial conditions of the processing technology technical hydrocarbon fractions C2-C5containing paraffin and unsaturated hydrocarbons, is as follows:
- in case of excessive content of hydrocarbons, C5+in the feedstock is separated by distillation (as a gasoline component) to the level of content in the raw material is not more than 0.1 wt.%;
- in case of excessive content of active sulfur compounds (hydrogen sulfide and light mercaptans) are removed from the feedstock prior Hydrotreating or alkaline cleaning to the level of content in the raw material is not more than 0.01 wt.%;
- excessive content of other impurities (water, amines, ethers, methanol and ethanol) is removed by extraction, distillation, adsorption, or other known methods to the corresponding limiting the levels of these impurities specified in examples 1 and 2;
- the first hours of the operation carried out on hydrocarbon, C2-C5-raw materials are depleted alkenes (the content of alkenes C2-C4- not more than 20 wt. %, dienes C4-C5- not more than 0.25 wt.%), which is given in the first 5-10 hours of operation:
final oven heating raw materials, serial (series-parallel) reactors (1 to 3 depending on the content of alkenes C2-C4in raw materials) with a fixed bed catalyst system of heat exchangers and/or heat recovery (to generate steam or to heat raw materials), the system of separation and separation of the products of catalytic processing of raw materials, one or two columns - stabilization and perispomeni (depending on the received product - oligomerizate or gasoline).The results of pilot experiments are presented in table. 9 (used catalyst from the table. 2, N 1). 1. A method of processing technical hydrocarbon fractions WITH2- C5on the VK-zeolite catalyst, when heated, under pressure, to obtain the not less than 15 wt.% the liquid hydrocarbon product, wherein the used catalyst composition, wt.%: VK-zeolite (type WHC, DCM, ZSM-5, ZSM-8 with silicate module 30 - 80) - 50 - 80, zinc - 0,5 - 5 and alumina - rest to 100; the process is carried out at the installation at pressures of 0.1 - 2.0 MPa, the space velocity of the feedstock 1-6 h-1in terms of liquid temperature 230 - 560oC with pre-activation of the catalyst with water vapor in the bulk starosta, temporary reactivations of the catalyst in the fall of the conversion of raw materials is not more than 30% recycle WITH3- C4-hydrocarbon fraction with a content of alkenes is not more than 20 wt.% and dienes is not more than 0.01 wt.% at a temperature of 450 - 540oC for 0.5 - 5 h with intermediate regeneration zakoksovanie catalyst nitrogen-air mixture with an oxygen content of 0.5 - 5% vol. at a temperature of 250 - 595oC, with dilution steam at a mass ratio of nitrogen-air mixture: water vapor is 1 : 0.01 to 0.5, and using raw materials - technical fraction of hydrocarbons WITH2- C5- gas, gas-liquid or liquid mixture of hydrocarbons containing, wt.%:
Alkenes WITH2- C4- 18 - 95
Dieny4- C5- No more than 1
Sulfur compounds - Not more than 0,5
Water is Not more than 0.2
Ethers - Not more than 0.05
Ethanol and methanol are Not more than 0.05 total
Amines Not more than 0,01
Acetylene hydrocarbons and Traces of
Alkanes and hydrocarbons WITH5and above - No more than 15 total
Alkanes WITH3- C4- Rest
from which, before processing an excessive amount of hydrocarbons5+pre-allocate the rectification as the s sulfur-containing compounds are removed prior Hydrotreating or alkaline refining of the raw material up to the level of sulfides - not more than 0.01 wt.%.2. The method according to p. 1, wherein the method is performed on the installation, with pre-evaporation of the raw materials and/or heating stove of materials, from one to three serial or serial-to-parallel reactor with a fixed bed catalyst system of heat exchangers and heat recovery to generate steam or to heat the raw material, the system of separation and separation of the products of catalytic processing of raw material into a liquid product and a side of the fuel gas and/or gas recycle stream, or the first column stabilization of liquid product from excessive gas content1- C4products when only oligomerizate - high-octane component of gasoline, or the first specified stabilization column and the second column separating a heavy fraction 180oC-QC from oligomerizate upon receipt of gasoline and high-octane component of gasoline.3. The method according to PP.1 and 2, characterized in that at a concentration in the feedstock dienes WITH4- C5more than 0.5 wt.%, raw materials are pre-diluted gaseous hydrocarbon fraction recycle stream or other gas WITH2- C44- C5did not exceed 0.25 wt.%.4. The method according to PP.1 to 3, characterized in that during the start-up for 5 to 10 hours use raw materials containing, % wt.: alkenes WITH2- C4- not more than 20, dienes WITH4- C5is not greater than 0.25.5. The method according to p. 2, characterized in that additional chemical stabilization of the obtained product is used antioxidants: Agidol, BHT, tertBUTYLPEROXY in quantities of not more than 0.2 wt.%.6. The method according to PP. 2 and 4, characterized in that the liquid processing products, automotive gasoline, oligomerized contain not more than 25 wt.% aromatic hydrocarbons and can be used as organic diluents, solvents and absorbents, registertimer raw materials for the esterification WITH1- C2-alcohols, high-octane components of gasoline - octane additives and directly to high octane gasoline.
FIELD: petrochemical processes.
SUBSTANCE: feedstock olefins are submitted to oligomerization in contact with zeolite oligomerization catalyst and C4-hydrocarbons isolated from resulting products are then aromatized on zeolite aromatization catalyst. Hydrogen-containing dry gas recovered from aromatization products is used for oligomerization-preceding selective hydrogenation of butadiene in feedstock to give butylene-enriched starting material.
EFFECT: prolonged catalyst lifetime.
3 cl, 3 tbl
FIELD: petrochemical processes.
SUBSTANCE: at least one-step oligomerization (step b) is carried out or this oligomerization is carried out in two steps: limited oligomerization b1 and final oligomerization b3, wherein catalytic oligomerization of olefins having 4 carbon atoms is carried out in presence of other olefins also contained in charge, these other olefins belonging to group consisting, on one hand, of ethylene and, on the other hand, of C5- or C6-olefins to produce oligomers. Further, in step d, at least part of oligomers obtained is subjected to catalytic cracking in reactor differing from oligomerization reactor to produce, in particular, propylene. Process also allows fixed-, moving-, and fluidized-bed cracking to be performed and additional oligomers to be possibly obtained.
EFFECT: optimized yield, conversion, and propylene selectivity.
19 cl, 2 dwg, 5 tbl, 3 ex
FIELD: industrial organic synthesis.
SUBSTANCE: linear alpha-methylstyrene dimers that can be used as molecular weight regulators for various polymers, as varnish solvents, and as base material in production of synthetic oils are obtained via oligomerization of α-methylstyrene in presence of zeolite ZSM-12 in H form in amount 1 to 10% at temperature 60-120°C.
EFFECT: increased selectivity and simplified production process.
1 tbl, 8 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of linear unsaturated dimmers of α-methylstyrene that are used as modifying agents in manufacturing polymers. Method is carried out by the dimerization reaction in the presence of zeolite Y at the mole ratio SiO2/Al2O3 = 6.2-7.0 in NaH-form and ionic exchange degree 40-60%. The amount of catalyst is 1-5 wt.-%, the reaction temperature is 40-800C. Invention provides increasing working time of catalyst and improving indices of the process.
EFFECT: improved method of synthesis.
FIELD: chemical industry; methods of production of the linear dimmers of a-methylsterene.
SUBSTANCE: the invention is pertaining to the methods of production of the linear dimmers of a-methylsterene, which are used in the capacity of the modifiers in production of polymers. The method is exercised by dimerization of α- methylsterene in the presence of zeolite Y with the molar ratio of SiO2/Al2O3 = 6.2, with the stage of the ionic exchange of Na+ for Н+ - 40÷60 % containing 0.5÷2.0 mass % of copper (II). The catalyst amount makes 1÷4 mass %, the temperature of the reaction is 80÷100°С. The output of the dimmers compounds - 92.8÷94.8 % at conversion of the raw of 96.3÷99.4 %. The technical result of the invention is the raise of the selectivity of formation and output of the linear unsaturated dimmers of α- methylsterene.
EFFECT: the invention ensures the increased selectivity of formation and output of the linear unsaturated dimmers of α- methylsterene.
9 ex, 1 tbl
FIELD: industrial organic synthesis.
SUBSTANCE: process is accomplished by dimerization of styrene in presence of Y-type zeolite with molar ratio SiO2/Al203 = 6-7 in H-form and with ion exchange degree 94-97% undergone heat treatment and utilized in amount of 5-10 wt % based on styrene. Reaction is carried out at 80-120°C in pseudocumene solvent used in (1-2):1 proportion to styrene.
EFFECT: simplified process and increased yield of end product.
1 tbl, 9 ex