CN115703977A - Method for producing light aromatic hydrocarbon and clean fuel oil - Google Patents
Method for producing light aromatic hydrocarbon and clean fuel oil Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 77
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Images
Abstract
The invention relates to the technical field of petrochemical industry, and discloses a method for producing light aromatic hydrocarbon and clean fuel oil, which comprises the following steps: (1) Carrying out hydrofining reaction and gas-liquid separation on LCO raw oil to obtain a first liquid-phase material flow; (2) Carrying out deep hydrocracking reaction and gas-liquid separation on the first liquid phase material flow to obtain a second liquid phase material flow; (3) Fractionating the second liquid-phase material flow to obtain light aromatic hydrocarbons, a recycled light diesel oil fraction and a recycled heavy diesel oil fraction, (4) separating the light aromatic hydrocarbons to obtain a BTX fraction; and circulating the recycled light diesel oil fraction for deep hydrocracking reaction, and circulating the recycled heavy diesel oil fraction for hydrorefining reaction. The method provided by the invention improves the composition of hydrocarbon feed in a hydrofining/hydrocracking reaction zone, can effectively improve the yield of catalytic conversion of LCO into BTX, and realizes high-value utilization of LCO.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for producing light aromatic hydrocarbon and clean fuel oil.
Background
In the composition of diesel oil products in China, catalytic diesel oil accounts for about 30 percent. The catalytic cracking diesel oil comes from a catalytic cracking device and has the characteristics of high aromatic hydrocarbon content (60-80%), very low cetane number (15-25), high density and the like. The diesel oil for vehicles produced by the catalytic diesel oil through a hydrofining or hydro-upgrading route has the problems of harsh operating conditions, high hydrogen consumption and the like, and the cetane number is increased in a limited range, so that the diesel oil is not economical. And with the stricter environmental regulations, the content of polycyclic aromatic hydrocarbons in the national VI diesel oil standard is further reduced, and the upgrading form of the oil quality of oil refining enterprises is more severe, so that the reasonable utilization of catalytic diesel oil becomes a problem of great concern.
Light aromatics (mainly benzene, toluene and xylene, BTX for short) are basic organic chemical raw materials, and are mainly derived from catalytic reforming at present. In recent years, the dependence of aromatic hydrocarbon on the exterior in China is improved year by year, and new raw material sources are urgently needed to be developed. The catalytic cracking diesel oil is rich in aromatic hydrocarbons, wherein the content of the polycyclic aromatic hydrocarbons is even up to 50 percent, and the catalytic cracking diesel oil is a high-quality resource for preparing high-octane gasoline components and light aromatic hydrocarbons (BTX). Therefore, the catalytic cracking diesel oil is developed to produce high value-added gasoline components and light aromatic hydrocarbons and clean diesel oil blending components through hydro-conversion, so that the problems of excessive diesel oil productivity and high pressure on upgrading the quality of oil products of enterprises can be solved, the tension situation that the aromatic hydrocarbon productivity is seriously insufficient can be relieved, the value maximization of poor diesel oil is realized, and the method has good market application prospect.
Research institutions and petrochemical companies at home and abroad develop a great deal of research work on the catalytic cracking diesel oil hydro-conversion technology.
The LCO-X process of UOP company, the ARO technology of NOVA chemical company, the FD2G technology for producing high-octane gasoline blending components or light aromatics by catalytic cracking diesel oil hydroconversion developed by FRIPP of petrochemistry, and the RLG/RLA technology developed by RIPP of petrochemistry of china all adopt a hydrofining and hydrocracking conversion technical route to convert aromatics in LCO into light aromatics, but most of the above technologies realize the conversion of LCO into gasoline fractions or concurrently produce a part of light aromatics, do not realize the maximum utilization of LCO, convert all of LCO into light aromatics (BTX) as far as possible, and still have the problems of low single-pass conversion rate and low BTX yield. Within its preferred range of conditions, the BTX selectivity is between 40% and 45%, the BTX yield reaches 20% to 25%, and there is a large margin of improvement over the maximum theoretical yield of BTX of 42.5% relative to the monocyclic aromatics content of more than 60% in the hydrogenated LCO fraction.
A process for producing high octane gasoline is disclosed in US 4985134A. In the scheme, the raw material is LCO with the boiling point range of 150-327 ℃, namely a light component in the catalytic cracking light cycle oil. The adopted hydrocracking catalyst contains a Y-type molecular sieve, a USY molecular sieve or a dealuminized Y-type molecular sieve. In addition, middle fractions which are more than the gasoline fraction and less than 232 ℃ or less than 260 ℃ in the fractionated product oil are returned to the inlet of the hydrocracking reactor or a catalytic cracking reaction zone.
CN101987971A and CN103184073A disclose a method for producing high-octane gasoline from poor diesel oil, and the method can obtain high-octane gasoline and low-sulfur clean diesel oil blending components by controlling the aromatic hydrocarbon saturation rate in a refining zone and refining and modifying the gasoline once through a fixed bed reactor.
CN101191081A discloses a catalytic conversion method of hydrocarbon oil raw material, which adopts a hydrotreating + catalytic cracking mode, and diesel oil is subjected to hydrotreating and then returned to a catalytic cracking reactor, so as to achieve the purpose of increasing the yields of high-octane gasoline and propylene. The method has simple process flow, and for enterprises, the device can meet the requirements through simple modification. However, the following two problems exist: on one hand, the tetrahydronaphthalene substances obtained after the polycyclic aromatic hydrocarbon is hydrogenated are converted back to the polycyclic aromatic hydrocarbon through hydrogen transfer reaction under the catalytic cracking condition, the cracking proportion is low, and the yield of target products is low; on the other hand, returning the hydrogenated diesel oil to catalytic cracking occupies the processing capacity of the catalytic cracking unit.
CN103865577A discloses a method for producing light aromatic hydrocarbons and clean fuel oil from catalytic cracking diesel oil, which comprises the steps of firstly carrying out hydrofining on catalytic diesel oil, then cutting a hydrofined product, cutting off fractions with the temperature higher than 355 ℃, extracting cut distillate oil by a solvent to obtain extract oil rich in polycyclic aromatic hydrocarbons and raffinate oil rich in alkane, and carrying out hydrocracking reaction on the raffinate oil rich in aromatic hydrocarbons to obtain light aromatic hydrocarbons and clean gasoline blending components. The method also has the problems of limited raw materials and high solvent extraction cost of diesel oil.
The existing catalytic cracking diesel oil hydrocracking technology mainly aims at converting polycyclic aromatic hydrocarbons rich in catalytic diesel oil into high-octane gasoline components and improving the cetane number of the diesel oil, most of light aromatic hydrocarbons (BTX) produced in the existing published hydrocracking technology are in a technical assumption stage, and the BTX is separated from the gasoline fraction by a purification or fractionation method.
Aiming at the condition of carbon deposition inactivation of a hydrocracking catalyst, the prior art generally needs to improve the hydrogenation capability of the hydrocracking catalyst and control the cracking capability of the hydrocracking catalyst, which leads to insufficient cracking depth of catalytic cracking diesel oil, and meanwhile, gasoline components generated by cracking can be excessively hydrogenated, which leads to lower octane number of products and higher hydrogen consumption. Therefore, the prior art has conducted a great deal of research on catalysts and process technologies, and designs hydrocracking catalysts from the viewpoint of equilibrium hydrogenation and cracking, thereby increasing the selectivity of BTX production.
Disclosure of Invention
The invention aims to solve the technical problem of poor BTX selectivity so as to realize the maximum conversion of LCO into BTX.
The inventor is initiated in creative research, and aims to effectively reduce excessive hydrogenation of light aromatics and chemical hydrogen consumption while remarkably improving the hydrocracking depth of the catalytic cracking diesel oil, thereby maximally producing the light aromatics and realizing maximum utilization of the value of the poor catalytic diesel oil. Characteristics of aromatic hydrocarbon in the LCO need to be fundamentally considered, thermodynamic equilibrium analysis and kinetic analysis of aromatic hydrocarbon hydrogenation saturation and monocyclic aromatic hydrocarbon hydrocracking are fully analyzed, and an LCO catalytic conversion route is designed according to a real reaction network. The inventive idea of the invention is thus obtained.
In order to achieve the above objects, the present invention provides a method for producing light aromatic hydrocarbons and clean fuel oil, the method comprising:
(1) Introducing LCO raw oil and hydrogen into a first reaction zone for carrying out hydrofining reaction, and carrying out gas-liquid separation on a material flow obtained after the reaction to obtain a first liquid-phase material flow;
(2) Introducing the first liquid phase material flow and hydrogen into a second reaction zone for deep hydrocracking reaction, and carrying out gas-liquid separation on the material flow obtained after the reaction to obtain a second liquid phase material flow;
(3) Fractionating the second liquid phase material flow to obtain dry gas, liquefied gas, light aromatic hydrocarbon, recycled light diesel oil fraction and recycled heavy diesel oil fraction, wherein the fractionation point between the light aromatic hydrocarbon and the recycled light diesel oil fraction is 160-170 ℃, and the fractionation point between the recycled light diesel oil fraction and the recycled heavy diesel oil fraction is 310-330 ℃;
(4) Introducing the light aromatic hydrocarbon into an aromatic hydrocarbon separation system for separation to obtain BTX fraction; and
and recycling the recycled light diesel oil fraction to the second reaction zone to carry out the deep hydrocracking reaction, and recycling the recycled heavy diesel oil fraction to the first reaction zone to carry out the hydrofining reaction.
The method provided by the invention improves the composition of hydrocarbon feed in a hydrofining/hydrocracking reaction zone, can effectively improve the yield of catalytic conversion of LCO into BTX, and realizes high-value utilization of LCO.
Drawings
Many devices such as pumps, heat exchangers, compressors, etc. have been omitted from the figure, but are well known to those skilled in the art.
FIG. 1 is a process flow diagram for producing light aromatic hydrocarbons and clean fuel oil according to a preferred embodiment of the present invention.
Description of the reference numerals
1: a hydrogen pipe network is arranged in the pipeline,
2: a hydrogen gas compressor,
3: the raw oil of LCO is prepared,
4. 16: a heat exchanger is arranged on the upper surface of the shell,
5: a heating furnace is arranged in the furnace body,
6. 8, 10, 11, 12, 15, 17, 19, 20: a pipeline for the supply of the gas to the reaction chamber,
7: the first reaction area is provided with a first reaction area,
9. 18: a gas-liquid separator,
13: the hydrogen gas is used as the hydrogen gas,
14: the second reaction zone is a reaction zone with a reaction zone,
21: a fractionation system for fractionating the liquid by using a fractionating tower,
22: acid gas and dry gas, and the acid gas and the dry gas,
23: the liquefied gas is liquefied gas,
24: light aromatic hydrocarbon is obtained by reacting a light aromatic hydrocarbon,
25: an aromatic hydrocarbon separation system is provided,
26: a reflux tank at the top of the fractionating tower,
27: C6-C9 saturated hydrocarbon,
28：BTX，
29: c9+ heavy aromatics;
30: recycle of light diesel oil fractions
31: recycle of heavy diesel oil fractions
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The total aromatic hydrocarbon content of the invention is the sum of the mass fractions of monocyclic aromatic hydrocarbon and aromatic hydrocarbon above a bicyclic ring.
As previously mentioned, the present invention provides a method for producing light aromatic hydrocarbons and clean fuel oil, the method comprising:
(1) Introducing LCO raw oil and hydrogen into a first reaction zone for carrying out hydrofining reaction, and carrying out gas-liquid separation on a material flow obtained after the reaction to obtain a first liquid-phase material flow;
(2) Introducing the first liquid-phase material flow and hydrogen into a second reaction zone for deep hydrocracking reaction, and carrying out gas-liquid separation on the material flow obtained after the reaction to obtain a second liquid-phase material flow;
(3) Fractionating the second liquid phase material flow to obtain dry gas, liquefied gas, light aromatic hydrocarbon, a recycled light diesel oil fraction and a recycled heavy diesel oil fraction, wherein the fractionation point between the light aromatic hydrocarbon and the recycled light diesel oil fraction is 160-170 ℃, and the fractionation point between the recycled light diesel oil fraction and the recycled heavy diesel oil fraction is 310-330 ℃;
(4) Introducing the light aromatic hydrocarbon into an aromatic hydrocarbon separation system for separation to obtain BTX fraction; and
and recycling the recycled light diesel oil fraction to the second reaction zone to carry out the deep hydrocracking reaction, and recycling the recycled heavy diesel oil fraction to the first reaction zone to carry out the hydrofining reaction.
Preferably, the distillation range of the recycled light diesel oil fraction is 165-320 ℃.
Preferably, the distillation range of the remilled heavy diesel oil fraction according to the invention is a fraction at >320 ℃.
The hydrofining reaction in the first reaction zone of the invention leads the aromatic hydrocarbon with double rings or above to be hydrogenated and saturated to generate monocyclic aromatic hydrocarbon, and carries out the removal of sulfur and nitrogen compounds.
The first liquid phase material flow is a liquid phase material flow (hydrogenation LCO) rich in monocyclic aromatic hydrocarbon.
The distillation range of the light aromatic hydrocarbon is preferably 65-165 ℃, the light aromatic hydrocarbon enters an aromatic hydrocarbon separation system, C4-C6 saturated hydrocarbon, BTX products and C9+ heavy aromatic hydrocarbon are obtained in the fractionation system, and the BTX is used as a product output system. The separation system can adopt a mature separation system, and can be used for rectifying a train of products, comprising: a debutanizer, a dehexanizer and a BTX rectification column. BTX in the light aromatic hydrocarbon can also be separated by solvent extraction or adsorption.
Preferably, the sulfur content of the BTX fraction obtained by the invention is less than 2 mu g/g, and the BTX fraction can be used as a high-octane gasoline component.
Preferably, the process conditions of the present invention are controlled such that the total aromatics content in the recycle light diesel fraction is above 60wt% and the single ring aromatics content is above 50wt%.
Preferably, the process conditions of the present invention are controlled such that the total aromatics content in the recycle heavy diesel fraction is above 50wt% and the bicyclic aromatics content is above 20 wt%.
Preferably, compared with the LCO raw oil, the hydrofining reaction conditions in the first reaction zone are controlled so that the aromatics saturation rate of more than two rings in the first liquid phase material flow is greater than 80%, and the total aromatics saturation rate is less than 20%.
Preferably, the API degree of the LCO raw oil is 12-25, the total aromatic hydrocarbon content is higher than 60wt%, and the aromatic hydrocarbon content of double rings and above is higher than 50wt%. More preferably, the API degree of the LCO raw oil is 15-25, the total aromatic hydrocarbon content is higher than 70wt% and the aromatic hydrocarbon content of dicyclic and above is higher than 60wt% based on the total weight of the LCO raw oil.
Preferably, the LCO raw oil is diesel fraction from one or more of a catalytic cracking unit, a coking unit, a direct coal liquefaction unit and a coal tar hydrogenation unit.
Preferably, the first reaction zone is filled with a hydrofining catalyst, and the hydrofining catalyst contains a carrier and a group VIII non-noble metal element and/or a group VIB non-noble metal element supported on the carrier.
Particularly preferably, the hydrorefining catalyst of the present invention is a catalyst comprising a carrier selected from at least one of alumina, alumina-silica and titania, and an active metal element supported on the carrier selected from at least one of nickel, cobalt, molybdenum and tungsten; more preferably, in the hydrofinishing catalyst, the content of nickel and/or cobalt in terms of oxide is 1 to 10% by weight and the content of molybdenum and/or tungsten in terms of oxide is 15 to 35% by weight, based on the total weight of the hydrofinishing catalyst.
The hydrofining catalyst provided by the invention can also contain phosphorus and/or fluorine, wherein the phosphorus and/or fluorine is contained, and the content of the phosphorus and/or fluorine is not more than 8 weight percent calculated by elements and based on the catalyst.
Particularly preferably, in the hydrorefining catalyst, the group VIII non-noble metal elements are cobalt and/or nickel, and the group VIB non-noble metal elements are molybdenum and/or tungsten.
Preferably, in the hydrorefining catalyst, the content of the non-noble metal element in the group VIII is 1-10wt% and the content of the non-noble metal element in the group VIB is 10-25wt% calculated by oxides and based on the total amount of the catalyst.
The hydrorefining catalyst of the present invention may be, for example, RSA-100 hydrorefining catalyst produced by catalyst Changjingtian, inc., of petrochemical Co., ltd. The hydrofining catalyst provided by the invention has the advantages of good denitrification effect, good selectivity and the like.
According to a preferred embodiment, the conditions of the first reaction zone comprise at least: the hydrogen partial pressure is 3-10 MPa, the reaction temperature is 300-400 ℃, and the liquid hourly space velocity measured by the oil mixture I is 0.5-6 h -1 The volume ratio of hydrogen to oil mixture I is 300-1000 Nm 3 /m 3 The oil mixture I is fresh material and the refining weightSum of diesel fractions.
More preferably, the conditions of the first reaction zone comprise at least: the hydrogen partial pressure is 3.2-7.2 MPa, the reaction temperature is 300-380 ℃, and the liquid hourly space velocity is 1.0-3.0 h by the sum of liquid phase materials at the inlet of the first reaction zone -1 The volume ratio of the hydrogen to the oil mixture I is 500-1000 Nm 3 /m 3 。
The second reaction area is filled with a hydrocracking catalyst.
Preferably, a hydrocracking catalyst is filled in the second reaction zone, the hydrocracking catalyst contains a carrier and an active component element loaded on the carrier, and the active component element is Mo, or the active component element is Mo and a group VIII non-noble metal element; the support is a combination of zeolite and alumina.
Preferably, in the hydrocracking catalyst, the zeolite in the carrier is MoY type zeolite modified by Mo, and the content of Mo in the carrier accounts for the metal element molybdenum as an active component in the hydrocracking catalyst calculated by oxide and is MoO 3 The content is 20-80 wt%.
Particularly preferably, the properties of the MoY type zeolite modified with Mo are as follows: siO 2 2 /Al 2 O 3 The mol ratio is 5 to 18, the unit cell parameter is 2.437 to 2.453, and the specific surface area is 600m 2 /g～900m 2 The relative crystallinity is 80 to 130 percent, and the pore volume is 0.30 to 0.50mL/g.
More preferably, in the hydrocracking catalyst, the content of the zeolite is 20-90wt%, the content of the alumina is 10-80wt%, the content of the non-noble metal element in the VIII group is 1-15 wt%, and the content of the metal element molybdenum as an active component is 3-30 wt% calculated by oxide and based on the total amount of the catalyst.
The hydrocracking catalyst has excellent selective cracking function and moderate hydrogenation performance, has good selectivity on the reactions of monocyclic aromatic side chain breakage, selective ring opening and side chain breakage of tetrahydronaphthalene and the like, ensures that monocyclic aromatic hydrocarbon in diesel oil fraction is subjected to selective cracking reaction to generate benzene, toluene and xylene, and can avoid excessive hydrogenation saturation of monocyclic aromatic hydrocarbon components.
According to a preferred embodiment, the conditions of the second reaction zone comprise at least: the hydrogen partial pressure is 1-6 MPa, the reaction temperature is 360-520 ℃, and the liquid time volume airspeed is 0.5-3.0 h when the oil mixture II is used for measuring liquid -1 The volume ratio of hydrogen to the oil mixture II is 800-2000 Nm 3 /m 3 And the oil mixture II is the sum of fresh materials and the recycled light diesel oil fraction.
More preferably, the conditions of the second reaction zone comprise at least: the hydrogen partial pressure is 1.6-4.8 MPa, the reaction temperature is 380-520 ℃, and the liquid hourly space velocity measured by the oil mixture II is 0.5-2.5 h -1 The volume ratio of the hydrogen to the oil mixture II is 800-1600 Nm 3 /m 3 。
In the second reaction zone of the invention, the first liquid phase material flow is subjected to deep hydrocracking, and in the presence of hydrogen, under the action of a hydrocracking catalyst with weak hydrogenation activity, ring opening and side chain breaking of tetralin and indane and deep side chain breaking of alkylbenzene are realized, so that alkylbenzene with broken side chains, namely BTX, is obtained, and the purposes of improving BTX selectivity and yield are further achieved. And after separating hydrogen-rich gas from the reaction effluent of the second reaction zone, feeding the reaction effluent into a fractionation system to obtain a light hydrocarbon fraction rich in BTX, a recycled light diesel oil fraction and a recycled heavy diesel oil fraction.
The catalytic conversion process with two reaction zones includes the first reaction zone and the second reaction zone, and the first reaction zone is used in hydrorefining reaction, and may be upflow or downflow fixed bed reactor. The second reaction zone may be at the same or different pressure level as the first reaction zone, preferably at a lower pressure level than the first reaction zone.
A particularly preferred embodiment of the process for producing light aromatic hydrocarbons and clean fuel oil according to the present invention is described below with reference to fig. 1:
in fig. 1, hydrogen from a hydrogen pipe network 1 is firstly mixed with recycle hydrogen from a pipeline 10, the mixture is pressurized by a recycle hydrogen compressor, then mixed with LCO raw oil 3 and refined heavy diesel oil fraction 31, and then subjected to heat exchange in a heat exchanger 4, and then heated to a required reaction temperature by a heating furnace 5, and then enters a first reaction zone 7 through a pipeline 6 to perform polycyclic aromatic hydrocarbon hydrogenation saturation reaction, and simultaneously perform desulfurization and denitrification. The reaction product in the first reaction zone enters a gas-liquid separator 9 through a pipeline 8 after heat exchange, gas-liquid separation is carried out in the gas-liquid separator, and the separated gas phase is subjected to hydrogen sulfide removal treatment and then returns to the inlet of the hydrogen compressor 2 through a pipeline 10 to be used as recycle hydrogen. The liquid phase material flow is mixed with the recycled light diesel oil fraction 30 through the pipeline 11 and then mixed with the hydrogen 13, the mixed material flow enters the second reaction zone 14 through the pipeline 12, and the ring opening and side chain breaking reaction of the monocyclic aromatic hydrocarbon is carried out in the second reaction zone, so that the light hydrocarbon and the diesel oil fraction are generated. The reacted material flow enters a heat exchanger 16 through a pipeline 15 for heat exchange and then enters a gas-liquid separator 18 through a pipeline 17, the separated gas-phase material flow is led out of the gas-liquid separator through a pipeline 19, and the desulfurized gas-phase material flow can be used as recycle hydrogen of a second reaction zone and can also be used as make-up hydrogen of other devices. The liquid phase obtained from the gas-liquid separator 18 flows through a pipeline 20 and enters a fractionating system 21 for fractionation, a fractionating tower top reflux tank 26 is arranged at the top of the fractionating tower, acidic and dry gases 22 are obtained in the fractionating system, and liquefied gas 23, light aromatic hydrocarbons 24, recycled light diesel oil fraction 30 and recycled heavy diesel oil fraction 31 are obtained. The light aromatic hydrocarbon 24 enters an aromatic hydrocarbon separation system 25 for further separation to obtain BTX 28, C6-C9 saturated hydrocarbon 27 and C9+ heavy aromatic hydrocarbon 29, and the C9+ heavy aromatic hydrocarbon can be mixed with recycle light diesel oil fraction 30 and then returns to the second reaction zone. The aromatic hydrocarbon separation system 25 can adopt a rectifying tower or a solvent extraction tower, and can obtain high-quality light aromatic hydrocarbon BTX.
Compared with the prior art, the method for producing the light aromatic hydrocarbon and the clean fuel oil has the following beneficial effects:
(1) The hydrofining reaction zone with high polycyclic aromatic hydrocarbon saturation rate is adopted to realize low polycyclic aromatic hydrocarbon content in the hydrogenated LCO, and hydrogen sulfide and ammonia of the hydrocracking catalyst are influenced through gas-liquid separation, so that the hydrocracking catalyst in the hydrocracking reaction zone has low inactivation and low carbon deposition rate, and the defect of short running period caused by carbon deposition inactivation of the catalyst is avoided;
(2) The invention preferably adopts a hydrocracking catalyst with moderate hydrogenation activity, can effectively reduce the excessive hydrogenation of light aromatic hydrocarbon and reduce the chemical hydrogen consumption while obviously improving the hydrocracking LCO depth, thereby maximally producing the light aromatic hydrocarbon.
(3) The method has wide raw material application range, is suitable for diesel fractions of one or more of an autocatalytic cracking device, a coking device, a direct coal liquefaction device and a coal tar hydrogenation device, and can realize the maximum catalytic conversion to produce light aromatic hydrocarbons.
(4) By adopting the method, the higher BTX yield can be realized, and compared with the prior similar technology, the BTX yield is improved by more than 35 percent.
(5) The invention belongs to a full conversion process, mainly aims at producing light raw materials to the maximum extent, and realizes the light and high-value utilization of LCO.
In conclusion, the method utilizes thermodynamic equilibrium data of the reaction, refines reaction steps, controls a reaction network from a molecular level, converts aromatic hydrocarbon molecules in the diesel oil into light aromatic hydrocarbon with high added value to the maximum extent, has the advantages of strong raw material adaptability, high yield of the light aromatic hydrocarbon and low hydrogen consumption, has obvious economic benefit, and can be used for industrial production.
The method preferably adopts hydrofining with high bicyclic aromatic saturation rate and a hydrocracking catalyst with moderate hydrogenation activity, can effectively reduce excessive hydrogenation of light aromatic hydrocarbon and chemical hydrogen consumption while remarkably improving the hydrocracking depth of catalytic cracking diesel, and thus maximally produces the light aromatic hydrocarbon. Meanwhile, the deep removal of the polycyclic aromatic hydrocarbon is realized, and the defect of short running period caused by carbon deposition and inactivation of a hydrocracking catalyst is avoided.
The present invention will be described in detail below by way of examples. In the following examples, the raw materials used are all common commercial products unless otherwise specified.
Yield of BTX = yield of light aromatics × BTX content in light aromatics × 100%
In the examples, the hydrorefining catalyst used was RSA-100 and the hydrocracking catalyst was RHC-100, both of which were produced by Chang-Chang catalyst, a petrochemical Co., ltd.
In the examples, the reaction temperature of the first reaction zone and the reaction temperature of the second reaction zone are weighted average reaction temperatures of the respective hydrogenation reaction zones. The weighted average reaction temperature for a single hydrogenation reaction zone is calculated as:
weighted average reaction temperature = Σ (weight factor of reaction temperature measurement point x display temperature of reaction temperature measurement point)
Wherein the weighting factors are defined as follows:
(1) The weight of the catalyst from the inlet of the catalyst bed layer of each hydrogenation reaction zone to the first layer of temperature measuring point is represented by the first layer of temperature measuring point;
(2) Half of the catalyst weight between two adjacent temperature measuring points of each hydrogenation reaction zone is represented by the upper temperature measuring point, and the other half is represented by the lower temperature measuring point;
(3) The weight of the catalyst from the lowest temperature measuring point of the catalyst bed to the outlet of the catalyst bed is represented by the lowest temperature measuring point;
(4) When a plurality of thermocouples exist at each layer of temperature measuring point, the calculated average value of the temperature measuring values of all thermocouples in the layer is used as the temperature of the temperature measuring point of the layer.
In the example, the calculation formula of the correlation index is as follows:
the raw oil CO-A, CO-B and CO-C used in the examples are catalytically cracked diesel oil from three different units, and the basic properties are shown in Table 1.
Table 1:
| item | LCO-A | LCO-B | LCO-C |
| Density (20 deg.C)/g.cm 3 | 0.9668 | 0.977 | 0.9347 |
| API | 14.32 | 12.81 | 19.27 |
| Total sulfur content/. Mu.g/g | 7480 | 1940 | 2311 |
| Total nitrogen content/. Mu.g/g | 578 | 948 | 441 |
| Total aromatic hydrocarbons in wt.% | 82.8 | 89.7 | 80.7 |
| Monocyclic aromatic content, wt.% | 16.9 | 18.4 | 26.3 |
| Polycyclic aromatic hydrocarbons content, wt.% | 65.9 | 71.3 | 54.4 |
| ASTM-D86 | |||
| Initial boiling point | 217 | 201 | 186 |
| 50％ | 278 | 255 | 251 |
| End point of distillation | 344 | 338 | 330 |
Example 1
The catalytic cracking diesel oil is processed according to the method of the invention, light aromatic hydrocarbon and clean fuel oil are produced by hydrocracking, and the first reaction zone and the second reaction zone are both provided with fixed bed hydrogenation reactors.
Raw oil CO-A is pressurized, mixed with A hydrogen-containing stream and then enters A hydrogenation reactor together with recycle heavy diesel oil, firstly passes through A first hydrogenation reaction zone and contacts with A hydrogenation refining catalyst to be subjected to hydrogenation refining, then enters A gas-liquid separator to be subjected to gas-liquid separation, the obtained hydrogenated CO stream is mixed with hydrogen, then mixed with recycle light diesel oil and enters A second hydrogenation reaction zone to contact with A hydrocracking catalyst to be subjected to deep hydrocracking reaction.
The process conditions are shown in Table 2, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 6.0MPa, the reaction temperature of the first hydrogenation reaction zone is 330 ℃, and the liquid hourly volume space velocity of LCO of the first hydrogenation reaction zone is 2.0h -1 The liquid hourly volume space velocity of the mixed feeding is 2.2h -1 . The reaction temperature of the second hydrogenation reaction zone is 420 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 3.2MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.0h -1 . The liquid hourly volume space velocity of the feeding material after being mixed with the remilled heavy diesel oil is 1.3h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 500, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1100.
And the effluent of the second hydrogenation reaction zone is subjected to gas-liquid separation in a low-pressure separator, the gas-phase material flow obtained by separation in the low-pressure separator is desulfurized and then circulated back to the inlet of the reactor, the obtained liquid-phase material flow enters a fractionating tower for fractionation, dry gas, liquefied gas and light hydrocarbon fractions are produced at the tower top, and a recycle light diesel oil fraction and a recycle heavy diesel oil fraction at the tower bottom are extracted from the tower. The recycled light diesel oil fraction returns to the inlet of the second reaction area, and the recycled heavy diesel oil fraction at the bottom of the tower returns to the inlet of the first reaction area. And the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and is fractionated to obtain C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon.
The main properties of the product are shown in table 3.
Comparative example 1
CO-A is used as raw oil, and the technological process is conventional single-stage refining/cracking technological process, i.e. the pressure of two reaction zones is identical, and no diesel oil fraction is recycled. The method comprises the steps of mixing A raw oil CO-A after being boosted with pressure with A hydrogen-containing material flow, then enabling the mixture to enter A first hydrogenation reaction zone, contacting with A hydrofining catalyst, carrying out hydrofining, then enabling the mixture to enter A gas-liquid separator to carry out gas-liquid separation, mixing the obtained hydrogenated CO material flow with hydrogen, then enabling the mixture to enter A second hydrogenation reaction zone, contacting with A hydrocracking catalyst, and carrying out deep hydrocracking reaction. And the effluent of the second hydrogenation reaction zone is subjected to gas-liquid separation in a low-pressure separator, the gas-phase material flow obtained by separation in the low-pressure separator is desulfurized and then circulated back to the inlet of the reactor, the obtained liquid-phase material flow enters a fractionating tower for fractionation, and dry gas, liquefied gas, light hydrocarbon fractions and diesel fractions are produced at the tower top. And the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and is fractionated to obtain C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon.
The specific process conditions are shown in Table 4, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 6.0MPa, the reaction temperature of the first hydrogenation reaction zone is 330 ℃, and the liquid hourly volume space velocity of LCO of the first hydrogenation reaction zone is 2.0h -1 . The reaction temperature of the second hydrogenation reaction zone is 420 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 6.0MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.0h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 800, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1100.
The main properties of the product are shown in table 5.
Example 2
The process flow of the method for processing the catalytic cracking diesel oil is the same as that of the example 1, and the specific process conditions are shown in Table 2, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 3.6MPa, the reaction temperature of the first hydrogenation reaction zone is 340 ℃, and the liquid hourly volume space velocity of LCO of the first hydrogenation reaction zone is 1.5h -1 The liquid hourly volume space velocity of the mixed feeding is 1.6h -1 . The reaction temperature of the second hydrogenation reaction zone is 450 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 2.4MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.5h -1 . The liquid hourly volume space velocity of the feeding material after being mixed with the remilled heavy diesel oil is 1.8h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 800, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1600.
And (3) carrying out gas-liquid separation on the effluent of the second hydrogenation reaction zone in a low-pressure separator, desulfurizing the gas-phase stream obtained by separation in the low-pressure separator, circulating the gas-phase stream back to the inlet of the reactor, fractionating the obtained liquid-phase stream in a fractionating tower, producing dry gas, liquefied gas and light hydrocarbon fractions at the tower top, pumping a recycled light diesel fraction from the tower, and recycling the heavy diesel fraction at the tower bottom. The recycled light diesel oil fraction returns to the inlet of the second reaction area, and the recycled heavy diesel oil fraction at the bottom of the tower returns to the inlet of the first reaction area. And the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and is fractionated to obtain C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon.
The main properties of the product are shown in table 3.
Comparative example 2
CO-A is used as raw oil, the process flow is A conventional single-stage refining/cracking process flow, namely the pressure of two reaction zones is the same, and the first reaction zone and the second reaction zone are provided with gas-liquid separation, but no recycle diesel oil fraction is provided. The method comprises the steps of mixing A raw oil CO-A after being boosted with pressure with A hydrogen-containing material flow, then enabling the mixture to enter A first hydrogenation reaction zone, contacting with A hydrofining catalyst, carrying out hydrofining, then enabling the mixture to enter A gas-liquid separator to carry out gas-liquid separation, mixing the obtained hydrogenated CO material flow with hydrogen, then enabling the mixture to enter A second hydrogenation reaction zone, contacting with A hydrocracking catalyst, and carrying out deep hydrocracking reaction. And the effluent of the second hydrogenation reaction zone is subjected to gas-liquid separation in a low-pressure separator, the gas-phase material flow obtained by separation in the low-pressure separator is desulfurized and then circulated back to the inlet of the reactor, the obtained liquid-phase material flow enters a fractionating tower for fractionation, and dry gas, liquefied gas, light hydrocarbon fractions and diesel fractions are produced at the tower top. And (3) the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon are obtained through fractionation.
The specific process conditions are shown in Table 4, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 6.0MPa, the reaction temperature of the first hydrogenation reaction zone is 330 ℃, and the liquid hourly volume space velocity of LCO of the first hydrogenation reaction zone is 2.0h -1 . The reaction temperature of the second hydrogenation reaction zone is 420 ℃, the reactor inlet hydrogen partial pressure of the second hydrogenation reaction zone is 6.0MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.5h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 800, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1100.
The main properties of the product are shown in table 5.
Example 3
The process flow of the method for processing the catalytic cracking diesel oil adopts the raw oil CO-A and the specific process conditions are shown in Table 2, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 4.8MPA, the reaction temperature of the first hydrogenation reaction zone is 320 ℃, and the liquid hourly volume space velocity of the CO of the first hydrogenation reaction zone is 1.0h -1 The liquid hourly volume space velocity of the mixed feeding is 1.1h -1 . The reaction temperature of the second hydrogenation reaction zone is 450 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 2.0MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.5h -1 . The liquid hourly volume space velocity of the feeding material after being mixed with the recycled heavy diesel oil is 1.9h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 1100, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1100.
And the effluent of the second hydrogenation reaction zone is subjected to gas-liquid separation in a low-pressure separator, the gas-phase material flow obtained by separation in the low-pressure separator is desulfurized and then circulated back to the inlet of the reactor, the obtained liquid-phase material flow enters a fractionating tower for fractionation, dry gas, liquefied gas and light hydrocarbon fractions are produced at the tower top, the recycled light diesel fraction is extracted from the tower, and the heavy diesel fraction is recycled at the tower bottom. The recycled light diesel oil fraction returns to the inlet of the second reaction area, and the recycled heavy diesel oil fraction at the bottom of the tower returns to the inlet of the first reaction area. And the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and is fractionated to obtain C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon.
The main properties of the product are shown in table 3.
Example 4
The process flow of the method for processing the catalytic cracking diesel oil adopts the raw oil LCO-B, the specific process conditions are shown in Table 2, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 8.0MPa, the reaction temperature of the first hydrogenation reaction zone is 310 ℃, and the liquid hourly volume space velocity of the LCO of the first hydrogenation reaction zone is 3.0h -1 The liquid hourly volume space velocity of the mixed feeding is 3.3h -1 . The reaction temperature of the second hydrogenation reaction zone is 500 ℃, the reactor inlet hydrogen partial pressure of the second hydrogenation reaction zone is 4.8MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.5h -1 . With heavy diesel oilThe liquid hourly space velocity of the mixed feeding is 1.7h -1 。
The volume ratio of hydrogen to oil in the first hydrogenation reaction zone is 500, and the volume ratio of hydrogen to oil in the second hydrogenation reaction zone is 1200.
And the effluent of the second hydrogenation reaction zone is subjected to gas-liquid separation in a low-pressure separator, the gas-phase material flow obtained by separation in the low-pressure separator is desulfurized and then circulated back to the inlet of the reactor, the obtained liquid-phase material flow enters a fractionating tower for fractionation, dry gas, liquefied gas and light hydrocarbon fractions are produced at the tower top, the recycled light diesel fraction is extracted from the tower, and the heavy diesel fraction is recycled at the tower bottom. The recycled light diesel oil fraction returns to the inlet of the second reaction zone, and the recycled heavy diesel oil fraction at the bottom of the tower returns to the inlet of the first reaction zone. And the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and is fractionated to obtain C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon.
The main properties of the product are shown in table 3.
Example 5
The process flow of the method for processing the catalytic cracking diesel oil is the same as that of example 1, raw oil LCO-C is adopted, and the specific process conditions are shown in Table 2, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 3.2MPa, the reaction temperature of the first hydrogenation reaction zone is 360 ℃, and the liquid hourly volume space velocity of the LCO in the first hydrogenation reaction zone is 1.0h -1 The liquid hourly volume space velocity of the mixed feeding is 1.1h -1 . The reaction temperature of the second hydrogenation reaction zone is 400 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 1.6MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 0.8h -1 . The liquid hourly volume space velocity of the feed after mixing with the recycled heavy diesel oil is 1.0h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 1000, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 800.
And (3) carrying out gas-liquid separation on the effluent of the second hydrogenation reaction zone in a low-pressure separator, desulfurizing the gas-phase stream obtained by separation in the low-pressure separator, circulating the gas-phase stream back to the inlet of the reactor, fractionating the obtained liquid-phase stream in a fractionating tower, producing dry gas, liquefied gas and light hydrocarbon fractions at the tower top, pumping a recycled light diesel fraction from the tower, and recycling the heavy diesel fraction at the tower bottom. The recycled light diesel oil fraction returns to the inlet of the second reaction area, and the recycled heavy diesel oil fraction at the bottom of the tower returns to the inlet of the first reaction area. And (3) the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon are obtained through fractionation.
The main properties of the product are shown in table 3.
Comparative example 3
LCO-C is used as raw oil, the process flow is a conventional single-stage refining/cracking process flow, namely the pressure of two reaction zones is the same, and the first reaction zone and the second reaction zone are provided with gas-liquid separation, but no recycle diesel fraction is provided. The method comprises the steps of mixing a raw oil LCO-C after boosting pressure with a hydrogen-containing stream, then feeding the mixture into a first hydrogenation reaction zone, contacting with a hydrofining catalyst, hydrofining, then feeding the mixture into a gas-liquid separator for gas-liquid separation, mixing the obtained hydrogenated LCO stream with hydrogen, feeding the mixture into a second hydrogenation reaction zone, contacting with a hydrocracking catalyst, and carrying out deep hydrocracking reaction. And performing gas-liquid separation on the effluent of the second hydrogenation reaction zone in a low-pressure separator, desulfurizing the gas-phase stream obtained by separation in the low-pressure separator, circulating the gas-phase stream back to the inlet of the reactor, fractionating the obtained liquid-phase stream in a fractionating tower, and producing dry gas, liquefied gas, light hydrocarbon fraction and diesel fraction at the tower top. And (3) the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon are obtained through fractionation.
The specific process conditions are shown in Table 4, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 1.6MPa, the reaction temperature of the first hydrogenation reaction zone is 360 ℃, and the liquid hourly volume space velocity of LCO of the first hydrogenation reaction zone is 1.0h -1 . The reaction temperature of the second hydrogenation reaction zone is 450 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 1.6MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.5h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 1000, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1200.
The main properties of the product are shown in table 5.
Comparative example 4
LCO-C is used as raw oil, the process flow is a conventional single-stage refining/cracking process flow, namely, the pressure of the two reaction zones is the same, the first reaction zone and the second reaction zone are provided with gas-liquid separation, and all diesel oil fractions obtained by the fractionation system are returned to the second reaction zone for continuous hydrocracking reaction. The method comprises the steps of mixing a raw oil LCO-C after boosting pressure with a hydrogen-containing stream, then feeding the mixture into a first hydrogenation reaction zone, contacting with a hydrofining catalyst, hydrofining, then feeding the mixture into a gas-liquid separator for gas-liquid separation, mixing the obtained hydrogenated LCO stream with hydrogen, then feeding the mixture into a second hydrogenation reaction zone with a recycle diesel oil fraction from a fractionation system, contacting with a hydrocracking catalyst, and carrying out deep hydrocracking reaction. And the effluent of the second hydrogenation reaction zone is subjected to gas-liquid separation in a low-pressure separator, the gas-phase material flow obtained by separation in the low-pressure separator is desulfurized and then circulated back to the inlet of the reactor, the obtained liquid-phase material flow enters a fractionating tower for fractionation, and dry gas, liquefied gas, light hydrocarbon fractions and diesel fractions are produced at the tower top. The diesel fraction is returned to the inlet of the second reaction zone. And the light hydrocarbon fraction enters an aromatic hydrocarbon separation system, and is fractionated to obtain C5-C6 non-aromatic alkane, BTX and C9+ heavy aromatic hydrocarbon.
The specific process conditions are shown in Table 6, wherein the reactor inlet hydrogen partial pressure of the first hydrogenation reaction zone is 5.5MPa, the reaction temperature of the first hydrogenation reaction zone is 340 ℃, and the liquid hourly volume space velocity of LCO of the first hydrogenation reaction zone is 1.5h -1 . The reaction temperature of the second hydrogenation reaction zone is 420 ℃, the reactor inlet hydrogen partial pressure of the second reaction zone is 5.5MPa, and the liquid hourly volume space velocity of the second hydrogenation reaction zone is 1.0h -1 The liquid hourly volume space velocity of the feed after mixing with the recycled heavy diesel oil is 1.3h -1 。
The hydrogen-oil volume ratio of the first hydrogenation reaction zone is 800, and the hydrogen-oil volume ratio of the second hydrogenation reaction zone is 1100.
The main properties of the product are shown in table 7.
TABLE 2
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Raw oil | LCO-A | LCO-A | LCO-A | LCO-B | LCO-C |
| A first reaction zone | |||||
| Catalyst and process for producing the same | RSA-100 | RSA-100 | RSA-100 | RSA-100 | RSA-100 |
| Partial pressure of hydrogen, MPa | 6.0 | 3.6 | 4.8 | 8 | 3.2 |
| Weighted average reaction temperature,. Deg.C | 330 | 340 | 320 | 310 | 360 |
| LCO space velocity, h-1 | 2 | 1.5 | 1 | 3 | 1 |
| Total volume space velocity, h -1 | 2.2 | 1.6 | 1.1 | 3.3 | 1.1 |
| Volume ratio of hydrogen to oil, nm 3 /m 3 | 500 | 800 | 1100 | 500 | 1000 |
| A second reaction zone | |||||
| Catalyst and process for producing the same | RHC-100 | RHC-100 | RHC-100 | RHC-100 | RHC-100 |
| Partial pressure of hydrogen, MPa | 3.2 | 2.4 | 2 | 4.8 | 1.6 |
| Weighted average reaction temperature,. Deg.C | 420 | 450 | 450 | 500 | 400 |
| Space velocity of hydrogenated LCO, h-1 | 1.5 | 1.5 | 1.5 | 1.5 | 0.8 |
| Total cracking volume space velocity, h -1 | 1.3 | 1.8 | 1.9 | 1.7 | 1.0 |
| Volume ratio of hydrogen to oil, nm 3 /m 3 | 1100 | 1600 | 1100 | 1200 | 800 |
TABLE 3
TABLE 4
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Raw oil | LCO-A | LCO-A | LCO-C |
| First reaction zone | |||
| Catalyst and process for producing the same | RSA-100 | RSA-100 | RSA-100 |
| Partial pressure of hydrogen, MPa | 6.0 | 3.6 | 1.6 |
| Weighted average reaction temperature,. Degree.C | 330 | 330 | 360 |
| LCO space velocity, |
2 | 2 | 1 |
| Volume ratio of hydrogen to oil, nm 3 /m 3 | 800 | 800 | 1000 |
| A second reaction zone | |||
| Catalyst and process for producing the same | RHC-100 | RHC-100 | RHC-100 |
| Partial pressure of hydrogen, |
6 | 6 | 1.6 |
| Weighted average reaction temperature,. Deg.C | 420 | 420 | 450 |
| LCO space velocity of hydrogenation, h -1 | 1.0 | 1.5 | 1.5 |
| Volume ratio of hydrogen to oil, nm 3 /m 3 | 1100 | 1100 | 1200 |
TABLE 5
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| First reaction zone product Properties | |||
| Total aromatic content, wt% | 67 | 67 | 70 |
| Aromatic content over bicyclo ring, wt% | 7 | 7 | 45 |
| Total aromatics saturation ratio,% | 25.31 | 25.31 | 2.78 |
| Percent of aromatic hydrocarbons of bicyclo ring or more | 90.18 | 90.18 | 27.42 |
| Product of separation systemProperties and yield | |||
| Dry gas, wt% | 4.2 | 4.5 | 3.2 |
| Liquefied gas, wt% | 8.2 | 8.5 | 4.5 |
| Yield of light hydrocarbon fraction, wt% | 35 | 30 | 25 |
| Yield of diesel oil, wt% | 52.6 | 57.0 | 67.3 |
| Aromatics separation system yield | |||
| BTX yield, wt.% | 22.8 | 18.72 | 15 |
| Get rid of C9+ heavy aromatics yield by weight percent | 5.6 | 6.9 | 6.2 |
TABLE 6
TABLE 7
| Item | Comparative example 4 |
| First reaction zone product Properties | |
| Total aromatic content, wt% | 67 |
| Aromatic hydrocarbon content over bicyclo ring, wt% | 7 |
| Total aromatics saturation ratio,% | 25.31 |
| Percent of aromatic hydrocarbons of bicyclo ring or more | 90.18 |
| Product properties of the second reaction zone | |
| Dry gas, wt% | 4.5 |
| Liquefied gas, wt% | 11.5 |
| Yield of light hydrocarbon fraction, wt% | 52 |
| Yield of diesel oil, |
29 |
| Aromatics separation system yield | |
| BTX yield, wt.% | 27.5 |
| Yield of externally thrown C9+ heavy arene, wt% | 5.0 |
From the results, the method can effectively reduce the excessive hydrogenation of light aromatics, the content of aromatics in the obtained naphtha fraction is more than 65wt%, the yield of BTX is up to 36% or more, dry gas, liquefied gas and light alkanes are rich, and LCO is completely converted into light aromatics.
The method of the invention preferably matches different reaction conditions required in a reaction network by controlling reaction process conditions, and flexibly controls the hydrocracking depth on the basis of ensuring the polycyclic aromatic hydrocarbon in LCO to be hydrogenated and saturated; according to the process, the staged utilization is realized according to the diesel oil fraction obtained by the primary cracking reaction, different types of diesel oil fractions are returned to the matched reaction depth node on the process flow, and the further reaction of the diesel oil fraction is controlled, so that the catalytic diesel oil is converted into light hydrocarbon fraction to the maximum extent, and the BTX is further obtained by the separation of an aromatic hydrocarbon separation system. The yield of light aromatic hydrocarbon BTX is up to 36wt% based on the treated catalytic cracking diesel oil raw material. Therefore, the method provided by the invention adopts a double-reaction-zone process flow, can effectively reduce excessive hydrogenation of light aromatic hydrocarbon and simultaneously obviously improve the hydrocracking depth of hydrogenated LCO, thereby maximally producing the light aromatic hydrocarbon.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A process for producing light aromatic hydrocarbons and clean fuel oil, the process comprising:
(1) Introducing LCO raw oil and hydrogen into a first reaction zone for carrying out hydrofining reaction, and carrying out gas-liquid separation on a material flow obtained after the reaction to obtain a first liquid-phase material flow;
(2) Introducing the first liquid-phase material flow and hydrogen into a second reaction zone for deep hydrocracking reaction, and carrying out gas-liquid separation on the material flow obtained after the reaction to obtain a second liquid-phase material flow;
(3) Fractionating the second liquid phase material flow to obtain dry gas, liquefied gas, light aromatic hydrocarbon, recycled light diesel oil fraction and recycled heavy diesel oil fraction, wherein the fractionation point between the light aromatic hydrocarbon and the recycled light diesel oil fraction is 160-170 ℃, and the fractionation point between the recycled light diesel oil fraction and the recycled heavy diesel oil fraction is 310-330 ℃;
(4) Introducing the light aromatic hydrocarbon into an aromatic hydrocarbon separation system for separation to obtain BTX fraction; and
and recycling the recycled light diesel oil fraction to the second reaction zone to carry out the deep hydrocracking reaction, and recycling the recycled heavy diesel oil fraction to the first reaction zone to carry out the hydrofining reaction.
2. A process as claimed in claim 1, wherein the conditions are controlled such that the total aromatics content in the recycle light diesel fraction is above 60wt% and the single ring aromatics content is above 50wt%.
3. A process according to claim 1 or claim 2, wherein the conditions are controlled such that the total aromatics content in the recycle heavy diesel fraction is above 50wt% and the bicyclic aromatics content is above 20 wt%.
4. The process of any one of claims 1-3, wherein the conditions of the hydrofinishing reaction in the first reaction zone are controlled such that the double ring plus aromatics saturation in the first liquid phase stream is >80% and the total aromatics saturation is <20%.
5. The method according to any one of claims 1 to 4, wherein the API degree of the LCO raw oil is 12 to 25, the total aromatic hydrocarbon content is higher than 60wt%, and the aromatic hydrocarbon content over bicyclic rings is higher than 50wt%.
6. The process of any of claims 1-5, wherein the first reaction zone is packed with a hydrofinishing catalyst comprising a support and a group VIII non-noble metal element and/or a group VIB non-noble metal element supported on the support;
preferably, the group VIII non-noble metal elements are cobalt and/or nickel, and the group VIB non-noble metal elements are molybdenum and/or tungsten.
7. The process of claim 6 wherein the group VIII non-noble metal element is present in the hydrofinishing catalyst in an amount of from 1 to 10 wt.% and the group VIB non-noble metal element, calculated as oxides and based on the total catalyst weight.
8. The process of any one of claims 1 to 7, wherein the conditions of the first reaction zone comprise at least: the hydrogen partial pressure is 3-10 MPa, the reaction temperature is 300-400 ℃, and the liquid hour volume airspeed is 0.5-6 h when measured by the oil mixture I -1 The volume ratio of hydrogen to oil mixture I is 300-1000 Nm 3 /m 3 The oil mixture I is the sum of fresh materials and the recycled heavy diesel oil fraction;
preferably, the conditions of the first reaction zone include at least: the hydrogen partial pressure is 3.2-7.2 MPa, the reaction temperature is 300-380 ℃, and the liquid hourly space velocity is 1.0-3.0 h by the sum of liquid phase materials at the inlet of the first reaction zone -1 The volume ratio of the hydrogen to the oil mixture I is 500-1000 Nm 3 /m 3 。
9. The process as claimed in any one of claims 1 to 8, wherein the second reaction zone is packed with a hydrocracking catalyst, the hydrocracking catalyst comprises a carrier and an active component element supported on the carrier, the active component element is Mo, or the active component element is Mo and a non-noble metal element of group VIII; the support is a combination of zeolite and alumina.
10. The process according to claim 9, wherein in the hydrocracking catalyst, the zeolite in the carrier is a MoY type zeolite modified with Mo, and the content of Mo in the carrier is MoO, which is a metal element molybdenum serving as an active component in the hydrocracking catalyst, calculated as an oxide 3 The content is 20-80 wt%.
11. The process as claimed in claim 9 or 10, wherein in the hydrocracking catalyst, the zeolite is present in an amount of 20 to 90wt%, the alumina is present in an amount of 10 to 80wt%, the non-noble group VIII metal element is present in an amount of 1 to 15wt%, and the metal element molybdenum as an active component is present in an amount of 3 to 30wt%, calculated as an oxide and based on the total amount of the catalyst.
12. The process of any one of claims 1 to 11, wherein the conditions of the second reaction zone comprise at least: the hydrogen partial pressure is 1-6 MPa, the reaction temperature is 360-520 ℃, and the liquid time volume airspeed is 0.5-3.0 h when the oil mixture II is used for measuring liquid -1 The volume ratio of the hydrogen to the oil mixture II is 800-2000 Nm 3 /m 3 The oil mixture II is the sum of fresh materials and the recycled light diesel oil fraction;
preferably, the conditions of the second reaction zone include at least: the hydrogen partial pressure is 1.6-4.8 MPa, the reaction temperature is 380-520 ℃, and the liquid hourly space velocity measured by the oil mixture II is 0.5-2.5 h -1 The volume ratio of the hydrogen to the oil mixture II is 800-1600 Nm 3 /m 3 。
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| CN101987971A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for producing high-octane petrol by inferior diesel |
| CN102311795A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-octane gasoline components by diesel oil raw material |
| CN103121897A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing arene by mixture containing hydrocarbon with condensed rings |
| CN103773487A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method for catalytic cracking diesel |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101987971A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for producing high-octane petrol by inferior diesel |
| CN102311795A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-octane gasoline components by diesel oil raw material |
| CN103121897A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing arene by mixture containing hydrocarbon with condensed rings |
| CN103773487A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method for catalytic cracking diesel |
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