CN106244232A - A kind of residuum hydrodesulfurization RFCC group technology of sour crude - Google Patents

A kind of residuum hydrodesulfurization RFCC group technology of sour crude Download PDF

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Publication number
CN106244232A
CN106244232A CN201610698320.8A CN201610698320A CN106244232A CN 106244232 A CN106244232 A CN 106244232A CN 201610698320 A CN201610698320 A CN 201610698320A CN 106244232 A CN106244232 A CN 106244232A
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oil
catalyst
rfcc
hydrogenation
hydrodesulfurization
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朱忠良
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Xishan Lvchun Plastic Products Factory
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Xishan Lvchun Plastic Products Factory
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses the hydrodesulfurization RFCC group technology of the decompression residuum of a kind of sour crude, decompression residuum and optional catalytic cracked oil pulp steam thing, optional heavy catalytic cycle oil, optional distillate together with enter residual hydrogenation equipment, carrying out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst, separating reaction product obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue；Hydrogenated residue individually or enters heavy oil catalytically cracking equipment together with vacuum gas oil (VGO), carries out cracking reaction in the presence of Cracking catalyst, and separating reaction product obtains dry gas, liquefied gas, gasoline, diesel oil, heavy-cycle oil and slurry oil；Described residual hydrogenation equipment uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors.Total sulfur content in High Sulfur Vacuum Residue catalytic cracking production can be reduced to below 5ppm by this technique, and makes Useful Time of Hydrogenation Catalyst reach more than 2 years.

Description

The residuum hydrodesulfurization of a kind of sour crude-RFCC group technology
Technical field
The present invention relates to a kind of residuum hydrodesulfurization-RFCC group technology, be specifically related to a kind of employing specific The residuum hydrodesulfurization of the sour crude that catalyst is carried out-RFCC group technology.
Background technology
Residual oil is primarily referred to as from atmospheric and vacuum distillation unit bottom heavy constituent out, and wherein atmospheric unit is out called normal pressure slag Oil, decompressor out be called decompression residuum.Decompression residuum darkish complexion thickness, in semi-solid under room temperature, its character and crude oil Character is relevant.In petroleum refinery, residual oil is usually used in processing and produces the products such as petroleum coke, residual lubricating oil, Colophonium, or as splitting Change raw material.
At present, alternative residuum conversion process technique has tens kinds, and hydrogenation technique is well recognized as economic and environment-friendly deeply Processing technique.After the impurity such as residual oil hydrogenated process removing metal, sulfur, nitrogen, improve hydrogen content, can urge as the heavy oil of high-quality Change cracked stock.Additionally residual hydrocracking heavy oil is due to molecular structure relation, processes through RFCC, octane number The highest, the productivity of C3, C4 alkene is the highest, and the sulfur content in product is the lowest simultaneously, can meet the requirement of modern environmental protection, therefore Now residual hydrogenation tail oil is obtained the most universal application directly as the technique of Rfcc Feedstock.
The residual hydrogenation technology of the most industrialization or technology maturation according to reactor types, can be divided into fixed bed, 4 types such as moving bed, ebullated bed (expanded bed) and suspension bed (slurry bubble bed).Wherein, fixed bed Residue Hydrotreating Technology is instead The different beds answering device load different types of catalyst, to remove metal heteroatom and sulfur, nitrogen element in heavy oil, heavy to it Component is changed a social system.This technique combines with catalytic cracking process and can be completely converted into market by being worth relatively low decompression residuum Costly gasoline, diesel oil, it is achieved making full use of of oil refining resource.
Although have the fixed bed hydrogenation technology with Chevron company and Uop Inc. at present, but current residual oil deep processing Based on the decompression residuum that Middle East light oil before being all based on and domestic crude oil produce, these residual oil compositions not very complexity, Heavy constituent is less, after the most described decompression residuum and the mixing of atmospheric tower base oil, can directly enter RFCC (RFCC) dress Put and process.
Along with heaviness, the in poor quality of world's crude oil are deepened day by day, crude oil sulfur content is more and more higher, and the lightweight of high-quality is former Oil is constantly reducing.The crude oil of refinery's processing in recent years mostly is imported crude oil, and relative density increases year by year, in several years of the beginning of this century The average density of whole world refinery processing crude oil rises to about 0.8633.The problem that sulfur content is high is the most extremely serious, the current world The yield of upper sour crude oil and sour crude accounts for more than the 75% of world's crude oil total output.20th century the mid-90 whole world refinery The crude oil average sulfur content of processing is 0.9%, and the beginning of this century has increased to 1.6%.
But existing Residue Hydrotreating Technology for be all domestic and the decompression residuum in the Middle East, the catalyst that it uses is used When High Sulfur Vacuum Residue, desulfurized effect difference and catalysqt deactivation are fast.The most how to provide the hydrodesulfurization of High Sulfur Vacuum Residue- RFCC group technology, effectively the sulfur content in product can control at below 5ppm, and improve the use longevity of catalyst Life, is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose the hydrodesulfurization-RFCC combination of the decompression residuum of a kind of sour crude Technique, effectively the sulfur content in product can control at below 5ppm, and improve the service life of catalyst.
For reaching this purpose, the present invention by the following technical solutions:
The hydrodesulfurization of the decompression residuum of a kind of sour crude-RFCC group technology, decompression residuum is with optional Catalytic cracked oil pulp steam thing, optional heavy catalytic cycle oil, optional distillate enter residual hydrogenation dress together Putting, carry out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst, separating reaction product obtains gas, hydrotreated naphtha, hydrogenation Diesel oil and hydrogenated residue；Hydrogenated residue individually or enters heavy oil catalytically cracking equipment, at cracking catalysis together with vacuum gas oil (VGO) Carrying out cracking reaction in the presence of agent, separating reaction product obtains dry gas, liquefied gas, gasoline, diesel oil, heavy-cycle oil and slurry oil.
Wherein optional, heavy-cycle oil is recycled to residual hydrogenation equipment.
Optionally, slurry oil is after separated goes out residue, and the thing that steams of slurry oil is back to hydrogenation plant.
Described residual hydrogenation equipment uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, described Catalyst includes carrier and active component.
Described carrier is complex or the mixture of MSU-G, SBA-15 and HMS.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing Thing.
The reaction condition of described fixed bed reactors is: reaction temperature is 350-450 DEG C, and hydrogen dividing potential drop is 12-17MPa, hydrogen Oil volume is than 600-1000, volume space velocity 0.15-0.4h-1。
In the decompression residuum of described sour crude, sulfur content is more than 1wt%, preferably more than 1.5wt%.
An object of the present invention is that, it is provided that the compound of a kind of 3 kinds of different mesopore molecular sieves works in coordination with effect to show Should be with special catalytic performance, described cooperative effect shows that desulfuration purification aspect, special catalytic performance are then to show right On the service life of catalyst and the raising of catalysis activity.
In catalyst field, according to the definition of IUPAC (IUPAC), the aperture title less than 2nm For micropore；The aperture referred to as macropore more than 50nm；Aperture the most mesoporous (or claiming mesopore) between 2 to 50nm.Mesoporous material Being a kind of aperture new material with huge specific surface area and three-dimensional open-framework between micropore and macropore, it has The excellent specific property that other porous material does not has: there is the pore passage structure of high-sequential；The single distribution in aperture, and aperture size Can change at relative broad range；Mesoporous various shapes, hole wall composition and character controllable；Height can be obtained by optimum synthesis condition Heat stability and hydrothermal stability.
But in present applications ' the tail must be taken, described mesoporous material, when for catalytic field, is all single use, such as MCM system Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU- 4, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA- 8, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Two kinds of carriers of a few studies literature research compound, such as Y/SBA-15, Y/SAPO-5 etc., majority is to be situated between Hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve are main.Use the compound with performance of 3 kinds of different mesopore molecular sieves Go out cooperative effect and the research of special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is complex or the mixture of MSU-G, SBA-15 and HMS.Described complex or mixed In compound, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15): (0.5-0.7)。
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention uses is all the existing molecular sieve of catalytic field, and it is Through obtaining widely studied and application at catalytic field.
MSU-G is a kind of to have vesicle structure shape particle shape and the mesopore molecular sieve of layered framework structure, and it has height Degree skeleton crosslinking and relatively thick skeleton wall and there is superpower heat stability and hydrothermal stability, its skeleton hole is with vertical Being cross-linked with each other in layer and the hole being parallel to layer, diffusion path is the shortest because its vesicle shell is thick.The vesicle shape particle of MSU-G molecular sieve Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is the highest.
SBA-15 belongs to the one of mesopore molecular sieve, has two-dimentional six square tube pore structures, has P3mm space group.At XRD In diffracting spectrum, main peak is near about 1 °, for (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively Weak, it is difficult to observe.Additionally, the silicon dioxide on SBA-15 skeleton is generally amorphous state, observe not in Radix Rumicis XRD diffraction To obvious diffraction maximum.SBA-15 has a bigger aperture (maximum up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because of And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the most unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S Type mesoporous material is thicker, thus hydrothermal stability is more preferable, and short distance is the most unordered simultaneously organizational structure and aperture modulation scope are more Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction The heart.
The present invention, from each mesoporous material, carries out compound pairing, screens through widely, filter out MSU-G, SBA-15 With the compound of HMS or mixing.Inventor finds, in numerous complex/mixture, and only MSU-G, SBA-15 and HMS tri- Compound or the mixing of person, could realize the collaborative lifting of hydrofinishing effect, and enables to catalysis activity and do not reduce for a long time, makes Can be greatly increased with the life-span.In other words, the only specific compound or mixing of MSU-G, SBA-15 and HMS three of the present invention, Solve collaborative and two technical problems in service life the most simultaneously.Other coordinate, or do not possess synergism, or use the longevity Order shorter.
Described complex, can use being simply mixed of MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two After mixing, such as MSU-G/SBA-15 complex, the mixing of MSU-G/HMS and SBA-15/HMS complex.Described being combined can To use known electrostatic matching method, ion exchange, two step crystallization methods etc. to be prepared.These mesopore molecular sieves are combined with it The preparation method of thing is the known method of catalyst field, and the present invention no longer repeats with regard to it.
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28- 0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists In the range of Gai, in can realizing, in coalite tar, sulfur content controls at below 10ppm and denitrification ability notable.Namely Saying, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just tool Standby cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize collaborative effect Should.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45- 0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0), Preferably 1:0.48:0.42:0.95.
The total content of described active component is the 1%-15% of vehicle weight, preferably 3-12%, further preferred 5-10%. Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% etc..
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains Having catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined ?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding, Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4 Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5, Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid, Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 370-420 DEG C, and hydrogen dividing potential drop is 14- 15MPa, hydrogen to oil volume ratio 700-900, volume space velocity 0.15-0.3h-1。
Preferably, described fixed bed reactors include 2-10 beds, further preferred 2-5 catalyst bed Layer.
The technological process of the present invention is as follows:
Residual oil and hydrogen enter residual hydrocracking device, react in the presence of a hydrogenation catalyst, separate residual oil and add The product of hydrogen, obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue, wherein gas, hydrotreated naphtha and hydrogenation Diesel oil respectively through pipeline ejector, hydrogenated residue then through pipeline together with the optional vacuum gas oil (VGO) from pipeline through pipeline Enter heavy oil catalytically cracking equipment, react in the presence of Cracking catalyst, the product of heavy oil separation catalytic cracking, To dry gas, liquefied gas, gasoline, diesel oil, heavy-cycle oil and slurry oil, wherein dry gas, liquefied gas, gasoline and diesel oil draw through pipeline respectively Going out device, heavy-cycle oil is recycled to residual hydrocracking device through pipeline successively, and slurry oil enters distilling apparatus through pipeline, isolates Residue go out device through pipeline, slurry oil steam thing successively through pipeline enter residual hydrocracking device 3, optional distillate Residual hydrocracking device is entered successively through pipeline.
The hydrofining technology of the present invention is by choosing specific catalyst, and described catalyst is by choosing special ratios MSU-G, SBA-15 and HMS complex/mixture is as carrier, and chooses the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component, and described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture so that this catalyst produces cooperative effect, to the decompression residuum of sour crude Hydrodesulfurization can control at total sulfur content less than 5ppm, simultaneously the catalyst of catalytic hydrogenation unit can reach service life 2 years with On.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1: 1.1:0.5.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier The 10% of quality, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material is by Beijing satellite system The double plunger micro pump making factory's manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ZM gas by gas cylinder Weight effusion meter coutroi velocity, hydrogenation catalyst loadings is 2kg.Reacted product enters RFCC unit.
Raw materials used for Kazakhstan's decompression residuum, its sulfur content is up to 3.27%, i.e. 32700ppm.
Controlling reaction condition is: temperature 390 DEG C, hydrogen dividing potential drop 14.0MPa, hydrogen to oil volume ratio 800, volume space velocity 0.2h-1。
Testing final product, total sulfur content is reduced to 4ppm, and beds pressure drop is unchanged.
Embodiment 2
Preparing catalyst by infusion process, carrier is MSU-G/SBA-15 complex, MSU-G/HMS and SBA-15/ The mixing of HMS complex, wherein the ratio of MSU-G, SBA-15 and HMS is same as in Example 1.Described active component nitrogenizes two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is the 10% of carrier quality, and its mol ratio is 1:0.6: 0.45):1.2。
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 2ppm, and beds pressure drop is unchanged.
Comparative example 1
The carrier of embodiment 1 is replaced with MSU-G, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 29ppm, and beds pressure drop increases above 0.05%.
Comparative example 2
The carrier of embodiment 1 is replaced with SBA-15, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 33ppm, and beds pressure drop increases above 0.05%.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and beds pressure drop increases above 0.05%.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and beds pressure drop increases above 0.05%.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and beds pressure drop increases above 0.05%.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 35ppm, and beds pressure drop increases above 0.05%.
Embodiment 1 shows with comparative example 1-6, and the present invention uses MSU-G, SBA-15 and HMS complex of special ratios/mixed Compound is as carrier, when replacing with single carrier or complex carrier two-by-two, does not all reach the technique effect of the present invention, all reach Less than the present invention technique effect (desulfurization degree and beds change in pressure drop, change in pressure drop reflect catalyst inactivation speed Degree), therefore MSU-G, SBA-15 and HMS complex/mixture of the special ratios of the present invention as carrier and catalyst other Possessing cooperative effect between component, described hydrofining technology creates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 46ppm, and beds pressure drop increases above 0.05%.
Comparative example 8
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 50ppm, and beds pressure drop increases above 0.05%.
Above-described embodiment and the explanation of comparative example 7-8, hydrogenation catalyst several activity group of the hydrofining technology of the present invention The specific contact an of/existence, is omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that Which create cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and 3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same The beds pressure drop of time embodiment 1 reduces 15%.
Comparative example 9
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 3.2%.
Comparative example 10
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 4.3%.
Embodiment 3 shows with comparative example 9-10, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst, And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (7)

1. the hydrodesulfurization of the decompression residuum of sour crude-RFCC group technology, decompression residuum and optional Catalytic cracked oil pulp steam thing, optional heavy catalytic cycle oil, optional distillate enter residual hydrogenation equipment together, Carrying out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst, separating reaction product obtains gas, hydrotreated naphtha, hydrogenated diesel oil And hydrogenated residue；Hydrogenated residue individually or enters heavy oil catalytically cracking equipment together with vacuum gas oil (VGO), deposits in Cracking catalyst Carrying out cracking reaction under, separating reaction product obtains dry gas, liquefied gas, gasoline, diesel oil, heavy-cycle oil and slurry oil；Described slag Oil hydrogenation plant uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, and described hydrogenation catalyst includes Carrier and active component, it is characterised in that
Described carrier is complex or the mixture of MSU-G, SBA-15 and HMS；Described active component is nitridation two molybdenum MO2N, nitrogen Change tungsten W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture；
The reaction condition of described fixed bed reactors is: reaction temperature is 300-420 DEG C, and hydrogen dividing potential drop is 13-15MPa, hydrogen oil body Long-pending ratio 800-1200, volume space velocity 0.3-0.8h-1。
2. hydrodesulfurization-RFCC the group technology of the decompression residuum of sour crude as claimed in claim 1, it is special Levying and be, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15): (0.5-0.7)。
3. hydrodesulfurization-RFCC the group technology of the decompression residuum of sour crude as claimed in claim 1, it is special Levying and be, the total content of described active component is the 3-12% of vehicle weight, preferably 5-10%.
4. hydrodesulfurization-RFCC the group technology of the decompression residuum of sour crude as claimed in claim 1, it is special Levy and be, nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1: 0.48:0.42:0.95。
5. hydrodesulfurization-RFCC the group technology of the decompression residuum of sour crude as claimed in claim 1, it is special Levying and be, the reaction condition of described fixed bed reactors is: reaction temperature is 370-420 DEG C, and hydrogen dividing potential drop is 14-15MPa, hydrogen oil Volume ratio 700-900, volume space velocity 0.15-0.3h-1。
6. hydrodesulfurization-RFCC the group technology of the decompression residuum of sour crude as claimed in claim 1, it is special Levying and be, described fixed bed reactors include 2-10 beds, preferably 2-5 beds.
7. hydrodesulfurization-RFCC the group technology of the decompression residuum of sour crude as claimed in claim 1, it is special Levy and be, TiO2、CeO2、V2O5And NbOPO4Respective content is respectively the 1-7% of carrier quality, preferably 2-4%.
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