CN103480424A - Preparation method and application of super dispersing catalyst for quality improvement and viscosity reduction of thickened oil - Google Patents
Preparation method and application of super dispersing catalyst for quality improvement and viscosity reduction of thickened oil Download PDFInfo
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- CN103480424A CN103480424A CN201310428555.1A CN201310428555A CN103480424A CN 103480424 A CN103480424 A CN 103480424A CN 201310428555 A CN201310428555 A CN 201310428555A CN 103480424 A CN103480424 A CN 103480424A
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Abstract
The invention discloses a preparation method of a super dispersing catalyst for quality improvement and viscosity reduction of thickened oil. The super dispersing catalyst comprises the following raw materials in parts by weight: 150-200 parts of base oil, 5-15 parts of a surfactant, 1.5-2 parts of a transition metal compound and 1-1.5 parts of a cosurfactant; the preparation method comprises the steps as follows: mixing the raw materials at the temperature of 40-80 DEG C, stirring the mixture for 5-300 min at the speed of 100-8,000 rpm, and performing ultrasound concussion for 10-30 minutes at the ultrasonic frequency of 10-50 KHz to obtain the demanded super dispersing catalyst for quality improvement and viscosity reduction of thickened oil. The super dispersing catalyst can improve the quality of the thickened oil on the spot through the catalytic action, enables chemical bonds with lower bond energy in heavy components to break easily, enables the heavy components to be converted into light components with less carbon and can permanently reduce the viscosity of the thickened oil, so that the thickened oil becomes light to a great extent, and the difficulties of the thickened oil in the rockshaft lifting process, pipeline transportation and processing are reduced.
Description
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Technical field
The present invention relates to viscous crude, super-heavy oil deposit development field, concrete relate to a kind of for the upgrading viscosity reduction with the loose Catalysts and its preparation method of oversubscription field.
Background technology
Viscous crude is the important component part of Global Oil resource, usually estimates that the viscous crude resource is about more than 10 times of conventional oil.Viscous crude refers to that degassed crude viscosity is greater than 100mPas under reservoir temperature, the crude oil that relative density is greater than 0.92.Be commonly referred to as abroad heavy oil (comprising tar sand, maltha), belong to the non-conventional oil resource.
In thickened oil recovery, heat extraction by steam injection is main mining type, high-temperature steam heating oil reservoir, and the decrease viscosity of crude is eliminated the near wellbore zone oil layer blocking simultaneously, reduces the viscous crude flow resistance and increases heavy oil production.But due to interlayer, the in-layer heterogeneity ubiquity of oil reservoirs, and the density of steam and viscosity are all very low, so gravity segregation and viscous fingering have a strong impact on its effect.The former is because steam is less than oily density, thereby makes steam surmount oily wall, and latter is because the ratio of viscosities oil viscosity of steam is little, forms passage or tonguing.Therefore, steam is walked around the oil band, vapour occurs and alter.The onlap of steam and vapour are altered and are easy to occur, and produce the inhomogeneous oily efficiency of vertically sweeping, and cause in stratum the residue residual oil saturation high, and the steam sweep efficiency is little, and oil displacement efficiency and recovery ratio reduce.
Along with deepening continuously of oil field development, depend merely on the purpose that conventional production technique has been difficult to reach the whole viscosity reduction of stratum viscous crude and has improved the 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 that realizes the upgrading viscosity reduction.Technique and the corresponding catalyst of heavy charge oil-breaking have been arranged in modern petrochemical industry, and its reaction temperature is generally at least more than 400 ℃.By comparison, the temperature reached during heavy crude heat extraction is lower.But, if inject dispersed high, active high catalyst in oil reservoir, greatly reduce reaction activity, just likely under relatively low temperature conditions, realize the cracking of viscous crude in oil reservoir.
The people such as nineteen eighty-two Hyne point out that metal ion can accelerate aquathermolysis, and after this, people are to utilizing some catalyst to be studied in reaction.It is believed that superheated water can the transferring heat heated hydrocarbon, can be little molecule by pyrolysis and make some asphaltene molecules.Therefore, the viscosity of viscous crude and flow behavior also can improve.In addition, the heat of increase can provide driving force so that viscous crude is easy to flow, and improves its crude output.The normally used catalyst of aquathermolysis is all mineral, water-soluble, oil-soluble and disperse type catalyzer.The viscosity reducing effect of these catalyst is pressed mineral catalysis agent<water-soluble catalyst<oil-soluble catalyst<disperse type catalyzer.
Forefathers are more to the research of water-soluble, oil soluble metal salt catalyst, because the water-soluble metal salt catalyst is soluble in water, there is certain lipophile under high temperature, with the exposure level of crude oil, with oil-soluble catalyst, compare very poor, also insufficient, and in system, the content of water is higher, water is stronger to the 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 catalyst can not get fully playing like this.Therefore, the upgrading viscosity reduction extent of reaction will weaken.In addition, after moisture catalyst is distributed in viscous crude, also water must be removed, increase the cost of post processing.The metallic compound that oil-soluble catalyst contains organic group is 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 large to the upgrading viscosity reduction extent of reaction, after the organic group reaction, directly as product, do not need to separate, but oil-soluble catalyst is higher than the cost of water-soluble catalyst, and it is also not obvious to compare the water-soluble catalyst effect.
Summary of the invention
One of purpose of the present invention is, for decrease viscous crude or super viscosity of thickened oil, improves on the spot the viscous crude quality, and a kind of nanoscale reverse micelle microemulsion is provided, i.e. the loose catalyst of oversubscription;
For achieving the above object, the present invention adopts following technical scheme to realize:
A kind of for the upgrading viscosity reduction preparation method with the loose catalyst of oversubscription, 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 40 ~ 80 ℃ of temperature, after being controlled at 100 ~ 8000 rev/mins of stirring 5 ~ 300min, control supersonic frequency in 10 ~ 50KHz scope, through ultrasonic concussion 10 ~ 30min, obtain nanoscale reverse micelle microemulsion, required for the loose catalyst of oversubscription for the upgrading viscosity reduction;
Described transistion metal compound is at least one in VI B family's metallic compound or VIII B family non-noble metal compound;
Described VI B family metallic compound is at least one in chromium, molybdenum, tungsten and their compound thereof;
Described VIII B family non-noble metal compound is at least one in iron, cobalt, nickel and their compound thereof;
Described VI B family metallic compound is at least one in molybdate, tungstates, chromate, bichromate, molybdenum oxide, tungsten oxide, chromium oxide;
Described VIII B family 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, aviation kerosine, 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-butanol, n-amyl alcohol, isoamyl alcohol;
Another object of the present invention is: the application of the loose catalyst of above-mentioned oversubscription is provided, for this purpose, technical scheme provided by the invention is: this super loose type catalyst is for the reaction of upgrading viscosity reduction, its reaction temperature is controlled in 200 ℃ ~ 350 ℃ scopes, take the viscous crude quality as benchmark, described catalyst amount is 0.01 ~ 0.5% of viscous crude quality, and amount of water is 10 ~ 50% of viscous crude quality.
Adopt technical scheme provided by the invention, because super disperse type catalyzer can dissolve each other with raw material, the decentralization in raw material is very high, and catalytic activity is high, and the conversion ratio of upgrading is also just very high.The loose catalyst of oversubscription can improve the viscous crude quality on the spot by catalytic action, the chemical bond that in heavy component, bond energy is lower is easily ruptured, heavy component is transformed to the light components less containing carbon number, can realize permanently reducing the viscosity of viscous crude, thereby make to a great extent the viscous crude lighting, reduced the difficulty of viscous crude in the wellbore lift process, in pipeline transportation and processing.
The specific embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
embodiment 1
Molybdenum is the metal active center, prepares super disperse type catalyzer as upgrading viscosity reduction catalysis agent.The catalyst preparation takes following method to carry out:
The preparation of the loose DNAcarrier free molybdenum catalyst of oversubscription: non-ionic surface active agent Span80, lube base oil (350 ℃ of initial boiling points), viscosity are 6.8mPas (80 ℃), (NH
4)
6mo
7o
244H
2o is as the presoma of Kaolinite Preparation of Catalyst.Nanoscale microemulsion preparation experiment carries out under normal pressure, after the surfactant of use base oil 200g, 18g water, 9g and 1g help the ultrasonic dispersion of surfactant isoamyl alcohol, stir 6min under 4000r/min speed, the ultrasonic 10min of being treated to forms transparent reverse micelle microemulsion.The granularity of utilizing dynamic light scattering method to measure catalyst is 420nm.
The loose catalyst of the molybdenum base oversubscription of utilizing the method to prepare carries out upgrading viscosity reduction laboratory experiment to the super viscous crude in Liaohe Oil Field, when 200 ℃ of reaction temperatures, reaction, be 24h, oil-water ratio is 7:3, the catalyst addition is 0.3wt%, the reducing thick oil viscosity rate is up to 84.72%, wherein asphalt content is reduced to 5.35% by 8.78%, and gum level drops to 29.45% by 42.68%.Experiment shows, this catalyst, under 200 ℃ of cryogenic conditions, has the sticky effect of good catalytic reforming battle array to the super viscous crude in Liaohe Oil Field.
embodiment 2
Under the uniform temperature condition, the non-ionic surface active agent Tween80 aqueous solution, lube base oil (320 ℃ of initial boiling points), viscosity are 6mPas (80 ℃), the nickel acetate presoma as Kaolinite Preparation of Catalyst.Surfactant, the 2g of use base oil 150g, 16.8g water and 9g stirs 6min after helping surfactant n-butanol and nickel acetate 1.85g to mix under the 6500r/min rotating speed, and the ultrasonic 5min that is treated to, form stable nanometer micro-emulsion.The granularity of utilizing dynamic light scattering method to measure catalyst is 1400nm.
The loose catalyst of the Ni-based oversubscription of utilizing the method to prepare carries out upgrading viscosity reduction laboratory experiment to the super viscous crude in Liaohe Oil Field, when 250 ℃ of reaction temperatures, reaction, be 24h, oil-water ratio is 7:3, the catalyst addition is 0.3wt%, the reducing thick oil viscosity rate is up to 79.62%, wherein asphalt content is reduced to 5.76% by 8.78%, and gum level drops to 32.45% by 42.68%.Experiment shows, this catalyst, under 250 ℃ of cryogenic conditions, has the sticky effect of good catalytic reforming battle array to the super viscous crude in Liaohe Oil Field.
embodiment 3
Under 25 ℃, condition of normal pressure, non-ionic surface active agent Tween80 and Span80 are 6mPas (80 ℃), (NH according to 1:1 mixing, lube base oil (340 ℃ of initial boiling points), viscosity
4)
6mo
7o
244H
2o is as the presoma of Kaolinite Preparation of Catalyst.Surfactant is added in mixture to reduce the interfacial tension between oil-continuous phase and little water droplet.Use surfactant and the 2g of base oil 160g, 20g water and 9g to help surfactant n-butanol and (NH
4)
6mo
7o
244H
2o 1.87g stirs 6min after mixing under the 5000r/min rotating speed, and the ultrasonic 10min that is treated to, form stable nanometer micro-emulsion.The granularity of utilizing dynamic light scattering method to measure catalyst is 1800nm.
The loose catalyst of the molybdenum base oversubscription of utilizing the method to prepare carries out upgrading viscosity reduction laboratory experiment to the super viscous crude in Liaohe Oil Field, when 350 ℃ of reaction temperatures, reaction, be 24h, oil-water ratio is 7:3, the catalyst addition is 0.3wt%, the reducing thick oil viscosity rate is up to 81.45%, wherein asphalt content is reduced to 5.42% by 8.78 %, and gum level drops to 30.67% by 42.68%.Experiment shows, this catalyst, under 350 ℃ of cryogenic conditions, has the sticky effect of good catalytic reforming battle array to the super viscous crude in Liaohe Oil Field.
Claims (10)
- One kind for the upgrading viscosity reduction preparation method with the loose catalyst of oversubscription, it is characterized 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 40 ~ 80 ℃ of temperature, after being controlled at 100 ~ 8000 rev/mins of stirring 5 ~ 300min, control supersonic frequency in 10 ~ 50KHz scope, through ultrasonic concussion 10 ~ 30min, obtain nanoscale reverse micelle microemulsion, required for the loose catalyst of oversubscription for the upgrading viscosity reduction.
- According to claim 1 a kind of for the upgrading viscosity reduction preparation method with the loose catalyst of oversubscription, it is characterized in that, described transistion metal compound is at least one in VI B family's metallic compound or VIII B family non-noble metal compound.
- 3. according to claim 1ly for the upgrading viscosity reduction, with the loose catalyst of oversubscription, it is characterized in that, described VI B family metallic compound is at least one in chromium, molybdenum, tungsten and their compound thereof.
- 4. according to claim 1ly for the loose catalyst of oversubscription for the upgrading viscosity reduction, it is characterized in that, described VIII B family non-noble metal compound is at least one in iron, cobalt, nickel and their compound thereof.
- 5. according to claim 3ly for the loose catalyst of oversubscription for the upgrading viscosity reduction, it is characterized in that, described VI B family metallic compound is at least one in molybdate, tungstates, chromate, bichromate, molybdenum oxide, tungsten oxide, chromium oxide.
- 6. according to claim 4ly for the loose catalyst of oversubscription for the upgrading viscosity reduction, it is characterized in that, described VIII B family 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.
- According to claim 1 a kind of for the upgrading viscosity reduction preparation method with the loose catalyst of oversubscription, it is characterized in that, described base oil is at least one in lube base oil, aviation kerosine, straight-run diesel oil, straight run lubricating oil.
- According to claim 1 a kind of for the upgrading viscosity reduction preparation method with the loose catalyst of oversubscription, it is characterized in that, described surfactant is at least one in Span80, Tween80, Tween60, Span40.
- According to claim 1 a kind of for the upgrading viscosity reduction preparation method with the loose catalyst of oversubscription, it is characterized in that, described cosurfactant is at least one in normal propyl alcohol, n-butanol, n-amyl alcohol, isoamyl alcohol.
- 10. a kind of application with the loose catalyst of oversubscription for the upgrading viscosity reduction as claimed in claim 1, it is characterized in that, this super loose type catalyst is for the reaction of upgrading viscosity reduction, its reaction temperature is controlled in 200 ℃ ~ 350 ℃ scopes, take the viscous crude quality as benchmark, described catalyst amount is 0.01 ~ 0.5% of viscous crude quality, and amount of water is 10 ~ 50% of viscous crude quality.
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Cited By (4)
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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 |
| CN114058358A (en) * | 2021-12-08 | 2022-02-18 | 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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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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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