CN102019205B - Complex catalyst for viscosity reduction of thick oil by hydrothermal catalytic cracking and preparation and application thereof - Google Patents
Complex catalyst for viscosity reduction of thick oil by hydrothermal catalytic cracking and preparation and application thereof Download PDFInfo
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- CN102019205B CN102019205B CN200910092092XA CN200910092092A CN102019205B CN 102019205 B CN102019205 B CN 102019205B CN 200910092092X A CN200910092092X A CN 200910092092XA CN 200910092092 A CN200910092092 A CN 200910092092A CN 102019205 B CN102019205 B CN 102019205B
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Abstract
The invention relates to a complex catalyst for viscosity reduction of thick oil by hydrothermal catalytic cracking and application thereof. The complex catalyst is prepared by the following steps of: 1) selecting raw materials: selecting 2 to 3 mass parts of C12-C18 aliphatic carboxylic acid, 1 to 2 mass parts of ethylene dimine, 3 to 5 mass parts of sodium fluoroacetate, 1 to 2 mass parts of sodium hydroxide, 3 to 5 mass parts of nickel chloride hydrate and 140 to 180 mass parts of toluene; and 2) mixing the C12-C18 carboxylic acid and ethylene dimine, then heating to 160 to 180 DEG C in anoil bath and reacting for 2 to 3 hours, cooling to 90 to 95 DEG C, adding sodium chloroacetate-containing aqueous solution, stirring, reacting for 40 to 50 minutes and then adding NaOH, continuously reacting for 10 to 13 hours at the temperature of between 90 and 100 DEG C, finally adding the NiCl2.6H2O and the toluene, refluxing and splitting water for 3 to 5 hours and filtering, and performing reduced pressure desolvation on the filtrate to obtain the catalyst, wherein after the reaction is finished, the viscosity reduction rate of the thick oil reaches over 90 percent, and 9 to 15 percent of heavy component is cracked into a light component.
Description
Technical field:
The present invention relates to a kind of complex catalyst and preparation and application of thick oil hydrothermal catalytic cracking viscosity reduction.
Background technology:
Hydrothermal catalytic cracking is a kind of comparatively effectively thickened oil recovery method; Hydrothermal catalytic cracking viscosity reduction heavy crude producing technology is when in oil reservoir, injecting high pressure, high temperature vapor; Add suitable catalyst and other auxiliary agent, as an available hydrothermal cracking and catalyzing reactor of cheapness, make viscous crude under hydrothermal condition, realize catalytic pyrolysis on stratum itself; Irreversibly reduce heavy components content or change its molecular structure; Make the viscous crude lighting to a certain extent, reduce the viscosity of viscous crude, make viscous crude be easy to exploitation, collect defeated and processing.This is a kind of new approaches of thickened oil recovery.The hydrothermal catalytic cracking viscosity reduction has following technical advantage: become little molecule after the cracking of viscous crude bulky molecular catalysis; Irreversibly reduced the viscosity of crude oil; Improved the flow event of crude oil in formation pore, viscosity reduces to lifting and collection normal temperature under defeated the provide advantage of crude oil in pit shaft.Viscous crude medium pitch matter, wax and colloid become little molecule through catalytic cracking, can change the quality of viscous crude, after big molecule viscous crude cracking is little molecule thin oil or light oil; Not only viscosity reduces, and the vapour pressure rising, thereby has increased the oil reservoir energy; For utmost point advantageous conditions has been created in oil recovery, after viscous crude generation part catalytic pyrolysis becomes light oil, can dissolve and dilute still uncracked viscous crude; Thereby improve the seepage flow condition of oil product, save the outer light oil of mixing that is used to dilute.
Present thick oil hydrothermal catalytic cracking viscosity depressant mainly contains following several kinds: high price transition metal ions water-soluble catalyst, oil-soluble transition metal compound catalyst, super acidic catalyst, ionic-liquid catalyst.It is higher that these thinners exist serviceability temperature, and universality is poor, poor with the crude oil contact, and the shortcoming that working concentration is big, The field are difficult to prove effective.Therefore, develop new hydrothermal catalytic cracking viscosity depressant, the mining requirement that satisfies special ultra viscous crude has great significance.
Summary of the invention:
The purpose of this invention is to provide a kind of complex catalyst and preparation and application of thick oil hydrothermal catalytic cracking viscosity reduction; Complex catalyst can contact with crude oil more fully, and viscosity reducing effect is better at low temperatures, have certain universality, and working concentration is little.
A kind of preparation method with thick oil hydrothermal catalytic cracking viscosity depressant of chelation structure of the present invention is characterized in that it comprises the steps:
Choosing raw material is C
12～18Aliphatic carboxylic acid, ethylenediamine, sodium chloroacetate, NaOH and hydration nickel chloride, its mass ratio are 2～3,1～2,3～5,1～2,3～5.
With C
12～182～3 parts of carboxylic acids (mass number) are heated to 160～180 ℃ of reaction 2～3h with oil bath after 1～2 part of ethylenediamine mixes.Be cooled to 90～95 ℃ of addings and contain and add NaOH1～2 part behind the aqueous solution stirring reaction 40～50min of 3～5 parts of sodium chloroacetates again, continue reaction 10～13h in 90～100 ℃.Add 3～5 parts of NiCl at last
2.6H
2O and 140～180 parts of toluene filter behind reflux water-dividing 3～5h, promptly get catalyst behind the filtrate decompression precipitation.
(annotate: all reagent are chemical pure)
This catalyst is used for thick oil hydrothermal catalytic cracking viscosity reduction reaction, and reaction temperature is 170 ℃～200 ℃, and catalyst amount is for being benchmark with whole system quality, catalyst amount 0.03～0.1w%, and amount of water is more than or equal to 25%.
The invention has the beneficial effects as follows: the amphipathic thinner that can impel of part contacts with crude oil more fully in this thinner; Bring into play the catalytic activity of transition metal more fully; And this thinner can (be lower than 200 ℃) and make special ultra viscous crude generation part cracking at a lower temperature; Thereby reduce the viscosity of viscous crude, improve the viscous crude quality to a certain extent.This catalyst can be used for hydrothermal catalytic cracking viscosity reduction under the heavy oil wells, when carrying out steam soak, these article is injected oil reservoir by a certain percentage, can obtain the irreversible light components that changes into of part heavy component that obvious viscosity reducing effect also can make viscous crude.Because industrialization is made simple, and is free from environmental pollution, convenient site operation, consumption is little, and this catalyst is having wide application prospect aspect the thick oil underground well hydrothermal catalytic cracking viscosity reduction upgrading of oil field.
The specific embodiment:
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention not only is confined to following embodiment below in conjunction with embodiment.
Embodiment 1:
5gC
12Carboxylic acid mixes the back oil bath and is heated to 180 ℃ of reaction 2h with the 2.0g ethylenediamine.Be cooled to 90 ℃, add the aqueous solution that contains the 9.5g sodium chloroacetate.Add 3.8gNaOH again after stirring 40min, continue reaction 12h in 93 ℃.Add 8.0gNiCl
2.6H
2O and 150ml toluene filter behind the reflux water-dividing 3h, get catalyst behind the filtrate decompression precipitation.Commercial production can be amplified in proportion with industrial raw material and got final product.
These article are applied to flat 2 viscous crude of the cold 42-in Liaohe Oil Field; Getting proper catalyst and viscous crude and water and place autoclave, issue unboiled water thermocatalytic cracking reaction at 170 ℃～200 ℃, is benchmark with whole system quality wherein; Catalyst amount 0.03～0.1w%; Amount of water is greater than 25%, and reaction back reducing thick oil viscosity rate reaches more than 90%, and has 11% heavy component to be cracked into light components.
Embodiment 2:
3gC
12Carboxylic acid mixes the back oil bath and is heated to 160 ℃ of reaction 3h with the 1.8g ethylenediamine.Be cooled to 95 ℃, add the aqueous solution that contains the 7.5g sodium chloroacetate.Add 2.0gNaOH again after stirring 45min, continue reaction 11h in 95 ℃.Add 6.1gNiCl
2.6H
2O and 150ml toluene filter behind the reflux water-dividing 3h, get catalyst behind the filtrate decompression precipitation.Commercial production can be amplified in proportion with industrial raw material and got final product.
These article are applied to Liaohe Oil Field Du 813-39-36 viscous crude; Getting proper catalyst and viscous crude and water and place autoclave, issue unboiled water thermocatalytic cracking reaction at 170 ℃～200 ℃, is benchmark with whole system quality wherein; Catalyst amount 0.03～0.1w%; Amount of water is greater than 25%, and reaction back reducing thick oil viscosity rate reaches more than 90%, and has 9.8% heavy component to be cracked into light components.
Embodiment 3:
4gC
16Carboxylic acid mixes the back oil bath and is heated to 180 ℃ of reaction 2.5h with the 1.7g ethylenediamine.Be cooled to 90 ℃, add the aqueous solution that contains the 6.5g sodium chloroacetate.Add 3.2gNaOH again after stirring 46min, continue reaction 12h in 90 ℃.Add 5.5.0gNiCl
2.6H
2O and 170ml toluene filter behind the reflux water-dividing 4h, get catalyst behind the filtrate decompression precipitation.Commercial production can be amplified in proportion with industrial raw material and got final product.
These article are applied to Henan Oil Field G540 viscous crude; Getting proper catalyst and viscous crude and water and place autoclave, issue unboiled water thermocatalytic cracking reaction at 150 ℃～200 ℃, is benchmark with whole system quality wherein; Catalyst amount 0.03～0.1w%; Amount of water is greater than 25%, and reaction back reducing thick oil viscosity rate reaches more than 90%, and has 15% heavy component to be cracked into light components.
Embodiment 4:
5gC
18Carboxylic acid mixes the back oil bath and is heated to 180 ℃ of reaction 3h with the 2.0g ethylenediamine.Be cooled to 90 ℃, add the aqueous solution that contains the 8.3g sodium chloroacetate.Add 3.5gNaOH again after stirring 50min, continue reaction 13h in 95 ℃.Add 7.2gNiCl
2.6H
2O and 180ml toluene filter behind the reflux water-dividing 5h, get catalyst behind the filtrate decompression precipitation.Commercial production can be amplified in proportion with industrial raw material and got final product.
These article are applied to flat 2 viscous crude of Shengli Oil Field Zheng 6-; Getting proper catalyst and viscous crude and water and place autoclave, issue unboiled water thermocatalytic cracking reaction at 150 ℃～200 ℃, is benchmark with whole system quality wherein; Catalyst amount 0.03～0.1w%; Amount of water is greater than 25%, and reaction back reducing thick oil viscosity rate reaches more than 90%, and has 10.5% heavy component to be cracked into light components.
Claims (4)
1. the preparation method of the complex catalyst of a thick oil hydrothermal catalytic cracking viscosity reduction is characterized in that: 5gC
12Carboxylic acid mixes the back oil bath and is heated to 180 ℃ of reaction 2h with the 2.0g ethylenediamine, be cooled to 90 ℃, adds the aqueous solution that contains the 9.5g sodium chloroacetate, adds 3.8g NaOH again behind the stirring 40min, in 93 ℃ of continuation reaction 12h, adds 8.0g NiCl
2.6H
2O and 150ml toluene filter behind the reflux water-dividing 3h, get catalyst behind the filtrate decompression precipitation.
2. the preparation method of the complex catalyst of a thick oil hydrothermal catalytic cracking viscosity reduction is characterized in that: 5gC
18Carboxylic acid mixes the back oil bath and is heated to 180 ℃ of reaction 3h with the 2.0g ethylenediamine, be cooled to 90 ℃, adds the aqueous solution that contains the 8.3g sodium chloroacetate, adds 3.5g NaOH again behind the stirring 50min, in 95 ℃ of continuation reaction 13h, adds 7.2g NiCl
2.6H
2O and 180ml toluene filter behind the reflux water-dividing 5h, get catalyst behind the filtrate decompression precipitation.
3. the complex catalyst of a thick oil hydrothermal catalytic cracking viscosity reduction is characterized in that: preparation method's preparation of the complex catalyst of thick oil hydrothermal catalytic cracking viscosity reduction according to claim 1.
4. the application of the complex catalyst of a thick oil hydrothermal catalytic cracking viscosity reduction according to claim 3; It is characterized in that: this complex catalyst is used for the reaction of thick oil hydrothermal catalytic cracking viscosity reduction; Reaction temperature is 170 ℃～200 ℃; Catalyst amount is for being benchmark with whole system quality, catalyst amount 0.03～0.1w%, amount of water＞25%.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103111327B (en) * | 2011-11-17 | 2015-11-25 | 中国石油化工股份有限公司 | Researches on Aquathermolysis Catalysts for Heavy Crude Oils and preparation method thereof and transition metal complex and part |
| CN103375157B (en) * | 2012-04-26 | 2016-03-30 | 中国石油化工股份有限公司 | Transmission method adopted by a kind of crude oil |
| CN103937467B (en) * | 2013-01-21 | 2016-08-03 | 中国石油化工股份有限公司 | Thick oil hydrothermal catalytic thinner and preparation method thereof and transient metal complex and part |
| CN103396779B (en) * | 2013-08-07 | 2015-10-14 | 中国海洋石油总公司 | A kind of oil by injecting air buffering catalytic oxidation of thick milk sap Catalysts and its preparation method |
| CN103566978B (en) * | 2013-10-25 | 2015-12-09 | 中国地质大学（武汉） | Copper, the agent of molybdenum bimetallic center reducing viscosity in hydrothermal cracking and catalyzing thick oil and preparation method thereof |
| CN104830305B (en) * | 2015-04-03 | 2018-03-13 | 长江大学 | Thickened oil recovery active form catalytic thinner and its preparation method and application |
| CN107880866B (en) * | 2017-05-23 | 2021-03-23 | 西南石油大学 | Heavy oil in-situ catalytic modified metal nanocrystalline viscosity reducer and preparation method thereof |
| CN108212213A (en) * | 2018-01-22 | 2018-06-29 | 西安石油大学 | A kind of preparation method of low temperature thick oil hydrothermal cracking viscosity reduction catalyst |
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| US4743357A (en) * | 1983-12-27 | 1988-05-10 | Allied Corporation | Catalytic process for production of light hydrocarbons by treatment of heavy hydrocarbons with water |
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| CN101440276A (en) * | 2007-11-19 | 2009-05-27 | 中国石化集团河南石油勘探局 | Aquathermolysis catalytic thinner for heavy oil exploration via steam injection and preparation thereof |
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