CN108102709A

CN108102709A - The processing and treating method of catalytic diesel oil

Info

Publication number: CN108102709A
Application number: CN201611045497.4A
Authority: CN
Inventors: 李本哲; 王仲义; 崔哲; 彭冲; 吴子明; 孙士可
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-11-24
Filing date: 2016-11-24
Publication date: 2018-06-01
Anticipated expiration: 2036-11-24
Also published as: CN108102709B

Abstract

The invention discloses a kind of catalytic cracking diesel oil processing and treating methods.Catalytic diesel oil raw material is cut into light component and heavy constituent；Light component carries out hydrofinishing and hydroconversion reactions, obtains gasoline and diesel component；Gained heavy constituent is separated, and obtains thrcylic aromatic hydrocarbon component and non-thrcylic aromatic hydrocarbon component；The non-thrcylic aromatic hydrocarbon of gained carries out hydrofinishing and hydro-conversion, and gained thrcylic aromatic hydrocarbon component carries out hydrofinishing and hydro-conversion, obtains gasoline component and diesel component；Gasoline products are obtained after the mixing of each several part gasoline, diesel product is obtained after the mixing of each several part diesel component.The present invention can be directed to the independent processing of making choice property of different type raw material by reasonably separating and process, so as to reasonably produce qualified gasoline and diesel product using poor quality catalytic cracking diesel.

Description

The processing and treating method of catalytic diesel oil

Technical field

The present invention relates to a kind of processing and treating method of catalytic diesel oil, specifically a kind of processing catalytic cracking diesel oil life The method for producing premium-type gasoline.

Background technology

Catalytic cracking is most important secondary processing process and the core of heavy oil lighting in current petroleum refining industry Technique.With Global Oil increasingly heaviness, the processing capacity of FCC apparatus is also continuously improved, and using various mink cell focuses as raw material, leads to It crosses catalytic cracking reaction and obtains major product high-knock rating gasoline, while generate substantial amounts of sulphur, nitrogen, arene content height, 16 Alkane value or Cetane lndex are low, and the catalytic diesel oil that stability is very poor.And the requirement of environmental regulation is also increasingly harsh, while bavin The index of oil product is also stepping up, and has strict requirements to sulfur content therein, arene content, Cetane lndex etc.. So while the yield of this part poor ignition quality fuel is reduced, it is also desirable to find a kind of suitable method and it is processed To meet the requirement that enterprise product dispatches from the factory.

Catalytic Hydrogenation Techniques, rationally using petroleum resources, improve product quality for improving the level of crude oil processing, improve light Matter oil yield and reduction atmosphere pollution all have great importance, the condition being especially deteriorated again in current this petroleum resources change Under, the importance of catalytic hydrogenation just more highlights, and by being suitably hydrogenated with, can improve the hydrogen-carbon ratio in fuel oil, Optimize product quality and improve discharge standard, become the indispensable component of petrochemical industry at present, it is main Process can be divided into hydrotreating and be hydrocracked.

It is very severe due to catalytic diesel oil property, so the means that can be currently handled are relatively simple, with regard to China For, catalytic diesel oil and hydrogen addition technology are predominantly combined processing by the means that can be relied on, such as by catalytic diesel oil and straight run bavin Oil mixing after carry out hydrofinishing, catalytic diesel oil is mixed with straight-run gas oil after be hydrocracked and occur in recent years general Catalytic diesel oil individually carries out the transformation technology of cracking production gasoline.

CN1955257A describes a kind of method of high-output qulified industrial chemicals, and poor quality mainly is catalyzed catalytic cracking bavin Oil mixes in proportion with hydrogenating materials, and then by controlling, reaction condition produces catalytic reforming raw material and quality steam cracks second processed Alkene raw material.Although catalytic cracking poor ignition quality fuel can be processed, add the processing approach of inferior raw material and be converted into quality product, But the ratio for mixing refining catalytic diesel oil is still subject to certain restrictions, accessible catalytic diesel oil amount very little, while in condition of high voltage The consumption of lower processing catalytic diesel oil hydrogen is very big.

CN103773455A is the invention discloses a kind of vegetable and animals oils, catalytic diesel oil Unionfining technological process, substantially Or catalytic diesel oil is handled by way of hydrofinishing, although catalytic diesel oil can be processed by suitable raw material proportioning, It is the catalytic diesel oil amount very little that refining can be mixed due to the limitation of diesel product index, can not thoroughly solves big catalysed refinery enterprise The process problem of a large amount of catalytic diesel oils.

CN104611029A discloses a kind of catalytic cracking diesel oil hydrogenating conversion process, and catalytic diesel oil is first after being mixed with hydrogen Hydrofining reaction is carried out into hydrofining reactor, hydrocracking reactor is then entered back into and carries out hydrocracking reaction. Although can process catalytic diesel oil component with effect by certain catalyst grade produces high-knock rating gasoline, chemical hydrogen consumption It is relatively high, it is larger to the hydrogen resources requirement of enterprise.

The content of the invention

In view of the problems of the existing technology, the technical problem to be solved in the present invention is to provide a kind of processing catalytic diesel oil is former The hydrocracking method of material.Carry out cutting separation after the catalytic diesel oil analysis that this method will be conventional, by tricyclic therein and Above aromatic hydrocarbons heavy constituent（Aromatic hydrocarbons simultaneously containing a small amount of monocyclic and bicyclic belt length side chain）And aromatic hydrocarbons light component separates, restructuring Divide by obtaining thrcylic aromatic hydrocarbon and non-thrcylic aromatic hydrocarbon after aromatics seperation device, by directly generating high-octane rating vapour after each autoreaction Oil after light component carries out either shallow conversion reaction, generates high-knock rating gasoline.While handling catalytic diesel oil raw material, Each component is individually processed, with strong points, can produce good gasoline products, while compared to other techniques, there is gasoline to receive The characteristics of rate is high, quality is good.

The present invention provides a kind of processing and treating methods of catalytic diesel oil, include the following steps：

a）Catalytic diesel oil raw material obtains light component and heavy constituent after cutting separates；

b）Step a）Gained light component enters the bed containing hydrofinishing and light aromatic hydrocarbons hydrogenation conversion catalyst as feedstock oil Middle carry out conversion reaction, obtained reaction effluent carry out the processes such as gas-liquid separation, fractionation, finally obtain conversion gasoline and conversion Diesel oil etc.；

c）Step a）The heavy constituent of gained enters aromatics seperation device, by thrcylic aromatic hydrocarbon component therein and non-thrcylic aromatic hydrocarbon component Separation；

d）Non- thrcylic aromatic hydrocarbon component enters as feedstock oil in the bed containing hydrofinishing and middle aromatic hydrogenation reforming catalyst Conversion reaction is carried out, obtained reaction effluent goes successively to step b）Light aromatic hydrocarbons hydrogenation conversion catalyst bed in carry out it is anti- It should；

e）Thrcylic aromatic hydrocarbon component as feedstock oil into the bed containing hydrofinishing and heavy aromatics hydrogenation conversion catalyst into Row conversion reaction, obtained reaction effluent carry out the processes such as gas-liquid separation, fractionation, finally obtain conversion gasoline and conversion bavin Oil etc.；

f）Step b）Middle gained conversion gasoline and step e）Described in conversion gasoline mixing after obtain gasoline products；Step e）Institute The conversion diesel oil stated directly with step b）The conversion diesel oil mixing returns step as diesel product or as feedstock circulation d）In mixed with non-thrcylic aromatic hydrocarbon component.

Step a）The initial boiling point of the catalytic diesel oil component is generally 160~240 DEG C, preferably 180~220 DEG C, evaporates eventually Generally 320~420 DEG C of point, preferably 350~390 DEG C, arene content is preferably generally 60~90 wt% in more than 50wt%, Middle thrcylic aromatic hydrocarbon is preferably generally more than 10wt% in more than 5wt%；The density of the diesel raw material is generally in 0.91gcm^-3With On, preferably 0.93gcm^-3More than.

The catalytic diesel oil raw material can be that any base of processing belongs to oily kind of obtained catalytic cracking production, such as can select The catalytic diesel oil obtained from processing middle-eastern crude can be specifically to process the catalytic diesel oil that Iran crude, Saudi Arabia's crude oil etc. obtain Component.

Step a）The cutting is separated into conventional gas-liquid separation process, and well known flash distillation point in the industry may be employed From or the separated mode of column plate, the purpose is to which catalytic diesel oil is divided into two parts of weight, according to the description in this method, Cut-point is generally 290~350 DEG C, preferably 300~340 DEG C.The light component is the liquid fraction less than cut-point, described Restructuring be divided into liquid fraction higher than cut-point.

Step b）With step c）Described in Hydrobon catalyst include carrier and the hydrogenation metal that is loaded.With catalysis On the basis of the weight of agent, metal component of group VIB in the periodic table of elements is generally included, as tungsten and/or molybdenum are calculated as 10% with oxide ~ 35%, it is preferably 15% ~ 30%；Group VIII metal such as nickel and/or cobalt are calculated as 1% ~ 7% with oxide, are preferably 1.5% ~ 6%.Carrier For inorganic refractory oxide, aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc. are selected generally from.It is wherein conventional hydrocracking Pretreatment catalyst can select existing various commercial catalysts, such as Fushun Petrochemical Research Institute（FRIPP）Development is opened Hair 3936,3996, the Hydrobon catalysts such as FF-16, FF-26, FF-36, UDS-6；This field can also be pressed as needed Common sense prepared.

Step b）With step c）Described in gas-liquid separation, fractional distillation process be content well-known to those having ordinary skill in the art. Gas-liquid separation is the separation process of hydro-upgrading process product, generally mainly contains high-low pressure separator, Xun Huan hydrogen system etc.； The process that fractional distillation process further refines for the liquid-phase product of gas-liquid separation, generally mainly contains stripper, fractionating column, side line tower Deng.

Step b）The light aromatic hydrocarbons hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is according to we The catalyst that method is especially prepared.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and carrying alumina Body.General hydrogenation conversion catalyst is by the hydrogenation active metal components such as Wo, Mo, Co, Ni, molecular sieve component and alumina support Deng composition.The hydrogenation conversion catalyst for being exclusively used in the present invention is to include WO by weight₃(or MoO₃) 5~25wt%, NiO (or CoO) 15~35wt% of 3~8wt%, 50~60wt% of molecular sieve and aluminium oxide, catalyst maximum are characterized in that molecular sieve Preparation process can obtain cell parameter 2.438~2.442nm by modification, infrared 0.6~0.8mmol/g of total acid, in strong acid The heart is 80%（mmol·g^-1/mmol·g^-1）Above modified molecular screen can be Y type molecular sieve.Its it is main effect be The reaction of the making choice property of double ring arene in raw material can be directed to, and it is poor to the selectivity of other aromatic hydrocarbons.This hydro-conversion Catalyst is the exclusive technology catalyst that can be prepared as described above according to the common sense of this field.

Step c）The middle aromatic hydrogenation reforming catalyst is the hydrogenation conversion catalyst containing molecular sieve, is according to we The catalyst that method is especially prepared.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and carrying alumina Body.General hydrogenation conversion catalyst is by the hydrogenation active metal components such as Wo, Mo, Co, Ni, molecular sieve component and alumina support Deng composition, on the basis of the weight of catalyst, the content of hydrogenation component is 2%~20%.The hydro-conversion for being exclusively used in the present invention is urged Agent is to include WO by weight₃(or MoO₃) 7~27wt%, NiO (or CoO) 4~9wt%, 30~49 wt% of molecular sieve and oxygen Change 30~50 wt% of aluminium, catalyst maximum is characterized in that the preparation process of molecular sieve, and can obtain structure cell by modification joins Number 2.434~2.439nm, infrared 0.4~0.6mmol/g of total acid, modified molecular screen of the strong acid center more than 60% can be with It is Y type molecular sieve.Its main effect is the reaction for the making choice property of aromatic hydrocarbons that can be directed in raw material.This hydro-conversion is catalyzed Agent is the exclusive technology catalyst that can be prepared as described above according to the common sense of this field.

Step c）The heavy aromatics hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is according to we The catalyst that method is especially prepared.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and carrying alumina Body.General hydrogenation conversion catalyst is by the hydrogenation active metal components such as Wo, Mo, Co, Ni, molecular sieve component and alumina support Deng composition.The hydrogenation conversion catalyst for being exclusively used in the present invention is to include WO by weight₃(or MoO₃) 9~29 wt%, NiO (or CoO) 35~60 wt% of 5~10 wt%, 15~45 wt% of Y type molecular sieve and aluminium oxide.

In the heavy aromatics hydrogenation conversion catalyst, Y type molecular sieve is small crystal grain Y-shaped molecular sieve.Small-grain Y-type molecule The grain size of sieve be 400~600nm, infrared 0.3~0.7mmol/g of total acid, middle strong acid ratio be more than 85%, cell parameter 2.435~ 2.440nm；0.5~0.7 cm of pore volume³/ g, wherein secondary pore pore volume account for the ratio of total pore volume more than 50%.The Y type molecular sieve With acid centre that is more accessible and exposing, be conducive to the diffusion of hydrocarbon molecule, cyclic hydrocarbon particularly tricyclic can be improved The preferential conversion ability of aromatic hydrocarbons orients and the aromatic ring among thrcylic aromatic hydrocarbon is carried out saturation and is broken, the maximum amount of production Gaoxin The gasoline component of alkane value.Hydrogenation conversion catalyst containing the small crystal grain Y-shaped molecular sieve, main function are can be directed to raw material In making choice property of thrcylic aromatic hydrocarbon reaction, and the selectivity of two rings and mononuclear aromatics to non-tricyclic is poor.The Y type molecules Sieve is with conventional Y type molecular sieve there are certain difference, and conventional modified molecular screen grain size is generally 800~1200nm, and pore volume is 0.35~0.50 cm³The secondary pore pore volume of/g, 2-8nm account for the ratio general 30~50% of total pore volume, and the ratio of middle strong acid is 50 ~70%.The hydrogenation conversion catalyst can prepare satisfactory catalysis according to the common sense of this field as described above Agent.

In the present invention, technical term " middle strong acid ", " strong acid " are the conventional conception of field of catalyst preparation.It is used NH₃- TPD is analyzed, and 150-250 DEG C of desorption is defined as weak acid, and 250-400 DEG C of desorption is defined as middle strong acid, 400-500 DEG C desorption be defined as strong acid.

Step c）In, the heavy aromatics hydrogenation conversion catalyst preferably matches somebody with somebody filling scheme using catalyst grade.Hydrogenation turns Changing catalyst includes at least two catalyst beds, according to the engagement sequence with reaction mass, Y types in the catalyst of upstream bed The cell parameter of molecular sieve is generally 2.435~2.438nm, infrared 0.3~0.5 mmol/g of total acid；Catalyst in down stream The cell parameter of middle Y type molecular sieve is generally 2.438~2.440nm, infrared 0.5~0.7 mmol/g of total acid.With upstream bed In catalyst compare, in down stream in catalyst secondary pore account for total pore volume ratio it is 2~15 percentage points low, and Y types point The content of son sieve is higher by 5~15 percentage points.Ability may be employed in the modification process of the Y type molecular sieve wherein met the requirements The routine techniques in domain carries out, and the method as described in being referred to CN104588073A handles Y type molecular sieve.

According to the difference of the cell parameter of Y type molecular sieve in hydrogenation conversion catalyst and infrared total acid content, can will be catalyzed Agent carries out grading according to the difference of activity.So can along the flow direction of reaction mass, by the Hydrogenation of catalyst and Cracking performance carries out more reasonably transition, and tricyclic complexity aromatic hydrocarbons therein is particularly to reactant, is more targetedly added In-between aromatic ring is carried out saturation cracking, directs it to further maximum and be converted into high-octane rating by hydrogen and cracking process Gasoline component so that the content of polycyclic aromatic hydrocarbon can be reduced significantly in product, and the selectivity of hydro-conversion further improves.

In the present invention, heavy aromatics hydrogenation conversion catalyst is preferably using grading loading technology, and the catalyst of upstream is first It is in contact and is reacted with the catalytic diesel oil heavy constituent containing a large amount of thrcylic aromatic hydrocarbons and appropriate two cycloaromatics, due to thrcylic aromatic hydrocarbon Polarity is stronger, and adsorption capacity is strong, and it is little to crack difficulty, therefore the catalyst of upstream has suitable molecular sieve content and secondary Boring ratio example, it is acid moderate, can thrcylic aromatic hydrocarbon be effectively converted into the high octane gasoline component containing mononuclear aromatics； And the molecular sieve content and secondary pore ratio in the catalyst in downstream are slightly higher, and it is acid stronger, it can be further by two cycloaromatics It is converted into the high octane gasoline component containing mononuclear aromatics.Therefore above-mentioned catalyst grading distribution scheme is used, it can be according to original The complexity that different component reacts in material, is converted into target product by wherein most aromatic hydrocarbons, further improves choosing Selecting property.

Step c）The aromatics seperation device is the technical process of physical extraction, and principle is for not jljl using solvent The difference of matter solubility is extracted, then separated process again.Extraction solvent used can be sulfolane, furfural, NMP or Person's phenol etc..The process can utilize industrial widely used Aromatics Extractive Project or furfural extraction unit to be achieved, preferably furfural essence Unit processed.Furfural treatment unit extracting part operating condition be：0.01~0.8MPa of tower pressure interior force, 50~150 DEG C of temperature are molten Agent mass ratio 1~8 cycles mass ratio 0~0.6；Preferably operating condition is：0.02~0.1MPa of tower pressure interior force, temperature 60~ 110 DEG C, solvent quality cycles mass ratio 0.2~0.5 than 2~7.Step c）The aromatics seperation device or absorption Separated technical process, using the difference of different type bulk of molecule, selecting or prepare suitable molecular sieve has it The adsorption process of effect, then using desorption separation and etc., so as to which ideal composition and undesirable components be separated.

Step b）With step c）The reaction condition of the conversion reaction is：Volume space velocity is 0.5~4.0h^-1, preferably 0.8 ~2.5h^-1, hydrogen partial pressure is 4~13MPa, and preferably 6~10MPa, entrance hydrogen to oil volume ratio is 300:1~800:1, preferably 400:1 ~700:1, reaction temperature is 360~430 DEG C, preferably 380~420 DEG C.According to the difference that cut point and aromatic hydrocarbons are distributed, conversion Reaction can control certain conversion level according to the content of thrcylic aromatic hydrocarbon in raw material.General control of the present invention is more than step a）In cut The mass transitions rate of cutpoint is not higher than 80%, is preferably no greater than 60%.

Step f）The gasoline products and diesel product are that can enter the high-quality component that reconciliation pond carries out product oil reconciliation.

Compared with prior art, catalytic diesel oil Combined machining process of the invention has the following advantages：

1st, the higher catalytic diesel oil of arene content is processed, it, will after the separated cutting process of weight and aromatics seperation device Different types of aromatic hydrocarbons mixture is independently processed, can will be most suitable as the thrcylic aromatic hydrocarbon of hydro-conversion raw material, two rings And monocyclic heavy constituent, two rings and monocyclic light component carry out conversion reaction, coordinate in preparation, grading technology and the technique of catalyst State modulator, can the high-octane gasoline component of high yield to greatest extent.The method of the present invention is by reasonably separating and adding Work process targetedly can individually be processed different types of raw material, and complicated petroleum refining process is carried out Simplify, in processing catalytic diesel oil inferior, while considering difficulty of processing, the processing suitability and specific aim of each component are mentioned Maximum has very big advantage.It according to the difference of catalyst preparation process, is reacted for specific raw material, wherein gently Aromatic hydrogenation reforming catalyst can specifically be reacted for two ring light aromatic hydrocarbons, and the middle aromatic hydrogenation conversion that activity is slightly lower Catalyst can specifically be reacted for two cycloaromatics, and the lower heavy aromatics hydrogenation conversion catalyst of activity can be directed to three Cycloaromatics is specifically reacted, they are played jointly is converted into high-knock rating gasoline group to greatest extent by the aromatic hydrocarbons in raw material The purpose divided.

2nd, the method for the present invention will separate in technological process and different types of hydro-conversion carries out depth coupling, have On the basis of specific aim handles raw material and improves product quality, preferable comprehensive process effect is obtained.Although in the course of the description Each unit independence is stronger, but different units organically can be combined and shared in practical application, has and saves equipment, behaviour Make the advantages such as expense is low, simultaneously because the improvement for the heat-exchange system that assemblage zone comes, decrease the energy of device to a certain extent It consumes, reduce investment, be with a wide range of applications.

3rd, according to the method for the present invention, had developed again on the basis of original catalytic diesel oil hydrogenation conversion catalyst new The stronger sequence of transformations catalyst of specific aim and a gross appearance of technological progress, can provide more catalyst for enterprise Choice direction brings more intuitive economic benefit.The specific surface of small crystal grain molecular sieve used in invention hydrogenation conversion catalyst is big, Especially external surface area substantially increases, and the ratio between surface atom number and volume atomicity increased dramatically, and duct is shortened, and exposed aperture increases It is more, so that small crystal grain molecular sieve has higher reactivity and surface energy, show apparent bulk effect and surface effect It should.Specifically, there are following several respects：Since external surface area increases, more activated centres are exposed, are effectively eliminated Diffusion effect makes catalyst efficiency be not fully exerted, and the reactivity worth so as to make macromolecular is improved；Due to surface energy Increase, increase the adsorbance of molecular sieve, adsorption rate quickening, so that effective adsorption capacity of molecular sieve is improved；It is small The duct of crystal grain molecular sieve is short, and intracrystalline diffusion resistance is small, and huge external surface area makes small crystal grain molecular sieve have more in addition Exposed to outside, this not only improves the quick disengaging of reactant or product molecule, and can prevent or reduce because product is in hole in aperture Accumulation in road and form knot carbon, improve the turnover rate of reaction and the service life of molecular sieve；With uniform backbone moiety footpath To distribution, so as to improve activity and selectivity；It is more advantageous to the realization of Zeolite synthesis post-modification technology；It is carried on a shoulder pole for molecular sieve For the catalyst for carrying metal, be conducive to improve the payload amount of metal component using small crystal grain molecular sieve and improve metal group The dispersion performance divided.It additionally can further increase the secondary pore ratio in molecular sieve by subsequent modification, freely Logical molecular sieve pore passage structure is more conducive to macromolecules adsorption reaction and desorption, enhances the orientation hydrogenation of macromolecular heavy aromatics significantly High octane gasoline component is more in the product that conversion capability, intermediate ring filling and cracking can make.

Description of the drawings

Fig. 1 is the flow diagram of present invention process method.

Specific embodiment

The combined technical method of the present invention is described in detail below in conjunction with the accompanying drawings.Technological process is only listed in Fig. 1 It is main to illustrate, it is omitted some necessary equipment and container in schematic diagram.

As shown in Figure 1, present invention processing catalytic diesel oil group technology flow is as follows：Catalytic diesel oil raw material 1 enters separator 2 Afterwards, top obtains light component 3, and lower part obtains heavy constituent 4, and for heavy constituent 4 into aromatics seperation device 5, top obtains non-tricyclic group Divide 6, bottom is obtained into heavy aromatics hydroconversion reactions area after tricyclic component 7 is mixed with hydrogen 8, with catalyst 9,10（For grade Heavy aromatics the hydrogenation conversion catalyst A and B matched somebody with somebody）After haptoreaction, effluent 11 is discharged into separation, fractionating system 12, top Gasoline 13 is converted, bottom obtains conversion diesel oil 14；After light component 3 is mixed with hydrogen 15, into light aromatic hydrocarbons hydroconversion reactions area, After catalyst 16,17 haptoreactions, effluent 18 is into separation, fractionating system 19, and top discharge conversion gasoline 20, bottom obtains To conversion diesel oil 21；Aromatic hydrogenation conversion reaction zone during non-tricyclic component 6 enters after being mixed with hydrogen 22, with catalyst 23,24 After haptoreaction, effluent enters light aromatic hydrocarbons hydroconversion reactions area according still further to logistics direction；Convert gasoline 13 and conversion vapour Oil 20 is mixed to get specification gasoline 26；Conversion diesel oil 14 can be recycled back to middle aromatic hydrogenation conversion reaction zone and non-tricyclic component 6 Mixing can also be mixed to get qualified diesel oil 25 with conversion diesel oil 21.Wherein catalyst 9,16 and 23 is Hydrobon catalyst.

The combined technical method of the present invention is further described followed by specific embodiment.

Aromatics seperation device involved in following embodiment and/or comparative example, operating condition are as follows：Furfural is selected to take out the most Extraction solvent, tower 0.04~0.13MPa of voltage-controlled system, temperature are 50~90 DEG C, and solvent is than 3, recycle ratio 0.3, can will be different types of Aromatic hydrocarbons is compared preferable separation.

Embodiment 1

Using group technology flow shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, weight component is selected to cut Cutpoint is 300 DEG C, and purpose product is premium-type gasoline and diesel oil.The catalyst used in embodiment is commercial catalyst FF-36 Hydrotreating catalyst and the special hydrogenation conversion catalyst of this technology（Light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics A.Catalyst forms In, surplus is aluminium oxide）.

Embodiment 2

Using group technology flow shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, weight component is selected to cut Cutpoint is 300 DEG C, and purpose product is premium-type gasoline and diesel oil.The catalyst used in embodiment is commercial catalyst FF-36 Hydrotreating catalyst and the special hydrogenation conversion catalyst of this technology（Light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics A and B）.

Embodiment 3

Using group technology flow shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, weight component is selected to cut Cutpoint is 310 DEG C, and purpose product is premium-type gasoline and diesel oil.The catalyst used in embodiment is commercial catalyst FF-36 Hydrotreating catalyst and the special hydrogenation conversion catalyst of this technology.（Light aromatic hydrocarbons, middle aromatic hydrocarbons, heavy aromatics A and B）

Comparative example 1

Using technological process shown in FIG. 1, catalytic diesel oil is selected to carry out hydrogenation production as raw material, select the cutting of weight component Point is 300 DEG C, and purpose product is premium-type gasoline and diesel oil.The catalyst used in comparative example adds for commercial catalyst FF-36 Hydrogen handles the hydrogenation conversion catalyst C of catalyst, 3963 catalyst for hydro-upgrading and routine.

Comparative example 2

Comparative example 2 is Conventional catalytic diesel oil hydrogenation conversion process process, and catalytic diesel oil is selected to carry out hydrogenation production, mesh as raw material Product be premium-type gasoline and ordinary diesel oil.The catalyst used in comparative example is urged for commercial catalyst FF-36 hydrotreatings The hydrogenation conversion catalyst C of agent and routine.

Special and conventional hydrogenation conversion catalyst property is shown in Table 1, and the property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3 And continued 3, major product property are shown in Table 4.

The main physico-chemical property of the special catalyst of 1 this technology of table.

Type	Light aromatic hydrocarbons	Middle aromatic hydrocarbons	Heavy aromatics A	Heavy aromatics B	Conventional agent C
						Chemical composition	Mo-Ni	Mo-Ni	Mo-Ni	Mo-Ni	Mo-Ni
Metal oxide content, wt%	17.8	19.3	21.5	20.7	17.1
						Physical property
Face shaping	Cylindrical bars	Cylindrical bars	Cylindrical bars	Cylindrical bars	Cylindrical bars
						Crushing strength, N/cm	≥150	≥150	≥150	≥150	≥150
Particle diameter, mm	1.1~1.3	1.1~1.3	1.1~1.3	1.1~1.3	1.1~1.3
						Y type molecular sieve, wt%	55	49	35	45	50
Y type molecular sieve property
						Grain size, nm	750	800	550	450	990
Cell parameter, nm	2.442	2.439	2.435	2.438	2.438
						Secondary pore accounts for total pore volume ratio, v%	44.0	55.0	66.0	61.0	50.1
Infrared total acid, mmol/g	0.65	0.56	0.35	0.55	0.60
						（In）Strong acid ratio, %	81	62	85	87	58

2 feedstock oil property list of table.

3 reaction condition of table.

3 reaction condition of continued.

It can be seen from table 2 and 3 embodiment of table and comparative example for a large amount of catalytic diesel oil production gasoline are processed, this Technology has very big advantage in hydrogen consumption.

4 product main character of table.

	Embodiment 1	Embodiment 2	Embodiment 3	Comparative example 1	Comparative example 2
						Naphtha
Research octane number (RON)	90.9	91.7	91.9	90.4	92.7
						Sulphur/μ gg^-1	4.1	2.6	3.5	5.4	2.8
Yield/benchmark	Benchmark+2.2%	Benchmark+3.2%	Benchmark+3.0%	Benchmark+1.8%	Benchmark
						Diesel oil
Cetane number	36.5	38.5	38.5	35.7	35.0
						Sulphur/μ gg^-1	9.0	6.5	5.6	4.0	9.6

Using present invention processing catalytic diesel oil raw material it can be seen from examples detailed above, compared with comparative example, in identical operating mode Lower processing catalytic diesel oil, the naphtha produced and diesel product property and yield are respectively provided with certain advantage.

It can be seen that from above example and comparative example and processed respectively after this method cuts catalytic diesel oil raw material, The maximum amount of diesel component inferior can be handled, can be flexible to adjust diesel and gasoline ratio example according to the actual conditions of enterprise, according to city The changes in demand of field is produced.

Different types of hydroconversion process is combined in terms of technological process and catalyst, it is former in targeted processing On the basis of expecting and improving product quality, preferable comprehensive process effect is obtained.Although each unit independence in the course of the description It is relatively strong, but different units can be combined in practical application and organically combine and share, with saving, equipment, operating cost are low The advantages that, simultaneously because the improvement for the heat-exchange system that assemblage zone comes, decreases the energy consumption of device, reduces to a certain extent Investment, is with a wide range of applications.

Claims

1. a kind of processing and treating method of catalytic diesel oil, includes the following steps：

a）Catalytic diesel oil raw material obtains light component and heavy constituent after cutting separates；The segmentation of the light component and heavy constituent Temperature is 290~350 DEG C；

b）Step a）Gained light component enters the bed containing hydrofinishing and light aromatic hydrocarbons hydrogenation conversion catalyst as feedstock oil Middle carry out conversion reaction, obtained reaction effluent carry out gas-liquid separation, fractional distillation process, obtain conversion gasoline and convert diesel oil；

d）Step c）The non-thrcylic aromatic hydrocarbon component of gained enters as feedstock oil and contains hydrofinishing and middle aromatic hydrogenation conversion catalyst Conversion reaction is carried out in the bed of agent, obtained reaction effluent goes successively to step b）Light aromatic hydrocarbons hydrogenation conversion catalyst bed It is reacted in layer；

e）Step c）Gained thrcylic aromatic hydrocarbon component enters as feedstock oil and contains hydrofinishing and heavy aromatics hydrogenation conversion catalyst Bed in carry out conversion reaction, obtained reaction effluent carries out gas-liquid separation, fractionation operation, obtains conversion gasoline and conversion Diesel oil；

f）Step b）Middle gained conversion gasoline and step e）Gasoline products are obtained after middle gained conversion gasoline mixing；Step e）Gained Convert diesel oil directly with step b）The conversion diesel oil mixing returns step d as diesel product or as feedstock circulation）In It is mixed with non-thrcylic aromatic hydrocarbon component.

2. according to the method for claim 1, which is characterized in that the initial boiling point of the catalytic diesel oil raw material is 160~240 DEG C, the end point of distillation is 320~420 DEG C, and arene content is in more than 50wt%, and the density of diesel raw material is in 0.91gcm^-3More than.

3. according to the method for claim 2, which is characterized in that the initial boiling point of the catalytic diesel oil raw material is 180~220 DEG C, the end point of distillation is 350~390 DEG C, and arene content is 60~90 wt%；The density of diesel raw material is 0.93gcm^-3More than.

4. according to the method for claim 1, which is characterized in that the segmentation temperature of light component and the heavy constituent is 300 ~340 DEG C.

5. according to the method for claim 1, which is characterized in that the light aromatic hydrocarbons hydrogenation conversion catalyst wraps by weight Include WO₃Or MoO₃5~25wt%, NiO or 15~35wt% of 3~8wt% of CoO, 50~60wt% of Y type molecular sieve and aluminium oxide.

6. according to the method for claim 5, which is characterized in that the cell parameter of the Y type molecular sieve for 2.438~ 2.442nm, infrared 0.6~0.8mmol/g of total acid, strong acid center are more than 80%.

7. according to the method for claim 1, which is characterized in that the middle aromatic hydrogenation reforming catalyst wraps by weight Include WO₃Or MoO₃7~27wt%, NiO or 30~50 wt% of 4~9wt% of CoO, 30~49 wt% of Y type molecular sieve and aluminium oxide.

8. according to the method for claim 7, which is characterized in that the cell parameter of the Y type molecular sieve for 2.434~ 2.439nm, infrared 0.4~0.6mmol/g of total acid, strong acid center is more than 60%.

9. according to the method for claim 1, which is characterized in that the heavy aromatics hydrogenation conversion catalyst wraps by weight Include WO₃Or MoO₃9~19 5~10 wt% of wt%, NiO or CoO, 5~30 wt% of 15~45 wt% of Y type molecular sieve and aluminium oxide.

10. according to the method for claim 9, which is characterized in that the grain size of the Y type molecular sieve is 400~600nm, Infrared 0.3~0.7mmol/g of total acid, middle strong acid ratio are more than 85%, 2.435~2.440nm of cell parameter；Pore volume 0.5~0.7 cm³/ g, wherein secondary pore pore volume account for the ratio of total pore volume more than 50%.

11. according to the method for claim 10, which is characterized in that the heavy aromatics hydrogenation conversion catalyst is included at least Two catalyst beds according to the engagement sequence with reaction mass, compared with the catalyst in the bed of upstream, are urged in down stream In agent secondary pore account for total pore volume ratio it is 2~15 percentage points low, and the content of Y type molecular sieve is higher by 5~15 percentage points.

12. according to the method for claim 11, which is characterized in that the structure cell of Y type molecular sieve in the catalyst of upstream bed Parameter is 2.435~2.438nm, infrared 0.3~0.5 mmol/g of total acid；In down stream in catalyst Y type molecular sieve crystalline substance Born of the same parents' parameter is 2.438~2.440nm, infrared 0.5~0.7 mmol/g of total acid.

13. according to the method for claim 1, which is characterized in that step c）The aromatics seperation device is using furfural essence Unit processed, the operating condition of furfural treatment unit extracting part are：0.01~0.8MPa of tower pressure interior force, 50~150 DEG C of temperature are molten Agent mass ratio 1~8 cycles mass ratio 0~0.6.

14. according to the method for claim 13, which is characterized in that the operating condition is：Tower pressure interior force 0.02~ 0.1MPa, 60~110 DEG C of temperature, solvent quality cycle mass ratio 0.2~0.5 than 2~7.

15. according to the method for claim 1, which is characterized in that step b）, step d and step e）Described in conversion reaction Reaction condition be：Volume space velocity is 0.5~4.0h^-1, hydrogen partial pressure is 4~13MPa, and entrance hydrogen to oil volume ratio is 300:1~ 800:1, reaction temperature is 360~430 DEG C.

16. according to the method for claim 15, which is characterized in that the reaction condition of the conversion reaction is：Volume space velocity For 0.8~2.5h^-1, hydrogen partial pressure is 6~10MPa, and entrance hydrogen to oil volume ratio is 400:1~700:1, reaction temperature is 380~420 ℃。

17. according to the method for claim 1, which is characterized in that step e）Middle control is more than step a）The matter of middle cut point It measures conversion ratio and is not higher than 80%.