CN109988639A

CN109988639A - Method of the catalyst grade with technology production gasoline and low solidifying oil

Info

Publication number: CN109988639A
Application number: CN201711468989.9A
Authority: CN
Inventors: 王仲义; 崔哲; 彭冲; 曹正凯; 孙士可; 吴子明
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2017-12-29
Filing date: 2017-12-29
Publication date: 2019-07-09
Anticipated expiration: 2037-12-29
Also published as: CN109988639B

Abstract

A kind of method with technology production gasoline and low solidifying oil that the invention discloses catalyst grades.This method comprises: passing through the reaction zone progressive hydrofining reaction containing Hydrobon catalyst bed after a) heavy oil feed is mixed with hydrogen；B) reaction effluent of step a) carries out hydroconversion reactions by the reaction zone containing gradation wax oil hydrogenation reforming catalyst bed, and reaction effluent enters flash tank by separation, obtains gas phase liquid phase；C) the resulting gas phase of step b) separated, stripped, be fractionated after obtain conversion gasoline；D) the resulting liquid phase of step b) carries out gas-liquid separation, fractional distillation process, obtains heavy naphtha, low-coagulation diesel oil and unconverted oil by the reaction zone containing Hydrodewaxing catalyst bed, gained reaction effluent.Method of the invention can produce premium blend component and low condensation point oil product, with good economic efficiency.

Description

Method of the catalyst grade with technology production gasoline and low solidifying oil

Technical field

The present invention relates to a kind of processing methods of wax oil component, specifically process wax oil with technology by catalyst grade Raw material produces high-quality gasoline, the production method of the liquid-phase products such as low solidifying oil of the high-quality high-quality of by-product.

Background technique

Gasoline is one of maximum oils of dosage, is a kind of important fuel of engine, can be by petroleum refining Different units obtain, in crude oil processing, distillation, catalytic cracking, thermal cracking, be hydrocracked, the units such as catalytic reforming all Output gasoline component, but octane number is different, it, cannot be separately as engine fuel if octane number of direct distillation gasoline is low；In addition, impurity Sulfur content is also different, therefore the high gasoline component of sulfur content also needs to be subject to desulfuration purification, finally, above-mentioned gasoline component is adjusted With, need when necessary be added antiknock component, finally obtain gasoline products that meet national standards.

The main path of the gasoline of China's production at present is catalytic cracking and catalytic reforming.Catalytic cracking is current petroleum refining Most important secondary processing process and the core process of heavy oil lighting in industry, with Global Oil increasingly heaviness, The processing capacity of FCC apparatus is also continuously improved, and using various mink cell focuses as raw material, obtains major product just by catalytic cracking reaction It is high-knock rating gasoline, but due to the raising of current gasoline discharge standard, the preceding essence of the production requirement raw material of catalytically cracked gasoline The rear purification of system and product；Catalytic reforming is to carry out being rearranged into new molecule to the hydrocarbon molecules structure in gasoline fraction The process of structure is the important means for improving quality of gasoline and producing petrochemical materials, is that current production gasoline is essential Technique, but due to its reaction process and the characteristic requirements of catalyst, source and cleanliness for raw material have very high Requirement.

Hydrocracking technology has that adaptability to raw material is strong, products scheme is flexible, liquid product yield is high, good product quality etc. Plurality of advantages is constantly subjected to the favor of countries in the world oil refining enterprise for many years.One of main technique as heavy oil deep processing Gasoline component can also be produced indirectly by being hydrocracked, due to the characteristic of its technique, the heavy naphtha impurity content of output it is extremely low but Octane number is not high, exactly the opposite with catalytic gasoline, this part adds the charging for splitting heavy naphtha as catalytic reforming units, is divided Minor structure can produce high-knock rating gasoline after resetting, in addition, industrially also occurring at present directly raw using catalytic cracking diesel oil The hydrogenating conversion process of high-knock rating gasoline is produced, hydrocracking reaction should be attributed in reacting quintessence, but on the whole, still Do not occur handling heavy oil ingredient (such as decompressed wax oil, catalytic slurry) and directly producing high-knock rating gasoline or blend component Method.In addition, hydro dewaxing technology itself passes through the adjustment of catalyst and technology, the low solidifying oil of high-quality can be produced Product, diesel component can be used as low-coagulation diesel oil product export, especially in northern high latitude area or extremely frigid zones, market effect It is beneficial significant；Tail oil component can also be used as Lube basic oil material feedstocks, and lubricating oil itself is needed due to production method and market The particularity asked is not limited in principle by macroeconomy price regulation, be major oil refining enterprise's extra earning synergy quality product it One, also receive the favor and attention of enterprise.Hydro dewaxing technical products increased quality limited extent, but condensation point the biggest drop, Therefore having certain limitation to the raw material processed, application also has certain specific aim.

CN104611029A discloses a kind of catalytic cracking diesel oil hydrogenating conversion process, and catalytic diesel oil is first after mixing with hydrogen Hydrofining reaction is carried out into hydrofining reactor, hydrocracking reactor is then entered back into and carries out hydrocracking reaction. Although producing high-knock rating gasoline by hydroconversion process, be substantially still using catalytic cracking diesel oil be raw material, and The raw materials for production range of premium is not expanded, there is certain limitation.

CN101724454A describes a kind of method for hydrogen cracking for producing high-knock rating gasoline, and feedstock oil is mixed with hydrogen Enter reactor afterwards and successively carry out hydrofinishing and hydrocracking reaction, although raw material more inferior can be processed, urge by having The features such as agent operation cycle is long and hydrocracked product is high-quality.But the raw material used is still diesel component, and weight is not used Matter oil directly produces high-knock rating gasoline.

CN103184073A describes a kind of method for hydrogen cracking for producing high-knock rating gasoline blend component, feedstock oil into Row controlled hydrofinishing and hydroconversion reactions, although it is high-octane rating that purpose product, which may be implemented, by technologic control Gasoline or blend component, but the range of choice of raw material is still relatively simple, can not be produced using heavy oil product, is catalyzed simultaneously It is not also improved effectively for technique in agent.

Summary of the invention

In view of the problems of the existing technology, it is raw that the technical problem to be solved in the present invention is to provide a kind of processing heavy charges High-knock rating gasoline is produced, and produces the hydrocracking method of the low solidifying oil of high-quality.This method carries out conventional heavy charge Hydroconversion reactions are carried out again after restricted plus hydrogen saturation, in the condition that certain process conditions limit and special catalyst grade is matched Lower production high-quality gasoline or blend component, while reaction product is separated, the liquid phase component of non-gasoline is dropped Solidifying reaction can produce low solidifying oil product, as fuel oil or lube base oil etc., selectively add realizing to heavy end On the basis of work, purpose product is produced to greatest extent.

A kind of method with technology production gasoline and low solidifying oil that the present invention provides catalyst grades, includes the following steps:

A) under Hydrofinishing conditions, heavy oil feed passes through reacting containing Hydrobon catalyst bed after mixing with hydrogen Area carries out restricted hydrofining reaction；

B) the resulting reaction effluent of step a) is under the conditions of hydroconversion process, by containing gradation wax oil hydrogenation conversion catalyst The reaction zone of agent bed carries out restricted hydroconversion reactions, and reaction effluent enters flash tank by separation, included The gas phase and boiling range of gasoline component are greater than the liquid phase of gasoline fraction；

C) the resulting gas phase of step b) obtains conversion gasoline after carrying out subsequent Hydrogen Separation, stripping, fractionation cutting；

D) the resulting liquid phase of step b) passes through the reaction zone containing Hydrodewaxing catalyst bed under hydro dewaxing process conditions Carry out hydro dewaxing reaction, gained reaction effluent carry out gas-liquid separation, fractional distillation process, obtain heavy naphtha, low-coagulation diesel oil and Unconverted oil.

The end point of distillation of heavy oil feed described in step a) is generally 450~580 DEG C, preferably 480~570 DEG C, density one As in 0.91g/cm³Hereinafter, it is preferred that 0.90g/cm³Hereinafter, total aromatic hydrocarbons is in 35wt% hereinafter, it is preferred that 30wt% is hereinafter, nitrogen contains in raw material Amount is in 600mgg^-1More than, preferably 800mgg^-1More than.One generally in decompressed wax oil, deasphalted oil or wax tailings Kind is perhaps several can be selected from the said components that processing Daqing crude oil or Changqing Crude Oil obtain, other contaminant characteristics of raw material It should be the general knowledge of this field, it is necessary to be to meet the requirement that can be used as hydrocracking unit charging.Due to hydro dewaxing mistake The reaction characteristics of journey, therefore the optimal raw material of the present invention should be above-mentioned limitation raw material.

Hydrofining technology condition described in step a) are as follows: 6.0~13.0 MPa of reaction pressure, hydrogen to oil volume ratio 200: 1 ~3000: 1, volume space velocity is 0.1~5.0 h^-1, 260 DEG C~435 DEG C of reaction temperature；Preferred operating condition is reaction pressure 7.0~12.0 MPa, hydrogen to oil volume ratio 300: 1~900: 1,1.0~3.0 h of volume space velocity^-1, reaction temperature 300 DEG C~430 ℃。

Restricted hydrofining reaction described in step a), which refers to, will control certain plus hydrogen saturation depth, avoid mink cell focus Aromatic component supersaturation in raw material is to influence the octane number of gasoline fraction product, according to aromatic hydrocarbons in raw material and nitrogen content Difference, generally require control refined oil (i.e. the resulting reaction effluent of step a)) nitrogen content be 50 ~ 250mgg^-1, excellent Select 100 ~ 200mgg^-1, the aromatic hydrocarbons in raw material can be retained to greatest extent while reducing refined oil nitrogen content in this way Component.What needs to be explained here is that during hydrofining reaction, by controlling above-mentioned refined oil nitrogen content, reaction stream The constituent content of tricyclic or more is less in the aromatic component in object out, and general total amount is in 1 ~ 20wt%, preferably 2 ~ 15wt%.

Hydroconversion process condition described in step b) are as follows: 6.0~13.0 MPa of reaction pressure, hydrogen to oil volume ratio 300: 1 ~2000: 1, volume space velocity is 0.1~5.0 h^-1, 280 DEG C~455 DEG C of reaction temperature；Preferred operating condition is reaction pressure 7.0~12.0 MPa, hydrogen to oil volume ratio 400: 1~1000: 1,1.0~3.0 h of volume space velocity^-1, reaction temperature 310 DEG C~440 ℃。

Restricted hydroconversion reactions described in step b), which refer to, will control certain hydro-conversion depth, avoid step a) In reaction effluent in non-aromatic component overcracking to influence the octane number of gasoline fraction product, according to raw material and Aromatic hydrocarbons difference in reaction effluent in step a), generally require control output aggregate in premium fraction yield 5 ~ 30wt% can retain the aromatic component in raw material to greatest extent and convert to vapour while processing heavy oil raw material in this way In oil distillate, to improve the octane number of gasoline products.

Flash separation described in step b) can choose independent knockout drum, and the heat that also can be used in hot high score boiling range is high It is allocated as gasoline flash separation tank, preferably the latter, process conditions 6.0~13.0MPa of reaction pressure, slightly below hydro-conversion mistake Stroke pressure, 150 ~ 300 DEG C of temperature, depending on the yield of conversion gasoline, product quality, the general Conventional wisdom according to this field Hot high score is controlled, main purpose is exactly to isolate the naphtha fraction of reaction process.

Hydro dewaxing process conditions described in step d) are as follows: 6.0~13.0 MPa of reaction pressure, hydrogen to oil volume ratio 500: 1 ~2000: 1, volume space velocity is 0.1~10.0 h^-1, 260 DEG C~455 DEG C of reaction temperature；Preferred operating condition is reaction pressure 7.0~12.0 MPa, hydrogen to oil volume ratio 600: 1~1200: 1,0.5~8.0 h of volume space velocity^-1, reaction temperature 310 DEG C~440 ℃。

The reaction of hydro dewaxing described in step d) refers to the pour point depression depth for needing to control according to product and entering this section of logistics, depending on The needs of reaction temperature should enter the preceding side for carrying out heat exchange logistics appropriate, separating due to using raw gasoline leading portion in logistics Formula, therefore the non-aromatic component in reaction feed object is not necessarily to deliberately be controlled, even if overcracking will not influence gasoline and evaporate Divide the octane number of product, only need to control the degree of pour point depression according to the demand of product, realize the production of purpose product, in this way Can be while processing heavy oil raw material produce high-knock rating gasoline, high-quality component in maximum pour point depression raw material is simultaneously protected It stays in product cut, to improve the content of target components in diesel oil and tail oil product, improves quality.

Hydrobon catalyst described in step a) includes carrier and the hydrogenation metal that is loaded.It is with the weight of catalyst Benchmark generally includes metal component of group VIB in the periodic table of elements, if tungsten and/or molybdenum are calculated as 10% ~ 35% with oxide, preferably It is 15% ~ 30%；Group VIII metal such as nickel and/or cobalt are calculated as 1% ~ 7%, preferably 1.5% ~ 6% with oxide.Carrier is inorganic refractory Oxide is selected generally from aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc..Wherein conventional hydrocracking pretreatment catalysis Agent can choose existing various commercial catalysts, for example, Fushun Petrochemical Research Institute (FRIPP) develop 3936, 3996, the Hydrobon catalysts such as FF-16, FF-26, FF-36, UDS-6；Also it can according to need the common sense progress by this field Preparation.The catalyst for refining should be seated in the upstream of reforming catalyst.

Gradation hydrogenation conversion catalyst described in step b) is the difference filling at least three according to aromatic hydrocarbon type in feedstock oil Hydrocracking catalyst of the kind containing molecular sieve, the type catalyst are the catalyst especially prepared according to this method.By reactant It flows direction and successively loads heavy aromatics hydrogenation conversion catalyst, light aromatic hydrocarbons hydrogenation conversion catalyst and mononuclear aromatics guarantor from top to bottom Stay catalyst.

Corresponding heavy aromatics hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is special according to this method The catalyst of preparation.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and alumina support.Generally Hydrogenation conversion catalyst by hydrogenation active metal components such as Wo, Mo, Co, Ni, molecular sieve component and alumina support etc. are constituted. It includes WO by weight₃(or MoO₃) 9~29wt%, NiO (or CoO) 5~10wt%, 15~45wt% of Y type molecular sieve and oxidation 20~50wt% of aluminium.In heavy aromatics hydrogenation conversion catalyst, the Y type molecular sieve is small crystal grain Y-shaped molecular sieve.Small-grain Y-type The partial size of molecular sieve is 400~600nm, and infrared 0.3~0.7mmol/g of total acid, middle strong acid ratio is greater than 50%(mmolg^-1/ mmol·g^-1), 2.435~2.440nm of cell parameter；Hole holds 0.5~0.7 cm³/ g, wherein the 2-8nm secondary pore hole hole Rong Zhanzong The ratio of appearance is 60% or more.The Y type molecular sieve has acid centre that is more accessible and exposing, is conducive to hydrocarbon molecule Diffusion, can be improved the preferential conversion ability of cyclic hydrocarbon especially tricyclic and the above aromatic hydrocarbons, orientation is by the virtue among thrcylic aromatic hydrocarbon Ring is saturated and is broken, the maximum amount of high-octane gasoline component of production.Containing the small crystal grain Y-shaped molecular sieve plus hydrogen Reforming catalyst, main function are the reactions that selectivity can be carried out for the thrcylic aromatic hydrocarbon in raw material, and to non-tricyclic The selectivity of two rings and mononuclear aromatics is poor.The Y type molecular sieve has a certain difference with conventional Y type molecular sieve, conventional modified Zeolite crystal degree is generally 800~1200nm, 0.35~0.50 cm of Kong Rongwei³/ g, the ratio of secondary pore Kong Rongzhan total pore volume General 30~50%, 50~70%(mmolg of middle strong acid ratio^-1/mmol·g^-1).The hydrogenation conversion catalyst can root Satisfactory catalyst is prepared according to the common sense of this field according to above description.

Corresponding light aromatic hydrocarbons hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is special according to this method The catalyst of preparation.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and alumina support.Generally Hydrogenation conversion catalyst by hydrogenation active metal components such as Wo, Mo, Co, Ni, molecular sieve component and alumina support etc. are constituted. It is exclusively used in the preferred Ni of hydrogenation conversion catalyst promoter metal of the invention, by weight includes WO₃(or MoO₃) 5~15wt%, NiO (or CoO) 3~8wt%, 5~30wt% of 50~60wt% of molecular sieve and aluminium oxide；The molecular sieve can be Y type molecular sieve. Further, the Y type molecular sieve has the property that 600~800nm of partial size, cell parameter 2.438~2.442nm, red Outer 0.6~0.8mmol/g of total acid, middle strong acid ratio is in 80%(mmolg^-1/mmol·g^-1), wherein 2-8nm secondary pore hole holds The ratio of total pore volume is accounted for 50% or more.The modified Y molecular sieve can be modified by the conventional method of this field It arrives.The main function of light aromatic hydrocarbons hydrogenation conversion catalyst is the reaction that selectivity can be carried out for the double ring arene in raw material, And it is poor to the selectivity of other aromatic hydrocarbons.This hydrogenation conversion catalyst is can be as described above according to the common sense system of this field Standby exclusive technology catalyst out.

It is the hydrogenation conversion catalyst containing molecular sieve that corresponding mononuclear aromatics, which retains catalyst, the hydro-conversion catalysis Agent includes hydrogenation active metals, molecular sieve component and alumina support.General hydrogenation conversion catalyst is by Wo, Mo, Co, Ni etc. Hydrogenation active metal component, molecular sieve component and alumina support etc. are constituted.It is exclusively used in hydrogenation conversion catalyst gold of the invention Belong to and form preferred Mo-Co, by weight includes MoO₃5~25wt%, 3~8wt% of CoO, 20~40wt% of molecular sieve and oxidation 30~50wt% of aluminium, the molecular sieve can be Y type molecular sieve.Further, preferred Y type molecular sieve has the property that grain Diameter is 500~700nm, and 2.438~2.440nm of cell parameter, infrared 0.6~0.7mmol/g of total acid, middle strong acid ratio is 70% (mmolg^-1/mmol·g^-1) more than, the ratio of 2-8nm secondary pore Kong Rongzhan total pore volume is 51 ~ 55%.The catalyst is maximum It is characterized in that the preparation process of molecular sieve, the non-framework aluminum more modification Y that is conducive to mononuclear aromatics reservation moderate using acid strength Type molecular sieve.Its main function is the mononuclear aromatics that can retain in the transmitting logistics of top, to other components of non-monocycle into Row selectively reaction.This hydrogenation conversion catalyst is to prepare as described above according to the common sense of this field.

In the present invention, technical term " strong acid " is Conventional wisdom well known to those skilled in the art.Field of catalyst preparation In, middle strong acid, strong acid are all made of NH₃- TPD is analyzed, and 150-250 DEG C of desorption is defined as weak acid, 250-400 DEG C of desorption It is defined as middle strong acid, 400-500 DEG C of desorption is defined as strong acid.

Above-mentioned three kinds of catalyst will consider the excessive of cracking performance, i.e. the heavy aromatics hydro-conversion at top during gradation Catalyst touches nitrogenous refined oil, and it is reacted mainly for polycyclic aromatic hydrocarbon, therefore cracking performance need not be excessively high；Its underpart The light aromatic hydrocarbons hydrogenation conversion catalyst of filling bears the task of production high octane gasoline, while needing to carry out double ring arene anti- It answers, lytic activity is higher than heavy aromatics hydrogenation conversion catalyst；The effect that the mononuclear aromatics of lowest part retains catalyst is to protect Mononuclear aromatics is stayed, while low octane rating component being avoided to enter in gasoline fraction, so its lytic activity is also unsuitable excessively high, and again Aromatic hydrogenation reforming catalyst is close or slightly lower.

Hydrodewaxing catalyst described in step d) is using the catalyst of the molecular sieve containing shape slective cracking, including carrier and institute The metal component of load.The catalyst generally using shape slective cracking molecular sieve and adhesive as carrier, with group VIB and/or Group VIII metal is hydrogenation active metal component.The shape slective cracking molecular sieve is hydrogen type molecular sieve, and the molecular sieve can be with Selected from one of Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve or a variety of, It is preferred that ZSM-5 molecular sieve；The silica alumina ratio of the shape slective cracking molecular sieve is generally 10~150, preferably 20~120.Institute The group VIB metal stated is Mo and/or W, and the group VIII metal is Co and/or Ni.On the basis of the weight of catalyst, add Content of the hydrogen activity metal component in terms of oxide is 1%~16wt%, and the content of shape slective cracking molecular sieve is 50%~85wt%, is glued The content of mixture is 10%~40wt%.The Hydrodewaxing catalyst can choose existing various commercial catalysts, such as The Hydrodewaxing catalysts such as FDW-1, FDW-3 that Fushun Petrochemical Research Institute (FRIPP) develops；Also it can according to need Prepared by the common sense of this field, for example, be referred to CN1952074A, CN1352231A, CN101143333A, Content disclosed in CN102451748A prepares satisfactory Hydrodewaxing catalyst.

The process of Hydrogen Separation described in step c), that is, cold high score separation liquid phase and gas phase, conversion gasoline can be by final stone The extraction of naphtha splitter bottom；Gas-liquid separation described in step c) and step d), stripping, fractional distillation process are those skilled in the art Content known to member.Gas-liquid separation is the separation process of hydro-conversion/pour point depression process product, generally mainly contains high-low pressure point From device, circulation hydrogen system etc., converting in the present invention is needed on the separation and Extraction process principle of gasoline using the high split flow of heat；It was fractionated Journey is the process that the liquid-phase product of gas-liquid separation further refines, and generally mainly contains stripper, fractionating column, side line tower etc..

Conversion gasoline described in step c) is the gasoline component that hydroconversion process obtains, and general sulfur content < 10 μ g/g is ground Study carefully method octane number > 85.

Heavy naphtha described in step d), low-coagulation diesel oil and unconverted oil due to being product that the non-aromatic component of processing obtains, Therefore arene content is extremely low, heavy naphtha is preferably as preparing ethylene by steam cracking raw material；Since the isomery of Hydrodewaxing catalyst is made With, therefore diesel oil and unconverted oil condensation point are extremely low, can be used as low-coagulation diesel oil and Lube basic oil material feedstocks use.

Compared with prior art, the method for production premium of the invention has the advantage that

1, the suitable heavy oil feed of selection will after the hydro-conversion of proprietary catalyst selectively saturation and open loop chain rupture Polycyclic aromatic hydrocarbon in raw material is converted into premium component, and resulting gasoline component has sulfur content low, the high feature of octane number, It can carry out reconciliation production.After separation, the resulting diesel oil of subsequent reactions and tail oil have the characteristics that condensation point is low, and tail oil contains Good Lube basic oil material feedstocks component can produce lube base oil under conditions of not pour point depression；In this method condition Under, resulting other constitutive properties also have advantage, can be produced directly as ethylene cracking material or fuel oil. The present invention can convert to greatest extent heavy distillate as purpose product premium, at the same the good low-coagulation diesel oil of by-product and Lube base oil has found an economically viable route for the processing of inferior raw material and the production of gasoline, low solidifying oil, has Very big practical advantages.

2, mink cell focus hydro-conversion/hydro dewaxing is carried out gradation segmental machining in process flow by the method for the present invention, On the basis of improving gasoline products, low-coagulation diesel oil, feed of base oil quality, ideal comprehensive process effect is obtained.In technique stream Cheng Shang, the method for the present invention are not required to carry out device big transformation, can adjustment by the combination transitivity of catalyst and unit Coupling realize the purpose of fine quality production, it is low etc. to have the advantages that save equipment, operating cost, reduces investment, has extensively Application prospect.

3, the method for the present invention has made certain limitation in process conditions, has to the reaction depth of refining stage and conversion zone The requirement of hardness, the purpose is to as far as possible convert mononuclear aromatics for polycyclic aromatic hydrocarbon in heavy raw oil, and be retained in gasoline and evaporate It in point, while playing and avoiding low octane rating fraction excessive fragmentation, the generation of phenomenon is reduced so as to cause quality of gasoline, cooperation is urged The gradation of agent is excessive, before back segment reaction antiknock component is separated to extraction in advance, hydro dewaxing process may be implemented It is adjusted flexibly, is not required to the variation of misgivings product quality, diesel oil and tail oil targetedly convert, and are promoting product quality, are reducing On the basis of condensation point, the property that excessive fragmentation influences gasoline is avoided, processing heavy raw oil maximum can be fully achieved Produce the purpose of premium and the low solidifying oil of high-quality.

3, according to the method for the present invention, new hydrogenation conversion catalyst is developed, is a gross appearance of technological progress, can be incited somebody to action The production ways of premium are widened, in addition, according to the height of arene content in raw material to hydro-conversion newly developed Catalyst has carried out targeted gradation research and development and filling, and this method journey that main reaction carries out in the case where converting operating condition may be implemented Degree, in the past in process of production, for the hydrogenation process of wax oil raw material, if production light fraction, is only catalytic reforming Device provides the heavy naphtha raw material of Gao Fangqian, and can not directly produce premium, and uses this method, can be directly by wax Oily raw material is converted into the gasoline products of the market demand, technically has very big competitive advantage, while the low solidifying product produced It can also be used as low-coagulation diesel oil and Lube basic oil material feedstocks, provide more production chains for enterprise, bring intuitive warp Ji benefit.

Detailed description of the invention

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

Specific embodiment

Combined technical method of the invention is described in detail with reference to the accompanying drawing.Process flow is only listed in Fig. 1 It is main to illustrate, some necessary equipment and container are omitted in schematic diagram.

As shown in Figure 1, to produce process of gasoline process as follows by the present invention: after heavy charge 1 is mixed with hydrogen 2, into adding hydrogen Refining reaction area and 3 haptoreaction of Hydrobon catalyst；Reaction effluent 4 enters hydroconversion reactions area and gradation plus hydrogen 5,6,7 haptoreaction of reforming catalyst；After reaction effluent 8 enters separative unit 9, gaseous stream 10 is discharged in top, into containing The treatment region 11 of the units such as Hydrogen Separation, stripping, fractionation, final bottom discharge conversion gasoline 13, light component 12 is discharged in top；Point Liquid phase stream 14 is discharged from 9 bottom of unit, hydro dewaxing reaction zone and Hydrodewaxing catalyst 16 are entered after mixing with hydrogen 15 Haptoreaction, effluent 17 enter the treatment region 18 containing units such as gas-liquid separation, stripping, fractionation, and top obtains high-quality naphtha 19, middle part obtains low-coagulation diesel oil 20, and bottom obtains low solidifying tail oil 21.Catalyst 3 is Hydrobon catalyst, and 5,6 and 7 are respectively Heavy aromatics, light aromatic hydrocarbons and mononuclear aromatics retain hydro-conversion class catalyst, and 16 be Hydrodewaxing catalyst.

Combined technical method of the invention is further described followed by specific embodiment.

Embodiment 1

Using group technology process shown in FIG. 1, straight-run gas oil is selected to carry out adding hydrogen production gasoline as conversion/pour point depression raw material, Control certain purification (nitrogen content 100ppm) and conversion level (yield of gasoline 20%).Catalyst used in embodiment is quotient Product catalyst FF-36 hydrotreating catalyst, special hydrogenation conversion catalyst A, B and C mononuclear aromatics retain hydro-conversion and urge Agent, commercial catalyst FDW-3 Hydrodewaxing catalyst.

The property of catalyst A, B and C are shown in Table 1, and the property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.

Embodiment 2

Using group technology process shown in FIG. 1, straight-run gas oil is selected to carry out adding hydrogen production gasoline as conversion/pour point depression raw material, Control certain purification (nitrogen content 200ppm) and conversion level (yield of gasoline 20%).Catalyst used in embodiment is quotient Product catalyst FF-36 hydrotreating catalyst, special hydrogenation conversion catalyst A, B and C mononuclear aromatics retain hydro-conversion and urge Agent, commercial catalyst FDW-3 Hydrodewaxing catalyst.

Embodiment 3

Using group technology process shown in FIG. 1, straight-run gas oil is selected to carry out adding hydrogen production gasoline as conversion/pour point depression raw material, Control certain purification (nitrogen content 200ppm) and conversion level (yield of gasoline 10%).Catalyst used in embodiment is quotient Product catalyst FF-36 hydrotreating catalyst, special hydrogenation conversion catalyst A, B and C mononuclear aromatics retain hydro-conversion and urge Agent, commercial catalyst FDW-3 Hydrodewaxing catalyst.

Comparative example 1

Comparative example 1 is the hydrocracking process for processing straight-run gas oil, according to conventional hydrofinishing depth and controls naphtha receipts Rate ~ 10%, contrast product are heavy naphtha, and catalyst used in comparative example is commercial catalyst FF-36 hydrorefining catalyst Agent, FDW-3 Hydrodewaxing catalyst.

The property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.

Comparative example 2

Comparative example 1 is the hydrocracking process for processing straight-run gas oil, according to conventional hydrofinishing depth and controls naphtha receipts Rate ~ 20%, contrast product are heavy naphtha, and catalyst used in comparative example is commercial catalyst FF-36 hydrorefining catalyst Agent, FDW-3 Hydrodewaxing catalyst.

The 1 main physico-chemical property of special reforming catalyst of table

2 feedstock oil property list of table

3 reaction condition of table

4 main character of table

Catalytic reforming can be saved compared with comparative example using present invention processing heavy oil feed it can be seen from examples detailed above Process, directly production high-octane rating, low-sulfur gasoline products, take into account the liquid product for producing low condensation point, technically have Advantage.

Claims

1. a kind of method of catalyst grade with technology production gasoline and low solidifying oil, includes the following steps:

2. according to the method for claim 1, which is characterized in that total arene content is in 40wt% in the heavy oil feed More than, preferably 45wt% or more, nitrogen content is in 800mgg^-1More than, preferably 1000mgg^-1More than.

3. according to the method for claim 2, which is characterized in that the end point of distillation of the heavy oil feed is 450~580 DEG C, It is preferred that 480~570 DEG C；Density is 0.92g/cm³More than, preferably 0.93g/cm³More than.

4. according to method described in claim 2 or 3, which is characterized in that the heavy raw oil is selected from decompressed wax oil, depitching One of oil or wax tailings are several.

5. according to the method for claim 1, which is characterized in that Hydrofinishing conditions described in step a) are as follows: reaction pressure 6.0~13.0 MPa, hydrogen to oil volume ratio 200: 1~3000: 1, volume space velocity are 0.1~5.0 h^-1, 260 DEG C of reaction temperature~ 435℃。

6. according to the method for claim 1, which is characterized in that restricted hydrofinishing described in step a) refers to control step The nitrogen content of rapid a) gained refined oil is 50 ~ 250mgg^-1, preferably 100 ~ 200mgg^-1。

7. according to the method for claim 6, which is characterized in that tricyclic in aromatic component in reaction effluent obtained by step a) And the content of the above component is 1 ~ 20wt%, preferably 2 ~ 15wt%.

8. according to the method for claim 1, which is characterized in that the condition of flash separation described in step b) are as follows: pressure 6.0 ~13.0MPa, temperature are 150 ~ 300 DEG C.

9. according to the method for claim 1, which is characterized in that hydroconversion process condition described in step b) are as follows: reaction 6.0~13.0 MPa of pressure, hydrogen to oil volume ratio 300: 1~2000: 1, volume space velocity are 0.1~5.0 h^-1, 280 DEG C of reaction temperature ~455 DEG C.

10. according to the method for claim 1, which is characterized in that hydro dewaxing process conditions described in step d) are as follows: reaction 6.0~13.0 MPa of pressure, hydrogen to oil volume ratio 500: 1~2000: 1, volume space velocity are 0.1~10.0 h^-1, reaction temperature 260 DEG C~455 DEG C.

11. according to the method for claim 1, which is characterized in that restricted hydroconversion reactions described in step b) refer to The yield for controlling gasoline fraction in output aggregate is 10~40wt%.

12. according to the method for claim 1, which is characterized in that Hydrobon catalyst described in step a) includes carrier With the hydrogenation metal loaded, hydrogenation metal includes group VIB metal and/or group VIII metal, and carrier is inorganic refractory oxidation Object；On the basis of the weight of catalyst, content of the metal component of group VIB in terms of oxide is 10% ~ 35%, and group VIII metal is such as The content of nickel and/or cobalt in terms of oxide is 1% ~ 7%.

13. according to the method for claim 1, which is characterized in that the gradation wax oil hydrogenation reforming catalyst refer to by Reaction stream direction successively includes that heavy aromatics hydrogenation conversion catalyst, light aromatic hydrocarbons hydrogenation conversion catalyst and mononuclear aromatics retain Catalyst.

14. according to the method for claim 13, which is characterized in that the heavy aromatics hydrogenation conversion catalyst includes adding hydrogen Active metal, Y type molecular sieve and alumina support；The heavy aromatics hydrogenation conversion catalyst includes WO by weight₃Or MoO₃ 9 5~10wt% of~29wt%, NiO or CoO, 20~50wt% of 15~45wt% of Y type molecular sieve and aluminium oxide.

15. according to the method for claim 14, which is characterized in that the partial size of the Y type molecular sieve is 400~600nm, red Outer 0.3~0.7mmol/g of total acid, middle strong acid ratio is 50% or more, 2.435~2.440nm of cell parameter；Hole holds 0.5~0.7 cm³/ g, wherein the ratio of 2-8nm secondary pore Kong Rongzhan total pore volume is 60% or more.

16. according to the method for claim 13, which is characterized in that the light aromatic hydrocarbons hydrogenation conversion catalyst includes adding hydrogen Active metal, Y type molecular sieve and alumina support；The light aromatic hydrocarbons hydrogenation conversion catalyst includes WO by weight₃Or MoO₃ 5 3~8wt% of~15wt%, NiO or CoO, 5~30wt% of 50~60wt% of Y type molecular sieve and aluminium oxide.

17. according to the method for claim 16, which is characterized in that the cell parameter of the Y type molecular sieve be 2.438~ 2.442nm, infrared 0.6~0.8mmol/g of total acid, middle strong acid ratio is 80% or more, the wherein 2-8nm secondary pore hole hole Rong Zhanzong The ratio of appearance is 50% or more.

18. according to the method for claim 13, which is characterized in that it includes adding hydrogen living that the mononuclear aromatics, which retains catalyst, Property metal, Y type molecular sieve and alumina support；Catalyst includes MoO by weight₃5~25wt%, 3~8wt% of CoO, Y type 30~50wt% of 20~40wt% of molecular sieve and aluminium oxide.

19. according to the method for claim 18, which is characterized in that the partial size of the Y type molecular sieve is 500~700nm, brilliant 2.438~2.440nm of born of the same parents' parameter, infrared 0.6~0.7mmol/g of total acid, middle strong acid ratio is in 70% or more, 2-8nm secondary pore hole Hold the ratio for accounting for total pore volume 51 ~ 55%.

20. according to the method for claim 1, which is characterized in that the Hydrodewaxing catalyst includes carrier and bears The hydrogenation active metal component of load, catalyst carrier contain shape slective cracking molecular sieve and adhesive, hydrogenation active metal component packet Include group VIB and/or group VIII metal；On the basis of the weight of catalyst, hydrogenation active metal component containing in terms of oxide Amount is 1%~16wt%, and the content of shape slective cracking molecular sieve is 50%~85wt%, and the content of adhesive is 10%~40wt%.

21. according to the method for claim 20, which is characterized in that the shape slective cracking molecular sieve is selected from Hydrogen ZSM- 5, one of ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve or a variety of, the shape slective cracking The silica alumina ratio of molecular sieve is 10~150.