CN103480424B - A kind of for the upgrading viscosity reduction preparation method and applications of ultra-dispersed catalyst - Google Patents
A kind of for the upgrading viscosity reduction preparation method and applications of ultra-dispersed catalyst Download PDFInfo
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- CN103480424B CN103480424B CN201310428555.1A CN201310428555A CN103480424B CN 103480424 B CN103480424 B CN 103480424B CN 201310428555 A CN201310428555 A CN 201310428555A CN 103480424 B CN103480424 B CN 103480424B
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Abstract
The invention discloses a kind of preparation method for the ultra-dispersed catalyst of upgrading viscosity reduction, according to the mass fraction, required raw material is: base oil 150 ~ 200, surfactant 5 ~ 15, transistion metal compound 1.5 ~ 2, cosurfactant 1 ~ 1.5；Raw material described above is mixed at a temperature of 40 ~ 80 DEG C, control after 100 ~ 8000 revs/min of stirring 5 ~ 300min, control supersonic frequency in the range of 10 ~ 50KHz, through ultrasonic vibration 10 ~ 30min, obtain required for the ultra-dispersed catalyst of upgrading viscosity reduction, ultra-dispersed catalyst can improve viscous crude quality on the spot by catalytic action, the chemical bond making bond energy in heavy component relatively low is easily broken off, heavy component is made to convert to containing the less light components of carbon number, can realize permanently reducing thick oil viscosity, thus make viscous crude lighting to a great extent, reduce viscous crude during wellbore lift, difficulty in pipeline transportation and processing.
Description
Technical field
The present invention relates to viscous crude, super-heavy oil deposit development field, relate particularly to a kind of for upgrading viscosity reduction ultra-dispersed catalyst and preparation method thereof field.
Background technology
Viscous crude is the important component part of Global Oil resource, generally estimates that viscous crude resource is about more than 10 times of conventional oil.Viscous crude refers to that degassed crude viscosity is more than 100mPa s, the relative density crude oil more than 0.92 under reservoir temperature.It is commonly referred to as heavy oil (including tar sand, maltha) abroad, belongs to non-conventional oil resource.
In thickened oil recovery, heat extraction by steam injection is main mining type, high-temperature steam heating oil reservoir, viscosity of crude is greatly lowered, eliminates near wellbore zone oil layer blocking simultaneously, reduce viscous crude flow resistance and increase heavy oil production.But owing to interlayer, the in-layer heterogeneity of oil reservoirs generally exist, and the density of steam and viscosity are the lowest, and therefore gravity segregation and viscous fingering have a strong impact on its effect.The former is that so that steam surmounts oil wall, the ratio of viscosities oil viscosity that the latter is then because steam is little, forms passage or tonguing owing to steam is less than the density of oil.Therefore, steam walks around oil band, occurs vapour to alter.The onlap of steam and vapour are altered and are easy to occur, and produce and uneven vertically sweep oil efficiency, cause remaining residual oil saturation in stratum high, and steam sweep efficiency is little, and oil displacement efficiency and recovery ratio reduce.
Along with deepening continuously of oil field development, depend merely on conventional production technique and be extremely difficult to stratum viscous crude entirety viscosity reduction and improved the purpose of oil field overall efficiency.
Upgrading viscosity reduction heavy crude producing is a kind of irreversible viscosity reduction heavy crude producing mode, and selecting suitable catalyst is the key realizing upgrading viscosity reduction.Having had the technique of heavy charge oil-breaking and corresponding catalyst in modern petrochemical, its reaction temperature is general at least more than 400 DEG C.By comparison, the temperature reached during heavy crude heat extraction is the most relatively low.But, if injecting the catalyst that dispersibility is high, activity is high in oil reservoir, greatly reduce reaction activity, it is possible under relatively low temperature conditions, realize viscous crude cracking in oil reservoir.
Nineteen eighty-two Hyne et al. points out that metal ion can accelerate aquathermolysis, and hereafter, people utilize some catalyst to be studied in reaction.It is believed that superheated water can transmit heat hydro carbons, and make some asphaltene molecules can be pyrolyzed as little molecule.Therefore, thick oil viscosity and flow behavior also can be improved.Additionally, the heat increased can provide driving force so that viscous crude is readily flowed, improve its crude output.The normally used catalyst of aquathermolysis is all mineral, water solublity, oil-soluble and disperse type catalyzer.The viscosity reducing effect of these catalyst presses mineral catalysis agent < water-soluble catalyst < oil-soluble catalyst < disperse type catalyzer.
It is more that water solublity, oil soluble metal salt catalyst are studied by forefathers, owing to water-soluble metal salt catalyst is soluble in water, there is under high temperature certain lipophile, with the exposure level of crude oil compared with oil-soluble catalyst very poor, the most insufficient, and the content of water is the highest in system, water is the strongest to water-soluble catalyst diluting effect, metallic catalyst constituents is difficult to reach the effect of high dispersive in viscous crude, the utilization rate of metallic catalyst constituents is low, and the catalytic action of such catalyst can not get fully playing.Therefore, the modification viscosity reduction extent of reaction will weaken.Additionally, after aqueous catalyst is distributed in viscous crude, it is necessary to water is removed, adds the cost of post processing.Oil-soluble catalyst contains the metallic compound of organic group as disperse type catalyzer, the dispersion effect in viscous crude be improved significantly because it is oil soluble material, can dissolve each other with crude oil.Catalyst is big to the modification viscosity reduction extent of reaction, directly as product after organic group reaction, it is not necessary to separate, but oil-soluble catalyst is higher than the cost of water-soluble catalyst, and it is the most inconspicuous to compare water-soluble catalyst effect.
Summary of the invention
An object of the present invention is, in order to viscous crude or super-viscous oil viscosity are greatly lowered, improves viscous crude quality on the spot, it is provided that a kind of nanoscale reverse micelle microemulsion, the most ultra-dispersed catalyst；
For achieving the above object, the present invention adopts the following technical scheme that realization:
A kind of for the upgrading viscosity reduction preparation method of ultra-dispersed catalyst, according to the mass fraction, required raw material is: base oil 150 ~ 200, surfactant 5 ~ 15, transistion metal compound 1.5 ~ 2, cosurfactant 1 ~ 1.5；
Raw material described above is mixed at a temperature of 40 ~ 80 DEG C, control after 100 ~ 8000 revs/min of stirring 5 ~ 300min, control supersonic frequency in the range of 10 ~ 50KHz, through ultrasonic vibration 10 ~ 30min, obtain nanoscale reverse micelle microemulsion, i.e. required for the ultra-dispersed catalyst of upgrading viscosity reduction；
Described transistion metal compound is at least one in VI B race metallic compound or VIII B race non-noble metal compound；
VI described B race metallic compound is at least one in chromium, molybdenum, tungsten and their compound thereof；
VIII described B race non-noble metal compound is at least one in ferrum, cobalt, nickel and their compound thereof；
VI described B race metallic compound is at least one in molybdate, tungstates, chromate, bichromate, molybdenum oxide, tungsten oxide, chromium oxide；
VIII described B race non-noble metal compound is water-soluble metal salt；Water-soluble metal salt is at least one in acetate, carbonate, chloride, nitrate, acetyl tributyl citrate salt and oxalates；
Described base oil is at least one in lube base oil, aerial kerosene, straight-run diesel oil, straight run lubricating oil；
Described surfactant is at least one in Span80, Tween80, Tween60, Span40；
Described cosurfactant is at least one in normal propyl alcohol, n-butyl alcohol, n-amyl alcohol, isoamyl alcohol；
Another object of the present invention is: provide the application of above-mentioned ultra-dispersed catalyst, for this purpose, the technical scheme that the present invention provides is: this super scattered type catalyst reacts for upgrading viscosity reduction, its reaction temperature controls in the range of 200 DEG C ~ 350 DEG C, on the basis of viscous crude quality, described catalyst amount is the 0.01 ~ 0.5% of viscous crude quality, and amount of water is the 10 ~ 50% of viscous crude quality.
Using the technical scheme that the present invention provides, owing to ultra-dispersed type catalyst can dissolve each other with raw material, dispersion in the feed is the highest, and catalysis activity is high, and the conversion ratio of upgrading is the highest.Ultra-dispersed catalyst can improve viscous crude quality on the spot by catalytic action, the chemical bond making bond energy in heavy component relatively low is easily broken off, heavy component is made to convert to containing the less light components of carbon number, can realize permanently reducing thick oil viscosity, thus make viscous crude lighting to a great extent, reduce viscous crude difficulty during wellbore lift, in pipeline transportation and processing.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but present disclosure is not limited solely to the following examples.
Embodiment
1
Molybdenum is metal active centres, prepares ultra-dispersed type catalyst as modification viscosity reduction catalysis agent.Catalyst preparation takes following method to carry out:
The preparation of ultra-dispersed DNAcarrier free molybdenum catalyst: nonionic surfactant Span80, lube base oil (initial boiling point 350 DEG C), viscosity are 6.8mPa s (80 DEG C), (NH4)6Mo7O24· 4H2O is as the presoma preparing catalyst.The preparation experiment of nanoscale microemulsion is carried out at ambient pressure, after using base oil 200g, 18g water, the surfactant of 9g and 1g to help surfactant isoamyl alcohol ultrasonic disperse, stirring 6min under 4000r/min speed, supersound process is that 10min forms transparent reverse micelle microemulsion.The granularity utilizing dynamic light scattering method to measure catalyst is 420nm.
Liaohe Oil Field super-viscous oil is carried out modifying viscosity reduction laboratory experiment by the ultra-dispersed catalyst of molybdenio utilizing the method to prepare, it is 24h when 200 DEG C of reaction temperatures, reaction, oil-water ratio is 7:3, catalyst charge is 0.3wt%, reducing thick oil viscosity rate is up to 84.72%, wherein asphalt content is reduced to 5.35% by 8.78%, and gum level is dropped to 29.45% by 42.68%.Experiment shows, this catalyst, under 200 DEG C of cryogenic conditions, has good catalytic reforming battle array and glues effect Liaohe Oil Field super-viscous oil.
Embodiment
2
Under the conditions of uniform temperature, nonionic surfactant Tween80 aqueous solution, lube base oil (initial boiling point 320 DEG C), viscosity are that 6mPa s (80 DEG C), nickel acetate are as the presoma preparing catalyst.After using base oil 150g, 16.8g water and the surfactant of 9g, 2g to help surfactant n-butyl alcohol and nickel acetate 1.85g mixing, stirring 6min under 6500r/min rotating speed, supersound process is 5min, forms stable nanometer micro-emulsion.The granularity utilizing dynamic light scattering method to measure catalyst is 1400nm.
Liaohe Oil Field super-viscous oil is carried out modifying viscosity reduction laboratory experiment by the Ni-based ultra-dispersed catalyst utilizing the method to prepare, it is 24h when 250 DEG C of reaction temperatures, reaction, oil-water ratio is 7:3, catalyst charge is 0.3wt%, reducing thick oil viscosity rate is up to 79.62%, wherein asphalt content is reduced to 5.76% by 8.78%, and gum level is dropped to 32.45% by 42.68%.Experiment shows, this catalyst, under 250 DEG C of cryogenic conditions, has good catalytic reforming battle array and glues effect Liaohe Oil Field super-viscous oil.
Embodiment
3
25 DEG C, under condition of normal pressure, nonionic surfactant Tween80 and Span80 is 6mPa s (80 DEG C), (NH according to 1:1 mixing, lube base oil (initial boiling point 340 DEG C), viscosity4)6Mo7O24· 4H2O is as the presoma preparing catalyst.Surfactant is added in mixture to reduce the interfacial tension between oil-continuous phase and little water droplet.Base oil 160g, 20g water and the surfactant of 9g and 2g is used to help surfactant n-butyl alcohol and (NH4)6Mo7O24· 4H2After O 1.87g mixing, stirring 6min under 5000r/min rotating speed, supersound process is 10min, forms stable nanometer micro-emulsion.The granularity utilizing dynamic light scattering method to measure catalyst is 1800nm.
Liaohe Oil Field super-viscous oil is carried out modifying viscosity reduction laboratory experiment by the ultra-dispersed catalyst of molybdenio utilizing the method to prepare, it is 24h when 350 DEG C of reaction temperatures, reaction, oil-water ratio is 7:3, catalyst charge is 0.3wt%, reducing thick oil viscosity rate is up to 81.45%, wherein asphalt content is reduced to 5.42% by 8.78 %, and gum level is dropped to 30.67% by 42.68%.Experiment shows, this catalyst, under 350 DEG C of cryogenic conditions, has good catalytic reforming battle array and glues effect Liaohe Oil Field super-viscous oil.
Claims (2)
1. the preparation method for the ultra-dispersed catalyst of upgrading viscosity reduction, it is characterised in that according to the mass fraction, required raw material is: base oil 150 ~ 200, surfactant 5 ~ 15, transistion metal compound 1.5 ~ 2, cosurfactant 1 ~ 1.5；
Raw material described above is mixed at a temperature of 40 ~ 80 DEG C, controlling after 100 ~ 8000 revs/min of stirring 5 ~ 300min, control supersonic frequency is in the range of 10-50KHz, through ultrasonic vibration 10 ~ 30min, obtain nanoscale reverse micelle microemulsion, i.e. required for the ultra-dispersed catalyst of upgrading viscosity reduction；
Described transistion metal compound is at least one in VI B race metallic compound or VIII B race non-noble metal compound；VI described B race metallic compound is at least one in chromium, molybdenum, tungsten compound；At least one in the described compound that VIII B race non-noble metal compound is ferrum, cobalt, nickel；VI described B race metallic compound is at least one in molybdate, tungstates, chromate, bichromate, molybdenum oxide, tungsten oxide, chromium oxide；VIII described B race non-noble metal compound is water-soluble metal salt；Water-soluble metal salt is at least one in acetate, chloride, nitrate, acetyl tributyl citrate salt and oxalates；Described base oil is at least one in lube base oil, aerial kerosene, straight-run diesel oil, straight run lubricating oil；Described surfactant is at least one in Span-80, Tween-80, Tween-60, Span-40；Described cosurfactant is at least one in normal propyl alcohol, n-butyl alcohol, n-amyl alcohol, isoamyl alcohol.
2. a kind of application for the ultra-dispersed catalyst of upgrading viscosity reduction prepared by preparation method as claimed in claim 1, it is characterized in that: this ultra-dispersed type catalyst reacts for upgrading viscosity reduction, its reaction temperature controls in the range of 200 DEG C ~ 350 DEG C, on the basis of viscous crude quality, described catalyst amount is the 0.01 ~ 0.5% of viscous crude quality, and amount of water is the 10 ~ 50% of viscous crude quality.
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| CN109135703A (en) * | 2018-09-17 | 2019-01-04 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of heavy crude thinner |
| CN113444511A (en) * | 2021-08-03 | 2021-09-28 | 嘉仕嘉德(北京)能源工程技术有限公司 | Nano copper-based thickened oil modifier |
| CN114058358B (en) * | 2021-12-08 | 2023-01-17 | 胜利油田方圆化工有限公司 | Preparation method and application of viscosity-reducing oil displacement agent for thick oil |
| CN115058239A (en) * | 2022-06-22 | 2022-09-16 | 中国石油大学(华东) | Ionic liquid microemulsion thickened oil modifying viscosity reducer and preparation method thereof |
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| CN101024186A (en) * | 2007-02-02 | 2007-08-29 | 中国石油大学(华东) | Reversed phase micelle nano catalyst for dreg-oil suspension bed hydrogenation cracking and preparing method |
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Effective date of registration: 20191210 Address after: No. 1688, Yongxing Road, Pinghu Economic Development Zone, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Jiulongshan Industry Co., Ltd Address before: 163000 No. 199, development road, hi tech Development Zone, Heilongjiang, Daqing Patentee before: Northeast Petroleum University |
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