CN102516969A - Preparation method of thickened oil viscosity reducer with dual structure of hydrogen donor and catalytic center - Google Patents
Preparation method of thickened oil viscosity reducer with dual structure of hydrogen donor and catalytic center Download PDFInfo
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Abstract
The invention relates to a preparation method of aquathermolysis catalysis viscosity reducer for thickened oil recovery, in particular to a preparation method of thickened oil viscosity reducer with a dual structure of hydrogen donor and catalytic center, which is characterized by comprising the following steps: (1) selecting the following raw materials in parts by weight: 17-19 parts of p-toluenesulfonic acid, 4-5 parts of cupric oxide powder and 40-60 parts of water; and (2) dissolving the p-toluenesulfonic acid in the water, heating to 40-60 DEG C, adding the cupric oxide powder, stirring for 0.5-1 hour at the temperature of 80-90 DEG C, filtering while hot, putting filtrate in an oven for drying at the temperature of 50-70 DEG C for 10-12 hours, and obtaining the thickened oil viscosity reducer with the dual structure of hydrogen donor and catalytic center. The viscosity reducer prepared by the method has favorable viscosity reducing effect at the temperature below 200 DEG C, and the preparation process is simple.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the reducing viscosity in hydrothermal cracking and catalyzing agent of viscous oil recovery.
Background technology
Viscous crude is the important component part of global petroleum resources, has the resource potential than the high several times of conventional oil resource, and viscous crude accounts for more than 70% in the global residual petroleum resource.Along with the continuous development of global economy, countries in the world are more and more big to the demand of oil, take all factors into consideration the current mining and the heavy oil reserves of conventional crude, can predict that viscous crude will occupy extremely important status in national energy strategy from now on.
Reducing viscosity in hydrothermal cracking and catalyzing heavy crude producing technology is through to the oil reservoir injecting steam time, adds the reducing viscosity in hydrothermal cracking and catalyzing agent, with oil reservoir as a natural reactor drum; Utilize the heat of steam; Make viscous crude under hydrothermal condition, realize catalytic pyrolysis, the macromole in the viscous crude partly is cracked into small molecules, part changes the quality of viscous crude; The viscosity of irreversible reduction viscous crude, thus reach the purpose of heavy crude producing.The key of this technology is the development of reducing viscosity in hydrothermal cracking and catalyzing agent, and the problem of the reducing viscosity in hydrothermal cracking and catalyzing agent ubiquity universality difference of reporting at present.Chinese scholars is discovered; Some is used the not good viscous crude of reducing viscosity in hydrothermal cracking and catalyzing agent viscosity reducing effect separately; Some hydrogen supply agents of composite adding (like toluene, formic acid, naphthane etc.), viscosity reducing effect can improve a lot, and they think that hydrogen supply agent and catalytic thinner have synergy to the thick oil hydrothermal scission reaction; But when using at the scene; Composite use hydrogen supply agent and catalytic thinner can bring certain difficulty to preparation of construction and technology, also can increase Financial cost, are difficult to adapt to the needs of situ extraction.Therefore we have designed a kind of viscosity-depression agent that integrates hydrogen supply and katalysis, make it have general hydrogen supply agent with catalytic thinner the viscosity reducing effect when composite, reduce cost again simultaneously and make things convenient for the scene use.The development of this new catalytic viscosity-depression agent for the exploitation of the ultra viscous crude of spy with significant.
Summary of the invention
The object of the present invention is to provide the preparation method of the heavy crude thinner of a kind of tool hydrogen donor and catalytic center dual structure, the viscosity-depression agent of this method preparation is respond well at 200 ℃ of following viscosity reductions, and preparation technology is simple.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: the preparation method of the heavy crude thinner of tool hydrogen donor and catalytic center dual structure is characterized in that it comprises the steps:
1) choose raw material: the parts by weight by tosic acid, cupric oxide powder, water are: 17～19 parts of tosic acid, 4～5 parts of cupric oxide powders, 40～60 parts in water, choose tosic acid, cupric oxide powder and water;
2) with being heated to 40～60 ℃ in the tosic acid water-soluble (at container); Then add cupric oxide powder; (heating) stirring is 0.5～1 hour under 80～90 ℃; Filtered while hot places baking oven 50～70 ℃ of bakings 10～12 hours (oven dry) down filtrating, obtains the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.
The parts by weight of described tosic acid, cupric oxide powder, water are: 18 parts of tosic acid, 4.5 parts of cupric oxide powders, 50 parts in water.
Described tosic acid is soluble in water to be heated to 50 ℃.
Behind the described adding cupric oxide powder, stirred 0.5 hour down at 85 ℃.
The present invention uses MS4.4 (analog calculation of Materials Studio4.4-Materials science) software that the structure of viscosity-depression agent is designed, and to its hydrothermal cracking and catalyzing reaction carrying out analog calculation, confirms obviously to reduce the structure of the viscosity-depression agent of reaction activity.A kind of bifunctional reducing viscosity in hydrothermal cracking and catalyzing thick oil agent that has is provided, has instructed the preparation of new catalytic viscosity-depression agent, simulating starts with directly instructing synthesizes by calculating, and has shortened the development time of reducing viscosity in hydrothermal cracking and catalyzing thick oil agent greatly.
The viscosity-depression agent that adopts method of the present invention to obtain integrates hydrogen donor structure and catalytic center; Can bring into play the catalytic activity of transition metal; Can bring into play the synergy of hydrogen donor structure again, this viscosity-depression agent can (be lower than 200 ℃) at a lower temperature makes special ultra viscous crude generation part cracking, changes the chimeric mode of its molecular structure and family's component molecule thereof simultaneously; Obviously reduce the viscosity of viscous crude, promoted the quality of viscous crude to a certain extent.
The invention has the beneficial effects as follows: the viscosity-depression agent of this method preparation is respond well at 200 ℃ of following viscosity reductions.
This viscosity-depression agent not only can be used for the exploitation of common heavy oil; And the reducing viscosity in hydrothermal cracking and catalyzing that can be used for special ultra viscous crude is exploited; Preparation technology is simple, and is with low cost, and has and be superior to general hydrogen supply agent and the catalytic thinner viscosity reducing effect and strong universality when composite; Adapt to existing production practice, therefore good practicability and vast market prospect are arranged.
Embodiment
In order to understand the present invention better, further set forth content of the present invention below in conjunction with instance, but content of the present invention not only is confined to following embodiment.Related viscosity is that the DV-II+ type control type viscometer able to programme that adopts U.S. Briekfield company to produce records in the embodiment of the invention.
Embodiment 1:
Design: utilization MS4.4 (analog calculation of Materials Studio4.4-Materials science) software designs the structure of viscosity-depression agent; With thiophene C4H4S is model compound; Common hydrogen donor structure (toluene) and catalytic center (metallic copper atom) are combined; Hydrothermal cracking and catalyzing reaction carrying out analog calculation to thiophene C4H4S; The calculation result that the hydrothermal cracking and catalyzing that contrast has or not catalytic thinner to participate in reacts; The participation afterreaction activation energy that discovery is reflected at catalytic thinner has dropped to 0.955ev by 2.484ev, and the viscosity-depression agent of design is described, and reaction has obvious catalysis to the hydrothermal cracking of model compound, thereby confirms the structure of catalytic thinner.
Preparation: in there-necked flask, the 18g tosic acid is used the 50ml water dissolution, in thermostat water bath, be heated to 50 ℃; Under agitation condition; Slowly add the 4.5g cupric oxide powder, react 0.5h down at 85 ℃, reaction finishes the back filtered while hot; Place baking oven 60 ℃ of bakings 11 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the special viscous crude (50 ℃ of following viscosity are 39000mPas) of Xinjiang Karamay oilfield; This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of viscosity-depression agent accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 89%, and has 9.2% heavy component to be cracked into light component.The viscosity-depression agent of this method preparation is at 200 ℃ of following viscosity reductions respond well (viscosity break ratio reaches more than 85%).
Embodiment 2:
Design: with embodiment 1.
Preparation: in there-necked flask, the 17g tosic acid is used the 50ml water dissolution, in thermostat water bath, be heated to 50 ℃; Under agitation condition; Slowly add the 4g cupric oxide powder, react 0.5h down at 80 ℃, reaction finishes the back filtered while hot; Place baking oven 60 ℃ of bakings 12 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the special viscous crude (50 ℃ of following viscosity are 41000mPas) of Shengli Oil Field; This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 86%, and has 8.1% heavy component to be cracked into light component.
Embodiment 3:
Design: with embodiment 1.
Preparation: in there-necked flask, the 19g tosic acid is used the 50ml water dissolution, in thermostat water bath, be heated to 50 ℃; Under agitation condition; Slowly add the 5g cupric oxide powder, react 0.5h down at 90 ℃, reaction finishes the back filtered while hot; Place baking oven 60 ℃ of bakings 10 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the ultra viscous crude of Xinjiang Karamay oilfield (50 ℃ of following viscosity are 85000mPas); This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 94%, and has 10% heavy component to be cracked into light component.
Embodiment 4:
Design: with embodiment 1.
Preparation: in there-necked flask, the 17g tosic acid is used the 50ml water dissolution, in thermostat water bath, be heated to 50 ℃; Under agitation condition; Slowly add the 4.5g cupric oxide powder, react 0.5h down at 85 ℃, reaction finishes the back filtered while hot; Place baking oven 60 ℃ of bakings 12 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: with the present embodiment product application in Xinjiang the ultra viscous crude of Karamay oilfield (50 ℃ of following viscosity are 100000mPas); This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 90%, and has 11.2% heavy component to be cracked into light component.
Embodiment 5:
Design: with embodiment 1.
Preparation: in there-necked flask, the 19g tosic acid is used the 50ml water dissolution, in thermostat water bath, be heated to 50 ℃; Under agitation condition; Slowly add the 4.5g cupric oxide powder, react 0.5h down at 80 ℃, reaction finishes the back filtered while hot; Place baking oven 60 ℃ of bakings 10 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the ultra viscous crude of Xinjiang Karamay oilfield (50 ℃ of following viscosity are 85000mPas); This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 93%, and has 10.2% heavy component to be cracked into light component.
Embodiment 6:
Design: with embodiment 1.
Preparation: in there-necked flask, the 18g tosic acid is used the 50ml water dissolution, in thermostat water bath, be heated to 50 ℃; Under agitation condition; Slowly add the 5g cupric oxide powder, react 0.5h down at 90 ℃, reaction finishes the back filtered while hot; Place baking oven 60 ℃ of bakings 12 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the ultra viscous crude of Xinjiang Karamay oilfield (50 ℃ of following viscosity are 85000mPas); This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 92%, and has 9.8% heavy component to be cracked into light component.
Embodiment 7:
Preparation: in there-necked flask, the 18g tosic acid is used the 40ml water dissolution, in thermostat water bath, be heated to 40 ℃; Under agitation condition; Slowly add the 5g cupric oxide powder, react 1.0h down at 90 ℃, reaction finishes the back filtered while hot; Place baking oven 50 ℃ of bakings 11 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the ultra viscous crude of Xinjiang Karamay oilfield (50 ℃ of following viscosity are 85000mPas); This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 94%, and has 10.5% heavy component to be cracked into light component.
Embodiment 8:
Preparation: in there-necked flask, the 18g tosic acid is used the 60ml water dissolution, in thermostat water bath, be heated to 60 ℃; Under agitation condition; Slowly add the 5g cupric oxide powder, react 0.5h down at 90 ℃, reaction finishes the back filtered while hot; Place baking oven 70 ℃ of bakings 10 hours (oven dry) down filtrating, obtain the heavy crude thinner (blue colored crystal) of tool hydrogen donor and catalytic center dual structure.Industrial production can be amplified in proportion with industrial raw material and got final product.
Use: present embodiment product (heavy crude thinner of tool hydrogen donor and catalytic center dual structure) is applied to the ultra viscous crude of Xinjiang Karamay oilfield (50 ℃ of following viscosity are 85000mPas); This catalytic thinner (present embodiment product), water and viscous crude are placed autoclave; Issue unboiled water thermocatalysis scission reaction at 200 ℃; Be benchmark with whole system quality wherein, the consumption of catalytic thinner accounts for 0.2～0.3wt% (mass percent), and the consumption of water accounts for 25～40wt% (mass percent); Reaction back reducing thick oil viscosity rate reaches 91%, and has 9.7% heavy component to be cracked into light component.
Claims (4)
1. have a preparation method of heavy crude thinner of hydrogen donor and catalytic center dual structure, it is characterized in that it comprises the steps:
1) choose raw material: the parts by weight by tosic acid, cupric oxide powder, water are: 17～19 parts of tosic acid, 4～5 parts of cupric oxide powders, 40～60 parts in water, choose tosic acid, cupric oxide powder and water;
2) be heated to 40～60 ℃ with tosic acid is soluble in water; Then add cupric oxide powder, stirred 0.5～1 hour filtered while hot at 80～90 ℃ down; Place baking oven to dry by the fire 10～12 hours down filtrating, obtain the heavy crude thinner of tool hydrogen donor and catalytic center dual structure at 50～70 ℃.
2. the preparation method of the heavy crude thinner of tool hydrogen donor according to claim 1 and catalytic center dual structure is characterized in that: the parts by weight of described tosic acid, cupric oxide powder, water are: 18 parts of tosic acid, 4.5 parts of cupric oxide powders, 50 parts in water.
3. the preparation method of the heavy crude thinner of tool hydrogen donor according to claim 1 and catalytic center dual structure is characterized in that: described tosic acid is soluble in water to be heated to 50 ℃.
4. the preparation method of the heavy crude thinner of tool hydrogen donor according to claim 1 and catalytic center dual structure is characterized in that: behind the described adding cupric oxide powder, stirred 0.5 hour down at 85 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242815A (en) * | 2013-05-10 | 2013-08-14 | 中国地质大学（武汉） | Preparation method of thickened oil aqua-thermolysis catalysis viscosity reducer with double structures of hydrogen supply and catalytic activity center |
| CN104818009A (en) * | 2015-04-03 | 2015-08-05 | 中国地质大学（武汉） | Preparation method of viscous oil hydrothermal cracking catalysis viscosity reducer having double structures of hydrogen supply and metal catalysis center |
| CN105368433A (en) * | 2015-11-20 | 2016-03-02 | 中国石油天然气股份有限公司 | Heavy oil aquathermolysis catalytic viscosity reducer and preparation method thereof |
| CN107142096A (en) * | 2017-06-14 | 2017-09-08 | 西南石油大学 | A kind of method that biomass auxiliary viscous crude self-catalysis modifies viscosity reduction |
| CN106543998B (en) * | 2016-10-19 | 2020-06-12 | 中国石油化工股份有限公司 | Hydrothermal cracking catalytic viscosity reducer and preparation method thereof |
| CN112342005A (en) * | 2021-01-05 | 2021-02-09 | 山东奥士德石油技术有限公司 | Environment-friendly efficient thick oil viscosity reducer |
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| CN101722040A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Copper p-toluene sulfonate loaded catalyst and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242815A (en) * | 2013-05-10 | 2013-08-14 | 中国地质大学（武汉） | Preparation method of thickened oil aqua-thermolysis catalysis viscosity reducer with double structures of hydrogen supply and catalytic activity center |
| CN104818009A (en) * | 2015-04-03 | 2015-08-05 | 中国地质大学（武汉） | Preparation method of viscous oil hydrothermal cracking catalysis viscosity reducer having double structures of hydrogen supply and metal catalysis center |
| CN105368433A (en) * | 2015-11-20 | 2016-03-02 | 中国石油天然气股份有限公司 | Heavy oil aquathermolysis catalytic viscosity reducer and preparation method thereof |
| CN105368433B (en) * | 2015-11-20 | 2018-12-25 | 中国石油天然气股份有限公司 | A kind of reducing viscosity in hydrothermal cracking and catalyzing thick oil agent and preparation method thereof |
| CN106543998B (en) * | 2016-10-19 | 2020-06-12 | 中国石油化工股份有限公司 | Hydrothermal cracking catalytic viscosity reducer and preparation method thereof |
| CN107142096A (en) * | 2017-06-14 | 2017-09-08 | 西南石油大学 | A kind of method that biomass auxiliary viscous crude self-catalysis modifies viscosity reduction |
| CN107142096B (en) * | 2017-06-14 | 2020-01-14 | 西南石油大学 | Biomass-assisted thickened oil autocatalytic modification viscosity reduction method |
| CN112342005A (en) * | 2021-01-05 | 2021-02-09 | 山东奥士德石油技术有限公司 | Environment-friendly efficient thick oil viscosity reducer |
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Application publication date: 20120627 |