CN103121897A - Method for preparing arene by mixture containing hydrocarbon with condensed rings - Google Patents
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Abstract
The invention relates to a method for preparing arene by a mixture containing hydrocarbon with condensed rings, and is mainly used for solving the problems that in the prior art, monocyclic arene cannot be produced by the mixture containing hydrocarbon with condensed rings with high selectivity and the fractionation process is complex. The method combining hydrogenating pretreatment and selective hydrocracking comprises the following steps of: a) contacting the mixture containing hydrocarbon with condensed rings as a raw material with a catalyst in a hydrogenating reactor, and reacting to generate a material flow I; b) carrying out gas-liquid separation on the material flow I through a high separator, removing hydrogen sulfide and nitrides from the gaseous phase material flow through a deacidifying tower, returning the gaseous phase material flow to the hydrogenating reactor, and discharging a material flow II from the bottom of the high separator; c) entering the material flow II to a cracking reaction, wherein the mixture containing hydrocarbon with condensed rings is contacted with the catalyst in the cracking reactor to generate a material flow III after reaction; and d) carrying out gas-liquid separation on the material flow III discharged from the bottom of the cracking reactor through a high separator, and returning the gaseous phase material flow to the cracking reactor, wherein the liquid phase material flow discharged from the bottom of the high separator enters an arene fractionating tower to obtain an arene product V and tail oil VI, and the tail oil is partially or fully circulated to the cracking reactor. The technical scheme better solves the problems, and the method can be applied to production of monocyclic arene products in a line of the mixture containing hydrocarbon with condensed rings.
Description
Technical field
The present invention relates to a kind of method that contains the mixture preparing aromatic hydrocarbon of hydrocarbon with condensed rings, particularly the mixture through catalytic that contains hydrocarbon with condensed rings can be converted into about a kind of the method that comprises benzene,toluene,xylene, carbon nine mononuclear aromatics and carbon ten mononuclear aromatics.
Background technology
Condensed-nuclei aromatics refers to comprise that naphthalene is double ring arene, and anthracene, phenanthrene are a hydrocarbon of thrcylic aromatic hydrocarbon.Naphthalene is industrial most important condensed-nuclei aromatics, and sterling is the white crystal with Camphorwood smell, mainly for the production of Tetra hydro Phthalic anhydride, dyestuff intermediate, rubber ingredients and agrochemical.Part naphthalene generally contains naphthalene 10wt% from the by-product coal tar of coal tar.200～250 ℃ of cuts that obtain during Doak Tar Oil claim fraction of naphthalene oil, wherein contain approximately 50wt% of naphthalene.Another part naphthalene is from the heavy aromatics cut (205～295 ℃ of boiling range scopes) of the processes such as catalytic reforming, catalytic cracking and hydrocarbon cracking, and methylnaphthalene content (quality %) is about respectively 55,35 and 45.Along with the continuous intensification of the refining of petroleum degree of depth and the raising of vehicle fuel environmental protection standard, the utilization of being rich in condensed-nuclei aromatics more and more causes people's attention.
Catalytic cracking light cycle oil (LCO) mixes use as a kind of second-rate accent diesel component usually with straight-run diesel oil, or the oil that acts as a fuel directly uses.From the composition of LCO, total aromaticity content is up to 80%, and naphthalene is that double ring arene accounts for 70% left and right, and mononuclear aromatics and thrcylic aromatic hydrocarbon approximately respectively account for 15% left and right, and other is alkane, naphthenic hydrocarbon and alkene etc.Sulphur content 0.2～1.5wt% of LCO, nitrogen content 100～750ppm, cetane value only has 15～25, and ignition characteristic is poor.China's catalytic cracking (FCC) is installed year amount of finish near 100,000,000 tons, the year output 10 million ton of LCO.In China, a large amount of LCO call in without hydrotreatment in the total composition of diesel oil, cause diesel quality and stability variation, and there is larger gap in this compared with developed countries.In recent years, the environmental protection standard of diesel oil is more and more higher, and how the continuous atrophy of fuel oil market utilizes these low-quality LCO to seem more and more urgent.
At present, poor quality catalytic cracking diesel (being mainly LCO) the upgrading means that generally adopt both at home and abroad are hydrofining and hydrocracking.Catalytic diesel oil hydrofining, be in, under the condition of low pressure, carry out olefins hydrogenation, desulfurization, denitrogenation and the reaction of aromatic hydrocarbons fractional saturation, can improve its color and stability, and the cetane value increase rate is less, especially process the catalytic unit of inferior raw material, its catalytic diesel oil also far can not satisfy product to the requirement of cetane value by hydrofining.Except traditional hydroprocessing process, the high-pressure hydrogenation cracking can be cracked into LCO petroleum naphtha and lighter hydrocarbons, as Unicracking technique (USP 5026472) and the Sinopec graduate MCI technique of Fushun petrochemical industry (CN 1955262A) of Uop Inc., the purpose product is diesel oil and gasoline.A kind of hydrogenation modifying process technology (MCI) that improves the catalytic diesel oil cetane value of Fushun Petrochemical Research Institute's exploitation, have the saturated performance of good aromatic hydrogenation and selectivity of ring-opening, higher aromatic hydrocarbons depth of conversion is arranged, possess higher selectivity and make the cycloalkanes open loop and not chain rupture, guarantee that the cetane value increase rate is large and higher diesel yield is arranged.Yet all there are the deficiencies such as the large and petroleum naphtha subsequent processing steps complexity of hydrogen-consuming volume in these two kinds of techniques, also can't optionally generate the industrial aromatic hydrocarbon resource that important need is arranged.
Benzene and p-Xylol (PX) are important basic organic chemical industry raw materials, are widely used in products such as producing polyester, chemical fibre, and be closely related with the national economic development and people's clothing, food, lodging and transportion--basic necessities of life, in recent years sought-after, increment is rapid.The source of aroamtic hydrocarbon raw material mainly contains two operational paths: a raw material route is that petroleum naphtha obtains aroamtic hydrocarbon raw material through catalytic reforming, Aromatics Extractive Project; Another raw material route is that the byproduct of ethylene unit-cracking of ethylene gasoline is obtained aroamtic hydrocarbon raw material, thereby is low value-added feedstock conversion the high added value aromatic hydrocarbon product through hydrogenation, Aromatics Extractive Project.In petroleum chemical plant, Aromatic Hydrocarbon United Plant is usually take p-Xylol (coproduction o-Xylol) as the purpose product, as the raw material of downstream PTA device.P-Xylol that will the production maximum, dimethylbenzene in catalytic reforming and cracking of ethylene gasoline, be mainly to adopt the processing method of disproportionation transalkylation that toluene and C9 aromatic hydrocarbons (also comprising part monocycle C10 aromatic hydrocarbons) are carried out disproportionation and transalkylation reaction generation xylol and benzene under the molecular sieve catalyst effect, xylol is converted into p-Xylol by dimethylbenzene hydro-isomerization metallization processes again.Ethylene unit and Aromatic Hydrocarbon United Plant all derive from petroleum naphtha mostly, how to optimize aroamtic hydrocarbon raw material, reduce the degree of dependence to the raw material petroleum naphtha, are the important topics of current development petrochemical complex.Consider potential aromatic hydrocarbon resource huge in LCO, how by catalytic conversion technique, low value-added LCO to be converted into mononuclear aromatics, by Aromatic Hydrocarbon United Plant, these mononuclear aromatics further being changed into p-Xylol and/or the benzene of high added value, will be huge opportunities and challenges again.
For light cycle oil being converted into the higher mononuclear aromatics of industrial added value, patent USP 7265252 has introduced a kind of fuels from FCC LCO hydrocracking-alkylation selectivity and has shifted the method for producing dimethylbenzene and benzene.This processing method is that first pre-hydrotreating is removed the impurity such as sulphur in stock oil, nitrogen, be then mononuclear aromatics carrying out the catalytic hydrocracking reaction with the double ring arene Partial Conversion, transalkylation reaction by toluene and C9 aromatic hydrocarbons at last, generate target product dimethylbenzene and benzene, go back simultaneously by-product part liquefied gas, light naphthar and ultra-low-sulphur diesel component.Yet, to process the gained raw material and merge and enter serial separation column and carry out complex separations due to pre-hydrotreating and transalkylation, solid circulating rate is large, and equipment is numerous and jumbled; Transalkylation reaction zone is positioned at the lower floor of catalytic hydrocracking reaction zone, and reaction pressure is too high, will cause the open loop loss of mononuclear aromatics product.
Summary of the invention
Technical problem to be solved by this invention is to contain the problems such as condensed-nuclei aromatics material choice production aromatic hydrocarbons and fractionation process complexity, to provide a kind of new method with condensed-nuclei aromatics waste mononuclear aromatics.The method is used for containing the catalytic conversion reaction of condensed-nuclei aromatics mixture, but has the advantages such as highly selective manufacture order Polycyclic aromatic hydrocarbons, fractionation process are simple.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that combines by adding hydrogen pretreatment and selective hydrogenation cracking, technical scheme comprises the following steps: a) with the sulphur weight content between 0～5%, weight nitroxide content is raw material between 0～1% hydrocarbon with condensed rings mixture, is that 250～450 ℃, weight space velocity are 0.5～3 hour in temperature
-1, pressure is under 3～12MPa condition, raw material contacts with catalyzer in hydrogenator, generates stream I after reaction, wherein catalyzer used comprises following component by weight percentage: (a) γ-Al of 60～97%
2O
3Carrier; (b) 1～30% zeolite molecular sieve material; (c) 1～8% CoO; (d) 2～25% MoO
3B) stream I is after the gas-liquid separation of high score device, and gaseous stream loops back hydrogenator after removing hydrogen sulfide and nitride through extracting tower, and sulphur content is by weight percentage discharged less than 100ppm, the nitrogen content stream I I less than 50ppm in the bottom of high score device; C) stream I I enters cracking case, it is 2～6 face under hydrogen fixed bed reaction condition in 300～450 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa and hydrogen hydrocarbon mol ratio, containing the mixture material of condensed-nuclei aromatics contacts with catalyzer in cracking case, generate logistics III after reaction, wherein catalyzer used comprises following component: (a) at least a in ZSM-5 zeolite, 5～70% mordenite, Y zeolite, EU-1 zeolite, beta-zeolite molecular sieve; (b) at least a in 0.01～5.0% VIII family metal; (c) 15～80% binding agent; D) the stream I II that discharges bottom cracking case is after the gas-liquid separation of high score device, gaseous stream loops back cracking case, high score device bottom is discharged liquid phase stream and is entered the aromatic hydrocarbons separation column, obtains aromatic product V and tail oil VI, and tail oil partly or entirely loops back cracking case.
In technique scheme, raw material comes catalytic cracking light cycle oil, pyrolysis gasoline, Aromatic Hydrocarbon United Plant heavy aromatics tower bed material or coal tar; More specifically, raw material is a kind of solar oil component, from catalytic cracking unit, 180～360 ℃ of boiling spreads, 20 ℃ of density are not less than 0.80g/ml, and total aromatic ring content is greater than 50% by weight percentage, and dicyclo aromatic ring content is greater than 35%, sulphur content is between 0～5%, and nitrogen content is between 0～1%; After desulfurization, the selective opening reaction occurs in the hydrocarbon with condensed rings mixture in cracking case, generates the mononuclear aromatics mixture; The tower top pressure of separation column is between-0.1MPa～0.5Mpa, and tower top temperature is between 150～220 ℃; Reaction product cuts into low boiling point arene mixture and high boiling point tail oil by boiling point in separation column, comprise the light aromaticss such as benzene,toluene,xylene in the low boiling point arene mixture, directly deliver in Aromatic Hydrocarbon United Plant, the high boiling point tail oil partly or entirely loops back hydroeracking unit.
,, can efficiently generate and comprise benzene,toluene,xylene, C9 aromatic hydrocarbons and part monocycle C10 aromatic hydrocarbons etc. by the catalyzed conversion of pre-hydrogenation unit and selective hydrogenation cracking unit as raw material with the mixture that contains condensed-nuclei aromatics.Pre-hydrogenation unit efficiently removes the impurity such as sulphur, nitrogen, and the following light constituent content of carbon six is extremely low.After imurity-removal, one of them ring filling reaction and directional fracture under the catalyst action in selective hydrogenation cracking unit, only occur in mixture, and light constituent output is also lower.On whole flow process, only need a heavy aromatics tower is set after hydrocracking reactor, with the mononuclear aromatics product separation out, the technique integrated level is high, low equipment investment.
Can find out, such operational path can the mixture that contains condensed-nuclei aromatics that the added value of industry is lower be converted into the mononuclear aromatics mixture of high added value, has effectively simplified again fractionation process, reduce facility investment and running cost, obtained technique effect preferably.
The invention will be further elaborated below by embodiment.
Description of drawings
Fig. 1 is the schematic flow sheet that contains the mixture through catalytic conversion system of condensed-nuclei aromatics.
1 is pre-hydrogenator, and 2 is the high score device, and 3 is extracting tower, and 4 is circulating hydrogen compressor, and 5 is hydrocracking reactor, and 6 is the high score device, and 7 is circulating hydrogen compressor, and 8 is the aromatic hydrocarbons separation column.
Embodiment
[embodiment 1]
Get silica alumina ratio and be 30 Hydrogen ZSM-5 zeolite 10g, white carbon black 10g, pseudo-boehmite 128 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, passing through incipient impregnation method load 1.2wt%Ni and 4.5wt%Mo with nickelous nitrate and ammonium molybdate solution, is available catalyst for pre-hydrogenation after oven dry and roasting.Get silica alumina ratio and be 15 h-mordenite 55g, pseudo-boehmite 70 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, passing through incipient impregnation method load 1.0wt%Pt and 0.5wt%Ce with Platinic chloride and cerous nitrate solution, is available selective hydrogenation cracking catalyst after oven dry and roasting.
Under hydro condition, in two tandem reactors of respectively 20g catalyst for pre-hydrogenation and 10g selective hydrogenation cracking catalyst being packed into.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel, beds equal 3 millimeters granulated glass spherees of filling Φ up and down play air-flow distribution and supporting role.420 ℃ of pre-hydrogenator temperature of reaction, weight space velocity 2h
-1, reaction pressure 3.5MPa, hydrogen hydrocarbon mol ratio is 5.0.400 ℃ of cracking case temperature of reaction, weight space velocity 4h
-1, reaction pressure 4.0MPa, hydrogen hydrocarbon mol ratio is 3.0.
The raw material light cycle oil derives from refining catalytic cracking unit, H
2For processing electrolysis hydrogen through dehydrating, the product of pre-hydrotreating reaction is as the raw material of hydrocracking reaction, and the results are shown in Table 1 for raw material and product analysis.
Table 1 raw material and product weight percent form
Wherein, catalyst for pre-hydrogenation desulfurization degree 99.3%, denitrification percent 94.5%; The transformation efficiency of double ring arene under the cracking catalyst effect is 60.8%, and the mononuclear aromatics selectivity is 59.3%.
[embodiment 2]
Get silica alumina ratio and be 15 h-mordenite 10g, silica alumina ratio is 10.5 Hydrogen Y zeolite 10g, pseudo-boehmite 118 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, passing through incipient impregnation method load 1.5wt%Co and 2.8wt%Mo with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate solution, is available catalyst for pre-hydrogenation after oven dry and roasting.Get silica alumina ratio and be 40 Hydrogen EU-1 zeolite 35g, silica alumina ratio is 10.5 Hydrogen Y zeolite 25g, pseudo-boehmite 65 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, passing through incipient impregnation method load 1.0wt%Pd and 0.5wt%Sn with the acid of chlorine palladium and tin chloride solution, is available selective hydrogenation cracking catalyst after oven dry and roasting.
Under hydro condition, in two tandem reactors of respectively 20g catalyst for pre-hydrogenation and 10g selective hydrogenation cracking catalyst being packed into.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel, beds equal 3 millimeters granulated glass spherees of filling Φ up and down play air-flow distribution and supporting role.350 ℃ of pre-hydrogenator temperature of reaction, weight space velocity 1.5h
-1, reaction pressure 4.0MPa, hydrogen hydrocarbon mol ratio is 5.0.400 ℃ of cracking case temperature of reaction, weight space velocity 3.0h
-1, reaction pressure 6.0MPa, hydrogen hydrocarbon mol ratio is 6.0.
The raw material light cycle oil derives from refining catalytic cracking unit, H
2For processing electrolysis hydrogen through dehydrating, the product of pre-hydrotreating reaction is as the raw material of hydrocracking reaction, and the results are shown in Table 2 for raw material and product analysis.
Table 2 raw material and product weight percent form
Wherein, catalyst for pre-hydrogenation desulfurization degree 99.3%, denitrification percent 95.6%; The transformation efficiency of double ring arene under the hydrocracking catalyst effect is 57.9%, and the mononuclear aromatics selectivity is 65.6%.
[embodiment 3]
Silicon sol (containing silicon-dioxide 40%) 25g, pseudo-boehmite 150 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, by incipient impregnation method load 1.5wt%Co, 1.5wt%Ni and 1.0wt%W, be available catalyst for pre-hydrogenation after oven dry and roasting with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nickelous nitrate and ammonium tungstate solution.Get silica alumina ratio and be 10.5 Hydrogen β zeolite 45g, pseudo-boehmite 65 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, with ion exchange method, catalyst body is carried out ion-exchange at nitric acid iridium solution, containing 1.8wt%Ir, is available selective hydrogenation cracking catalyst after oven dry and roasting.
Under hydro condition, in two tandem reactors of respectively 20g catalyst for pre-hydrogenation and 10g selective hydrogenation cracking catalyst being packed into.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel, beds equal 3 millimeters granulated glass spherees of filling Φ up and down play air-flow distribution and supporting role.360 ℃ of pre-hydrogenator temperature of reaction, weight space velocity 2.5h
-1, reaction pressure 3.5MPa, hydrogen hydrocarbon mol ratio is 5.0.450 ℃ of hydrocracking reactor temperature of reaction, weight space velocity 5.0h
-1, reaction pressure 5.0MPa, hydrogen hydrocarbon mol ratio is 2.0.
The raw material light cycle oil derives from refining catalytic cracking unit (with embodiment 1), H
2For processing electrolysis hydrogen through dehydrating, the product of pre-hydrotreating reaction is as the raw material of hydrocracking reaction, and the results are shown in Table 3 for raw material and product analysis.
Table 3 raw material and product weight percent form
Wherein, catalyst for pre-hydrogenation desulfurization degree 99.2%, denitrification percent 94.5%; The transformation efficiency of double ring arene under the hydrocracking catalyst effect is 75.6%, and the mononuclear aromatics selectivity is 62.3%.
[embodiment 4]
Get silica alumina ratio and be 12 Hydrogen overstable gamma zeolite 25g, pseudo-boehmite 150 grams, after kneading, extrusion, oven dry, roasting obtain catalyst body, passing through incipient impregnation method load 1.5wt%Co and 5.0wt%Mo with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate solution, is available catalyst for pre-hydrogenation after oven dry and roasting.Get silica alumina ratio and be extrusion after 40 Hydrogen ZSM-5 zeolite 50g, pseudo-boehmite 79 gram kneadings, oven dry, roasting and obtain catalyst body, by dipping method load 0.5wt%Pt, 2.0wt%Mo and 0.5wt%La, be available selective hydrogenation cracking catalyst after oven dry and roasting with platinum acid chloride solution, ammonium molybdate solution and lanthanum nitrate hexahydrate.
Under hydro condition, in two tandem reactors of respectively 20g catalyst for pre-hydrogenation and 20g selective hydrogenation cracking catalyst being packed into.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel, beds equal 3 millimeters granulated glass spherees of filling Φ up and down play air-flow distribution and supporting role.360 ℃ of pre-hydrogenator temperature of reaction, weight space velocity 2.0h
-1, reaction pressure 4.0MPa, hydrogen hydrocarbon mol ratio is 2.0.400 ℃ of hydrocracking reactor temperature of reaction, weight space velocity 2.0h
-1, reaction pressure 4.0MPa, hydrogen hydrocarbon mol ratio is 2.0.
The raw material light cycle oil derives from refining catalytic cracking unit (with embodiment 1), H
2For processing electrolysis hydrogen through dehydrating, the product of pre-hydrotreating reaction is as the raw material of hydrocracking reaction, and the results are shown in Table 4 for raw material and product analysis.
Table 4 raw material and product weight percent form
Wherein, catalyst for pre-hydrogenation desulfurization degree 98.8%, denitrification percent 94.4%; The transformation efficiency of double ring arene under the hydrocracking catalyst effect is 54.8%, and the mononuclear aromatics selectivity is 76.2%.
[embodiment 5]
The present embodiment with in [embodiment 1] through adding the separating effect of product liquid in separation column after hydrogen pretreatment and selective hydrogenation cracking reaction, the operational circumstances of hydrocracking reactor aftercut tower is described.The working pressure 0.05Mpa of fractionator overhead, 208 ℃ of service temperatures.Under steady operation conditions, feed rate counts 100%, and tower top light constituent flow is 65%, and tail oil heavy constituent flow is 35%, and product composition and flow are as shown in table 5.
The product composition of table 5 fractionation tower top and Fractionator Bottom and flow
[embodiment 6]
The basic data that consists of with alkane, naphthenic hydrocarbon, mononuclear aromatics, double ring arene, thrcylic aromatic hydrocarbon and colloid in typical catalytic cracking light cycle oil in [embodiment 1], add the operational condition of hydrogen pretreatment and cracking catalyst also with [embodiment 1], the operational condition of separation column is as [embodiment 5], 40% of separation column tail oil loops back the hydrocracking reaction unit, investigates the present invention and presses the ability of the technical process manufacture order Polycyclic aromatic hydrocarbons shown in accompanying drawing 1 and the treatment scale situation of each unit.
The light cycle oil feed rate is 43930kg/h, and the thick mononuclear aromatics mixture flow rate that is transported to Aromatic Hydrocarbon United Plant is 33102kg/h, and effluxing low-sulfur heavy constituent tail oil flow is 10628kg/h.Composition and the flow of raw material, pilot process sample and product are as shown in table 6, and the treatment scale of each unit and thick mononuclear aromatics output are as shown in table 7.
As seen, process through processing method of the present invention, low-quality catalytic cracking light cycle oil can be converted into industrial thick mononuclear aromatics mixture with significant application value, is delivered directly to Aromatic Hydrocarbon United Plant and is used for maximizing production p-Xylol and benzene.And because the reaction preference of catalyzer is high, fractionation process is simple, has reduced facility investment and running cost, has obtained technique effect preferably.
Composition and the flow of table 6 raw material, pilot process sample and product
The treatment scale of each unit of table 7 and thick mononuclear aromatics output
Claims (7)
1. method by the mixture preparing aromatic hydrocarbon that contains hydrocarbon with condensed rings comprises the following steps:
A) with the sulphur weight content between 0～5%, weight nitroxide content is raw material between 0～1% hydrocarbon with condensed rings mixture, be that 250～450 ℃, weight space velocity are that 0.5～3 hour-1, pressure are under 3～12MPa condition in temperature, raw material contacts with catalyzer in hydrogenator, generate stream I after reaction, wherein catalyzer used comprises following component by weight percentage: (a) γ-Al of 60～97%
2O
3Carrier; (b) 1～30% zeolite molecular sieve material; (c) 1～8% CoO; (d) 2～25% MoO
3
B) stream I is after the gas-liquid separation of high score device, and gaseous stream loops back hydrogenator after removing hydrogen sulfide and nitride through extracting tower, and sulphur content is by weight percentage discharged less than 100ppm, the nitrogen content stream I I less than 50ppm in the bottom of high score device;
C) stream I I enters cracking case, it is 2～6 face under hydrogen fixed bed reaction condition in 300～450 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa and hydrogen hydrocarbon mol ratio, containing the mixture material of condensed-nuclei aromatics contacts with catalyzer in cracking case, generate logistics III after reaction, wherein catalyzer used comprises following component: (a) at least a in ZSM-5 zeolite, 5～70% mordenite, Y zeolite, EU-1 zeolite, beta-zeolite molecular sieve; (b) at least a in 0.01～5.0% VIII family metal; (c) 15～80% binding agent;
D) the stream I II that discharges bottom cracking case is after the gas-liquid separation of high score device, gaseous stream loops back cracking case, high score device bottom is discharged liquid phase stream and is entered the aromatic hydrocarbons separation column, obtains aromatic product V and tail oil VI, and tail oil partly or entirely loops back cracking case.
2. the method for a kind of mixture preparing aromatic hydrocarbon by containing hydrocarbon with condensed rings according to claim 1, it is characterized in that raw material comes catalytic cracking light cycle oil, pyrolysis gasoline, Aromatic Hydrocarbon United Plant heavy aromatics tower bed material or coal tar.
3. the method for a kind of mixture preparing aromatic hydrocarbon by containing hydrocarbon with condensed rings according to claim 1, it is characterized in that raw material is a kind of solar oil component, from catalytic cracking unit, 180～360 ℃ of boiling spreads, 20 ℃ of density are not less than 0.80g/ml, and total aromatic ring content is greater than 50% by weight percentage, and dicyclo aromatic ring content is greater than 35%, sulphur content is between 0～5%, and nitrogen content is between 0～1%.
4. the method for a kind of mixture preparing aromatic hydrocarbon by containing hydrocarbon with condensed rings according to claim 1, it is characterized in that desulfurization after the hydrocarbon with condensed rings mixture selective opening reaction occurs in cracking case, generate the mononuclear aromatics mixture.
5. the method for a kind of mixture preparing aromatic hydrocarbon by containing hydrocarbon with condensed rings according to claim 1, the tower top pressure that it is characterized in that separation column is between-0.1MPa～0.5Mpa, and tower top temperature is between 150～220 ℃.
6. the method for a kind of mixture preparing aromatic hydrocarbon by containing hydrocarbon with condensed rings according to claim 1, it is characterized in that reaction product cuts into low boiling point arene mixture and high boiling point tail oil by boiling point in separation column, the low boiling point arene mixture is directly delivered in Aromatic Hydrocarbon United Plant, and the high boiling point tail oil partly or entirely loops back hydroeracking unit.
7. the method for a kind of mixture preparing aromatic hydrocarbon by containing hydrocarbon with condensed rings according to claim 1 is characterized in that comprising the light aromaticss such as benzene,toluene,xylene in low boiling point arene mixture that separation column tells.
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| CN112691681A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Aromatic-rich light distillate selective hydrogenation catalyst, and preparation method and application thereof |
| CN114456035A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Aromatic hydrocarbon transalkylation method and system |
| CN115703977A (en) * | 2021-08-10 | 2023-02-17 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon and clean fuel oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101636472A (en) * | 2007-06-27 | 2010-01-27 | Hrd有限公司 | The system and method for hydrocracking |
| CN101687730A (en) * | 2007-07-06 | 2010-03-31 | 环球油品公司 | Process for the production of diesel and aromatic compounds |
| CN101730673A (en) * | 2007-07-06 | 2010-06-09 | 环球油品公司 | Be used to produce the method for dimethylbenzene |
-
2011
- 2011-11-18 CN CN201110369932.XA patent/CN103121897B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101636472A (en) * | 2007-06-27 | 2010-01-27 | Hrd有限公司 | The system and method for hydrocracking |
| CN101687730A (en) * | 2007-07-06 | 2010-03-31 | 环球油品公司 | Process for the production of diesel and aromatic compounds |
| CN101730673A (en) * | 2007-07-06 | 2010-06-09 | 环球油品公司 | Be used to produce the method for dimethylbenzene |
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| CN105378037B (en) * | 2013-07-02 | 2018-11-16 | 沙特基础工业公司 | It is the method for petroleum chemicals by refinery's heavy oil residue upgrading |
| CN106029842B (en) * | 2014-02-25 | 2018-11-13 | 沙特基础工业公司 | The method that BTX is produced by hydrocarbon mixture source using pyrolysis |
| US10131853B2 (en) | 2014-02-25 | 2018-11-20 | Saudi Basic Industries Corporation | Process for producing BTX from a mixed hydrocarbon source using pyrolysis |
| CN109593558B (en) * | 2014-02-25 | 2021-04-09 | 沙特基础工业公司 | Method for producing BTX from mixed hydrocarbon sources using pyrolysis |
| US10563136B2 (en) | 2014-02-25 | 2020-02-18 | Saudi Basic Industries Corporation | Process for producing BTX from a mixed hydrocarbon source using pyrolysis |
| CN109593558A (en) * | 2014-02-25 | 2019-04-09 | 沙特基础工业公司 | Using pyrolysis by the method for hydrocarbon mixture source production BTX |
| CN106029842A (en) * | 2014-02-25 | 2016-10-12 | 沙特基础工业公司 | Process for producing btx from a mixed hydrocarbon source using pyrolysis |
| CN105085135B (en) * | 2014-05-14 | 2017-03-15 | 中国石油化工股份有限公司 | The method that benzene and dimethylbenzene are directly produced by heavy aromatics inferior |
| CN105085135A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for direct production of benzene and xylene from inferior heavy aromatics |
| CN105085134B (en) * | 2014-05-14 | 2017-08-11 | 中国石油化工股份有限公司 | The method that aroamtic hydrocarbon raw material is directly produced by heavy aromatics inferior |
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| CN104447175A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Method for improving stability of heavy aromatic light catalyst |
| CN104357084A (en) * | 2014-11-11 | 2015-02-18 | 中国海洋石油总公司 | Combined process for conversion of C10+ heavy aromatics to light aromatics |
| CN104357083A (en) * | 2014-11-11 | 2015-02-18 | 中国海洋石油总公司 | Method for conversion of C10+ heavy aromatics into light aromatics by virtue of hydrogenation |
| CN104357084B (en) * | 2014-11-11 | 2016-08-24 | 中国海洋石油总公司 | A kind of C10+heavy aromatics lighting combined technical method |
| CN104357083B (en) * | 2014-11-11 | 2016-08-17 | 中国海洋石油总公司 | A kind of C10+heavy aromatics hydrogenation lightening method |
| CN106588540B (en) * | 2015-10-15 | 2020-02-07 | 中国石油化工股份有限公司 | Method for producing benzene and xylene from catalytic cracking light diesel oil |
| CN106588540A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Method of using LCO for producing benzene and dimethylbenzene |
| CN107286989A (en) * | 2017-06-19 | 2017-10-24 | 中国海洋石油总公司 | A kind of method that the high-knock rating gasoline rich in BTX is produced by heavy aromatics |
| CN112691681B (en) * | 2019-10-23 | 2022-07-12 | 中国石油化工股份有限公司 | Aromatic-rich light distillate selective hydrogenation catalyst, and preparation method and application thereof |
| CN112691681A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Aromatic-rich light distillate selective hydrogenation catalyst, and preparation method and application thereof |
| CN114456035A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Aromatic hydrocarbon transalkylation method and system |
| CN115703977A (en) * | 2021-08-10 | 2023-02-17 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon and clean fuel oil |
| CN115703977B (en) * | 2021-08-10 | 2024-02-09 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon and clean fuel oil |
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