CN110117501A - A kind of In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble - Google Patents
A kind of In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble Download PDFInfo
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- CN110117501A CN110117501A CN201910311821.XA CN201910311821A CN110117501A CN 110117501 A CN110117501 A CN 110117501A CN 201910311821 A CN201910311821 A CN 201910311821A CN 110117501 A CN110117501 A CN 110117501A
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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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
- 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
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Abstract
A kind of In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble, method include: by after the preheating of sulfur-bearing heavy oil feedstock with the organic homogeneous catalyst of oil-soluble, mixed containing hydrogen medium after from the bottom inlet of vulcanizing tank input vulcanizing tank from bottom to top；With containing hydrogen medium In-situ sulphiding react occurs for the organic homogeneous catalyst of sulfur-bearing heavy oil feedstock, oil-soluble in closed vulcanizing tank, nano level metal sulfide grain is converted by the organic homogeneous catalyst of oil-soluble, and convert sulfur-bearing heavy oil feedstock in the mixed hydrogen heavy oil of dopen Nano grade metal sulfide grain, the mixed hydrogen heavy oil of dopen Nano grade metal sulfide grain is exported from the top exit of vulcanizing tank, and enters preset reactor as reaction feed.The In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble provided in this embodiment is conducive to the organic homogeneous catalyst Efficient Conversion of oil-soluble be active nano level metal sulfide grain, and simple process, flexible operation, low energy consumption.
Description
[technical field]
The present invention relates to heavy oil (residual oil) modification technology field more particularly to a kind of originals of the organic homogeneous catalyst of oil-soluble
Position vulcanization process.
[background technique]
Residual oil processing is world-famous puzzle, if the product yield for continuing to use conventional delayed coking technology is about 60% or so；It adopts
With high temperature and pressure ebullated bed or the inorganic catalytic way of fixed bed, yield about 60-75% or so.Delayed Coking Technology is in state my father
Full production is difficult under the environmental requirement of lattice；Fixed bed residual hydrogenation is not only limited by the limitation of raw material impurity,
Even if being difficult to break through 22 months using state-of-the-art catalyst and its operation cycle of process technology, can not be overhauled with every 4 years
Time between overhauls(TBO) match.Boiling bed residual oil adds stability of the hydrogen due to not can guarantee product studies on asphaltene, and total conversion is difficult
More than 80%, and easily there is coking, blocking in fractionating system, and then influences the stable operation of device.
Slurry bed system faces hydrogen thermocracking process to the content of processed raw material middle impurity almost without limitation, it might even be possible to process
Pitch and oil-sand, slurry bed system hydrocracking process can achieve 90~95% or more due to high conversion rate, allow in appointed condition
Under the premise of almost without the device operation cycle limitation, no operation just, the difference in latter stage, thus be considered as inferior heavy, slag
It is flexible to increase substantially full factory's crude oil processing for one relatively effective approach of oily lighting, and the existing coking plant of substitution
Property and improve the important technical of full factory's light oil yield.
Slurry bed system faces hydrogen thermocracking process and is divided into different classes according to the difference of used catalyst performance, type,
The technology for such as using oil-soluble catalyst, using the technology of powder-type solid catalyst, using water-soluble catalyst
Technology etc..Wherein use the slurry bed technique of oil-soluble catalyst, the especially hydrogenation plant in processing liquid phase medium
In with catalyst suppression coke ability is strong, additive amount is few, be processing liquid phase medium the features such as to pipeline, equipment, valve without abrasion
Slurry bed technique developing direction.
It is catalyst precursor that slurry bed system, which faces the added organic homogeneous catalyst of oil-soluble in hydrogen thermocracking process process,
Active nano level metal sulfide grain could be generated through over cure, and the sulfidation of catalyst is by vulcanization reaction
How catalyst precursor is changed into nano-dispersion state by the influence of condition, such as temperature, pressure, concentration, hydrogen-oil ratio
Active catalyst granules becomes problem to be solved, and then influences the cost of investment of device, operating cost, stablizes behaviour
Make the important indicators such as period and performance.
[summary of the invention]
In view of this, being used the embodiment of the invention provides a kind of In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble
To solve how to realize that the metal sulfide grain for converting nano-dispersion state for oil-soluble organic homogeneous catalyst is asked
Topic.
To achieve the goals above, the present invention provides a kind of In-situ sulphiding method of organic homogeneous catalyst of oil-soluble, institute
The method of stating include: by after the heating of sulfur-bearing heavy oil feedstock with the organic homogeneous catalyst of oil-soluble, mixed containing hydrogen medium after from vulcanizing tank
Bottom inlet input the vulcanizing tank from bottom to top, wherein gas-liquid distributor is equipped in the vulcanizing tank；The sulfur-bearing heavy oil
Raw material, the organic homogeneous catalyst of the oil-soluble are In-situ sulphiding anti-with the generation containing hydrogen medium in the closed vulcanizing tank
It answers, converts nano level metal sulfide grain for the organic homogeneous catalyst of the oil-soluble, and by the sulfur-bearing heavy oil feedstock
It is converted into the mixed hydrogen heavy oil for adulterating the nano level metal sulfide grain；The nano level metal sulfide grain will be adulterated
The mixed hydrogen heavy oil is exported from the top exit of the vulcanizing tank, and enters preset reactor as reaction feed.
Optionally, the sulfur-bearing heavy oil feedstock includes reduced crude, decompression residuum, de-oiled asphalt, ethylene cracking tar, coal
At least one of tar, high viscous crude, oil plant sludge.
Optionally, the organic homogeneous catalyst of the oil-soluble is based on molybdenum and molten as the oil of auxiliary agent containing nickel, cobalt
Property organo-metallic compound.
Optionally, reaction time of the sulfur-bearing heavy oil feedstock in the vulcanizing tank is 0.1~2 hour, reaction pressure
In 0.1MPa~20MPa, reaction temperature is controlled at 250 DEG C~400 DEG C, described to contain hydrogen medium and the sulfur-bearing heavy oil feedstock for control
Volume ratio be 1:1~30:1, the quality of the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and the sulfur-bearing heavy oil feedstock
Than for 50ppm~2000ppm.
Optionally, reaction time of the sulfur-bearing heavy oil feedstock in the catalyst vulcanization tank is 0.3~1 hour, instead
Answer pressure control in 8MPa~15MPa, reaction temperature is controlled at 300 DEG C~360 DEG C, described to contain hydrogen medium and the sulfur-bearing heavy oil
The volume ratio of raw material is 10:1~20:1, the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and the sulfur-bearing heavy oil feedstock
Mass ratio is 100ppm~500ppm.
Optionally, the bottom of the vulcanizing tank is using cone.
Optionally, the gas-liquid distributor is set to the bottom of the vulcanizing tank.
Optionally, the particle size for the molybdenum disulfide particles that the In-situ sulphiding reaction generates is 0.1nm~1 μm, preferably
Ground, the particle size of the molybdenum disulfide particles are 0.1nm~50nm.
Optionally, the hydrogen medium that contains includes at least one of fresh hydrogen, circulating hydrogen.
The In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble provided in the present invention in vulcanizing tank by being arranged gas
Liquid distributor makes the organic homogeneous catalyst of sulfur-bearing heavy oil feedstock, oil-soluble and mixes more evenly containing hydrogen medium, appropriate anti-
It answers under control condition, the organic homogeneous catalyst of oil-soluble is enabled to be converted into metal sulfide (i.e. two sulphur of nano-dispersion
Change molybdenum particle), the nanoscale molybdenum disulfide particles of generation can effectively inhibit coking as active catalyst, and have
Good greasy property avoids equipment, pipeline, instrument etc. from wearing and block.And used process process is simple, behaviour
Work is flexibly, adaptability to raw material is strong, investment is low, low energy consumption.
[Detailed description of the invention]
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this field
For those of ordinary skill, without any creative labor, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the schematic diagram of vulcanizing tank provided by the embodiment of the present invention.
Description of symbols:
A- vulcanizing tank；B- gas-liquid distributor.
[specific embodiment]
It is clear in order to be more clear the purpose of the present invention, technical solution and advantageous effects, below in conjunction with attached drawing and
Specific embodiment, the present invention will be described in further detail.It should be understood that specific implementation described in this specification
Mode is not intended to limit the present invention just for the sake of explaining the present invention.
The present invention provides a kind of In-situ sulphiding method of organic homogeneous catalyst of oil-soluble, comprising the following steps:
By after the heating of sulfur-bearing heavy oil feedstock with the organic homogeneous catalyst of oil-soluble, mixed containing hydrogen medium after from the bottom of vulcanizing tank
Portion's entrance inputs vulcanizing tank from bottom to top, wherein gas-liquid distributor is equipped in vulcanizing tank.
With containing hydrogen medium sulphur in situ occurs for the organic homogeneous catalyst of sulfur-bearing heavy oil feedstock, oil-soluble in closed vulcanizing tank
Change reaction, converts nano level metal sulfide grain for the organic homogeneous catalyst of oil-soluble, and sulfur-bearing heavy oil feedstock is converted
For the mixed hydrogen heavy oil of dopen Nano grade metal sulfide grain.
It by the mixed hydrogen heavy oil of dopen Nano grade metal sulfide grain, is exported from the top exit of vulcanizing tank, and as anti-
It should feed into preset reactor.
Optionally, sulfur-bearing heavy oil feedstock includes reduced crude, decompression residuum, de-oiled asphalt, ethylene cracking tar, coal tar
At least one of oil, high viscous crude, oil plant sludge.Wherein, reduced crude refers to from the resulting remnants of air-distillation tower bottom
Oil；Decompression residuum refers to crude oil through being evaporated under reduced pressure resulting residual oil；De-oiled asphalt refers to the residue after crude distillation；Ethylene is split
Solution tar refers to ethylene cracking material in the excessively middle raw material of steam cracking and the product of product pyrocondensation；Coal tar is coking of coal mistake
The high temperature coal tar that journey obtains；High viscous crude is with high viscosity, highdensity heavy oil；Oil plant sludge refers to that oil plant is raw
The oily wastewater of production generated oily sludge in processing.
Sulfur-bearing heavy oil feedstock is very sticky liquid or solid at room temperature, and preheating can make heavy oil feedstock soft in advance
Change, and the viscosity of heavy oil feedstock is reduced.
Specifically, the temperature range upper limit of sulfur-bearing heavy oil feedstock heating is 360 DEG C, 350 DEG C, 340 DEG C, 330 DEG C, sulfur-bearing weight
The temperature range lower limit of oily raw material heating is 250 DEG C, 280 DEG C, 300 DEG C, 310 DEG C, 320 DEG C；The temperature of sulfur-bearing heavy oil feedstock heating
Degree range can be made of any number of the upper limit and lower limit.
The organic homogeneous catalyst of oil-soluble is based on molybdenum and containing nickel, cobalt as the oil-soluble organometallic of auxiliary agent
Close object.The organic homogeneous catalyst of oil-soluble can dissolve each other with heavy oil feedstock, compared to water-soluble catalyst, in heavy oil feedstock more
Easily dispersion has higher hydrogenation activity.It is to be appreciated that the organic homogeneous catalyst of oil-soluble that vulcanizing tank is added is catalyst
Presoma, under the In-situ sulphiding reaction condition drafted, so that the organic homogeneous catalyst of the oil-soluble being added generates nanometer fraction
The molybdenum disulfide particles (active catalyst) of bulk state.
In the embodiment of the present application, the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and the mass ratio of sulfur-bearing heavy oil feedstock are
50ppm~2000ppm, wherein the upper limit of the mass ratio of the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and sulfur-bearing heavy oil feedstock
For 2000ppm, 1500ppm, 1000ppm, 800ppm, 500ppm, the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and sulfur-bearing weight
The lower limit of the mass ratio of oily raw material is 50ppm, 100ppm, 150ppm, 175ppm, 200ppm, 250ppm, 300ppm；Oil-soluble
The range of the mass ratio of organic homogeneous catalyst (in terms of molybdenum) and sulfur-bearing heavy oil feedstock can be by the upper limit and any number group of lower limit
At.Preferably, the mass ratio of the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and sulfur-bearing heavy oil feedstock is 100ppm~500ppm.
Asphalitine in sulfur-bearing heavy oil feedstock can associate with metal sulfide, to inhibit coking.The organic homogeneous catalyst of oil-soluble
Additive amount ratio is relatively low, can be effectively reduced cost, is conducive to industrialized production.
It include at least one of fresh hydrogen, circulating hydrogen containing hydrogen medium.Wherein, fresh hydrogen refers to new hydrogen；
Circulating hydrogen refers to the hydrogen being recycled in entire reaction system；Volume ratio containing hydrogen medium and sulfur-bearing heavy oil feedstock is 1:
1~30:1, it is preferable that the volume ratio containing hydrogen medium and sulfur-bearing heavy oil feedstock is 5:1~20:1, it is highly preferred that containing hydrogen medium with
The volume ratio of sulfur-bearing heavy oil feedstock is 10:1~20:1.
Further, vulcanizing tank is configured with gas-liquid distributor, and gas-liquid distributor is former by the sulfur-bearing heavy oil inputted in vulcanizing tank
Material and is mixed into uniform gas-liquid mixed phase containing hydrogen medium at the organic homogeneous catalyst of oil-soluble, so that gas-liquid mixed is mutually in sulphur
Change and In-situ sulphiding reaction occurs in tank.It is to be appreciated that mixing is more uniform, more it is beneficial to the dispersion of the partial size of molybdenum disulfide,
Molybdenum disulfide particles also can more disperse in heavy oil feedstock.
Using cone, gas-liquid distributor is set to the conical lower section of vulcanizing tank for the bottom of vulcanizing tank, and sulfur-bearing heavy oil is former
Material and the organic homogeneous catalyst of oil-soluble are mixed into uniform gas-liquid mixed phase under the action of gas-liquid distributor.Mixed gas
Liquid mixed phase moves upwards, and is flowed from bottom to top in vulcanizing tank with flat-pushing stream mode, can effectively avoid material lagging heap
Product.Vulcanize simple jar structure, mixed high-efficient, without structure dead zone, the severe feedstock oil of various properties can be applicable in.
Specifically, the reaction temperature of vulcanizing tank is controlled at 250 DEG C~400 DEG C, and the reaction temperature of vulcanizing tank is relatively low, makes
The metal material requirement for obtaining vulcanizing tank is low, and then reduces cost, and can ensure the reaction efficiency and conversion ratio of In-situ sulphiding reaction.
Wherein, the upper limit of the reaction temperature of vulcanizing tank be 400 DEG C, 380 DEG C, 360 DEG C, 340 DEG C, 320 DEG C, the reaction temperature of vulcanizing tank
Lower limit is 250 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C；The range of reaction temperature of vulcanizing tank can be by any of the upper limit and lower limit
Numerical value composition.Preferably, the reaction temperature of vulcanizing tank is controlled at 300 DEG C~360 DEG C.
In one embodiment, the reaction pressure of vulcanizing tank is controlled in 0.1~20.0MPa, wherein the reaction of vulcanizing tank
Upper limit of pressure is 20MPa, 18MPa, 15MPa, 13MPa, 11MPa, the lower limit of the reaction pressure of vulcanizing tank be 0.1MPa,
The reaction pressure range of 1MPa, 5MPa, 8MPa, 10MPa, vulcanizing tank can be made of any number of the upper limit and lower limit.Preferably,
The reaction pressure of vulcanizing tank is controlled in 8~15MPa.
In one embodiment, reaction time of the sulfur-bearing heavy oil feedstock in vulcanizing tank is 0.1~2 hour.Its
In, the upper limit of reaction time of the sulfur-bearing heavy oil feedstock in vulcanizing tank is 2 hours, 1.5 hours, 1 hour, 0.8 hour,
0.7 hour, the lower limit of reaction time of the sulfur-bearing heavy oil feedstock in vulcanizing tank is 0.1 hour, 0.2 hour, 0.3 hour,
0.4 hour, 0.5 hour.It is highly preferred that reaction time of the sulfur-bearing heavy oil feedstock in vulcanizing tank is 0.3~1 hour, from
And ensure the conversion ratio of In-situ sulphiding reaction.
The particle size for the molybdenum disulfide that In-situ sulphiding reaction in vulcanizing tank generates is 0.1nm~1 μm.Preferably, sulphur
The particle size for changing the molybdenum disulfide that the In-situ sulphiding reaction in tank generates is 0.1nm~50nm.It is to be appreciated that actually generating
Molybdenum disulfide partial size by reaction controlling parameter adjusted have certain fluctuation.Specifically, the molecule of molybdenum disulfide is
Hexagonal, molybdenum disulfide are made of three layers of atomic layer, and upper layer and lower layer are sulphur atom, and centre is molybdenum atom layer.With curing
The partial size of molybdenum becomes smaller, and specific surface area is bigger, and adsorption capacity enhancing, reactivity improves.It is to be appreciated that occur in vulcanizing tank
Vulcanization reaction is more abundant, mixing it is more uniform, the size of the molybdenum disulfide particles of generation is smaller, and provided specific surface area is got over
Greatly.According to reaction controlling parameter provided by the present application can largely by catalyst precursor, (oil-soluble is organic homogeneously to be urged
Agent) molybdenum disulfide particles of active nano-dispersion state are generated, and simplify technique, reduce production cost.
In one embodiment, preset reactor is paste state bed reactor.Slurry bed system faces the reaction machine of hydrogen thermal cracking
Reason is that active hydrogen atom is replenished in time on the hydrocarbon free radical that thermal cracking generates, and is incited somebody to action with this to close the free radical of thermal cracking generation
Macromolecular hydrocarbon is changed into small molecule hydrocarbon.Hydrogen carries out Dissociative in molybdenum disulfide microparticle surfaces to generating dissociation hydrogen atom,
Dissociation hydrogen (atom) activity on these molybdenum disulfide microparticle surfaces is high, and the free radical that can be generated with heavy oil/slag oil cracking exists
It is reacted on molybdenum disulfide microparticle surfaces, generates light liquid oil.The light oil of generation is desorbed from molybdenum disulfide microparticle surfaces, thus
The active sites of molybdenum disulfide particle are vacated, these active sites vacated carry out Dissociative to hydrogen again.
In comparison, residual oil processing is existed using the yield of traditional decarbonization process (heavy oil catalytic cracking, delayed coking)
40% or so, using high temperature and pressure ebullated bed and the inorganic catalytic way yield of fixed bed 60~75% or so, and to equipment, behaviour
The requirement for making condition is high.And the In-situ sulphiding method provided in this embodiment using the organic homogeneous catalyst of oil-soluble, it obtains
The partial size of metal sulfide grain can reach nanoscale, and very high dispersion degree can be reached in sulfur-bearing heavy oil feedstock, improve
The activity of catalyst.Pass through many experiments (the decompression residuum test of such as Beijing Yanshan Petrochemical Company, Kelamayi vacuum residue
Test), the organic homogeneous catalyst of oil-soluble can effectively improve the yield of residual oil processing to 90~95% or so, and technique more may be used
Control, adaptability to raw material is strong, invests low, less energy consumption.
Below will by specific embodiment, the present invention will be described in detail, concrete technology flow process figure please refers to Fig. 1.
Embodiment 1
Sulfur-bearing heavy oil feedstock is heated up after being mixed with the organic homogeneous catalyst of oil-soluble, containing hydrogen medium after 320 DEG C~340 DEG C
Input vulcanizing tank A from the bottom inlet of vulcanizing tank A by pipeline, the gas-liquid distributor B in vulcanizing tank A by sulfur-bearing heavy oil feedstock,
The organic homogeneous catalyst of oil-soluble and uniform gas-liquid mixed phase is mixed into containing hydrogen medium.The reaction pressure of vulcanizing tank A be 8~
15MPa, substantially 320 DEG C of reaction temperature, material stops 1 hour in vulcanizing tank A, the body containing hydrogen medium Yu sulfur-bearing heavy oil feedstock
For product than being 20:1, the mass ratio of the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and sulfur-bearing heavy oil feedstock is 200ppm, hydrogeneous Jie
Matter is mixed by fresh hydrogen and recycle hydrogen.
In-situ sulphiding reaction occurs in vulcanizing tank A, converts molybdenum disulfide particles for the organic homogeneous catalyst of oil-soluble, and
The mixed hydrogen heavy oil for adulterating molybdenum disulfide particles is exported from the top of vulcanizing tank A and is entered in preset reactor, wherein doping
The particle size measured of being tested of molybdenum disulfide particles is 0.1nm~50nm.The property of sulfur-bearing heavy oil feedstock used in embodiment 1
Matter is shown in Table 1.
The property of 1. sulfur-bearing heavy oil feedstock of table
The In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble provided in the present invention in vulcanizing tank by being arranged gas
Liquid distributor makes the organic homogeneous catalyst of sulfur-bearing heavy oil feedstock, oil-soluble and mixes containing hydrogen medium more evenly, in original appropriate
The organic homogeneous catalyst of oil-soluble is enabled to be converted into the curing of nano-dispersion state under the vulcanization reaction control condition of position
Molybdenum particle, the molybdenum disulfide particles (i.e. active catalyst) of generation can effectively inhibit coking, and have good profit
Slip energy avoids equipment, pipeline, instrument etc. from wearing and block.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (9)
1. a kind of In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble, which is characterized in that the described method includes:
By after the heating of sulfur-bearing heavy oil feedstock with the organic homogeneous catalyst of oil-soluble, mixed containing hydrogen medium after enter from the bottom of vulcanizing tank
Mouth inputs the vulcanizing tank from bottom to top, wherein gas-liquid distributor is equipped in the vulcanizing tank；
The sulfur-bearing heavy oil feedstock, the organic homogeneous catalyst of the oil-soluble in the closed vulcanizing tank with hydrogeneous Jie
In-situ sulphiding reaction occurs for matter, converts nano level metal sulfide grain for the organic homogeneous catalyst of the oil-soluble, and will
The sulfur-bearing heavy oil feedstock is converted into the mixed hydrogen heavy oil for adulterating the nano level metal sulfide grain；
The mixed hydrogen heavy oil of the nano level metal sulfide grain will be adulterated, is exported from the top exit of the vulcanizing tank,
And enter preset reactor as reaction feed.
2. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 1, which is characterized in that described to contain
Sulphur heavy oil feedstock includes reduced crude, decompression residuum, de-oiled asphalt, ethylene cracking tar, coal tar, high viscous crude, oil plant
At least one of sludge.
3. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 1, which is characterized in that the oil
The organic homogeneous catalyst of dissolubility is based on molybdenum and containing nickel, cobalt as the oil-soluble organo-metallic compound of auxiliary agent.
4. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 3, which is characterized in that described to contain
Reaction time of the sulphur heavy oil feedstock in the vulcanizing tank is 0.1~2 hour, and reaction pressure is controlled in 0.1MPa~20MPa, instead
Answer temperature control at 250 DEG C~400 DEG C, the volume ratio containing hydrogen medium and the sulfur-bearing heavy oil feedstock is 1:1~30:1, institute
The mass ratio for stating the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and the sulfur-bearing heavy oil feedstock is 50ppm~2000ppm.
5. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 3, which is characterized in that described to contain
Reaction time of the sulphur heavy oil feedstock in the catalyst vulcanization tank be 0.3~1 hour, reaction pressure control 8MPa~
15MPa, reaction temperature are controlled at 300 DEG C~360 DEG C, and the volume ratio containing hydrogen medium and the sulfur-bearing heavy oil feedstock is 10:1
~20:1, the mass ratio of the organic homogeneous catalyst of oil-soluble (in terms of molybdenum) and the sulfur-bearing heavy oil feedstock be 100ppm~
500ppm。
6. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 1, which is characterized in that the sulphur
Change the bottom of tank using cone.
7. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 1, which is characterized in that the gas
Liquid distributor is set to the conical lower section of the vulcanizing tank.
8. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 4 or 5, which is characterized in that institute
The particle size for stating the molybdenum disulfide particles that In-situ sulphiding reaction generates is 0.1nm~1 μm, it is preferable that the molybdenum disulfide
The particle size of grain is 0.1nm~50nm.
9. the In-situ sulphiding method of the organic homogeneous catalyst of oil-soluble according to claim 1, which is characterized in that described to contain
Hydrogen medium includes at least one of fresh hydrogen, circulating hydrogen.
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| CN114181733A (en) * | 2021-11-25 | 2022-03-15 | 中国石油大学(华东) | Method for regulating and controlling particle size of oil-soluble catalyst vulcanization product |
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| CN106311341A (en) * | 2015-06-30 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst for slurry bed of heavy oil as well as catalyst and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181733A (en) * | 2021-11-25 | 2022-03-15 | 中国石油大学(华东) | Method for regulating and controlling particle size of oil-soluble catalyst vulcanization product |
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