CN103111327A - Thickened oil aquathermolysis catalyst, preparation method thereof, transition metal complex and ligand - Google Patents
Thickened oil aquathermolysis catalyst, preparation method thereof, transition metal complex and ligand Download PDFInfo
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- CN103111327A CN103111327A CN2011103646036A CN201110364603A CN103111327A CN 103111327 A CN103111327 A CN 103111327A CN 2011103646036 A CN2011103646036 A CN 2011103646036A CN 201110364603 A CN201110364603 A CN 201110364603A CN 103111327 A CN103111327 A CN 103111327A
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Abstract
The invention relates to a thickened oil aquathermolysis catalyst, a preparation method of the thickened oil aquathermolysis catalyst, a transition metal complex and a ligand. The catalyst comprises the transition metal complex as shown in the formula I, wherein R1 and R2 are independently the C1-C6 alkyls or C6-C10 aryls; M is the metal in VB, VIB, VIIB or VIII group; A is an end group; m is the integer ranging from 3 to 28; and n is the integer ranging from 1 to 3.
Description
Technical field
The present invention relates to a kind of Researches on Aquathermolysis Catalysts for Heavy Crude Oils and preparation method thereof, the invention still further relates to transient metal complex and part thereof that this catalyst contains.
Background technology
The reducing viscosity in hydrothermal cracking and catalyzing technology is a kind of effective the Technology of Heavy Oil Recovery, this technology is by adding catalyst and the auxiliary agent of special properties in oil reservoir injection steam, make the weak chemical bond fracture of bond energy in the viscous crude component, change viscous crude molecular aggregates state, reduce viscosity of thickened oil, improve liquidity, reach the purpose that improves recovery ratio.Existing hydrothermal cracking catalyst is generally transition metal salt, and its reaction efficiency is also undesirable, be embodied on the one hand need to be very high reaction temperature (240 ℃～300 ℃), be embodied on the other hand the reaction time (24～60 hours) that need to grow.CN1944572A has reported a kind of preparation method who contains the thick oil hydrothermal catalytic cracking viscosity depressant of amphiphilic structure, contains the thick oil hydrothermal catalytic cracking viscosity depressant of amphiphilic structure with aromatic sulfonic acid and iron oxide or iron powder preparation.CN102019205A has reported a kind of complex catalyst and preparation and application of thick oil hydrothermal catalytic cracking viscosity reduction, and this complex catalyst utilizes aliphatic carboxylic acid, ethylenediamine, sodium chloroacetate hydration nickel chloride etc. to prepare.Above technical scheme has realized the activated centre is incorporated on amphipathic main chain, and its transition metal central ion with catalytic activity all is in water-soluble end.CN1948349A and CN101007286A have reported respectively preparation and the application of cyclodextrin and surfactant inclusion catalyst, and the stability of this inclusion compound and the homogeneity of catalyst distribution are relatively poor, and the effect in practical application is had a negative impact.
Summary of the invention
The invention provides a kind of hydrothermal cracking catalyst and preparation method thereof, the present invention also provides transient metal complex that above-mentioned catalyst contains and for the preparation of the part of this transient metal complex.
A kind of Researches on Aquathermolysis Catalysts for Heavy Crude Oils contains the transient metal complex shown in formula I,
In formula I, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, M is the metal of VB, VIB, VIIB or VIII family, and A is end group, and m is 3～28 integer, and n is 1～3 integer.
Under preferable case, R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
M is preferably 13～18 integer.
M is preferably the metal of VIB, VIIB or VIII family, more preferably iron, cobalt, nickel, chromium or manganese.
Those skilled in the art know that the scope of end group A of the present invention, when it refers to prepare APEO, introduced the group of the polyethers end of the chain by initiator.Described end group A is preferably the alkoxyl of C12～C25 or the phenol oxygen base of C8～C20.
A kind of preparation method of Researches on Aquathermolysis Catalysts for Heavy Crude Oils comprises:
(1) with APEO and halogenating agent reaction, obtain the halo APEO;
(2) with the halo APEO of step (1) preparation and the formula II compound reaction of alkali treatment, obtain the compound shown in formula III;
(3) in solvent, formula III compound and transition metal reactant salt that step (2) is made;
In formula II and formula III, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, A is end group, and m is 3～28 integer, and transition metal salt is the slaine of VB, VIB, VIIB or VIII family.
M is preferably 13～18 integer.
The present invention has no particular limits the end group of APEO.The end group of described APEO is preferably the alkoxyl of C12～C25 or the phenol oxygen base of C8～C20.
Described halogenating agent can adopt conventional halogenating agent, is halogenating agent as adopting thionyl chloride, phosphorus trichloride, phosphorus pentachloride or hydrogen chloride.
Those skilled in the art know that the scope of alkali described in step (2) and the implication of " alkali treatment ", described alkali refers to remove the alkali of hydrogen on beta-diketon middle carbon atom, and described " alkali treatment " refers to remove hydrogen on beta-diketon middle carbon atom with alkali.The present invention can adopt alkali metal alcoholates, alkali metal hydride or alkali metal to remove hydrogen on beta-diketon middle carbon atom.
Under preferable case, R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
M is preferably the slaine of VIB, VIIB or VIII family, more preferably molysite, cobalt salt, nickel salt, chromic salts or manganese salt.
Those skilled in the art know that the scope of solvent described in step (3), it refers to can dissolve at least a kind of organic or inorganic solvent of reaction substrate.Described solvent is preferably one or more in C1～C6 alcohol, more preferably one or more in C1～C3 alcohol.
The reaction time of step (1) is preferably 3～24 hours, more preferably 3～10 hours.
The reaction temperature of step (1) is preferably-10～120 ℃, more preferably 40～100 ℃.
The reaction time of step (2) is preferably 2～10 hours, more preferably 4～8 hours.
The reaction temperature of step (2) is preferably 60～160 ℃, more preferably 80～120 ℃.
The reaction time of step (3) is preferably 2～12 hours, more preferably 4～8 hours.
The reaction temperature of step (3) is preferably 20～120 ℃, more preferably 40～80 ℃.
By the step in said method (1) and step (2), can prepare the organic ligand shown in formula III.After the reaction of step (3) finishes, can directly the reactant liquor that contains product be used for catalysis thick oil hydrothermal cracking reaction, need not to separate solvent; Also can steam solvent, obtain solid product, then use it for catalysis thick oil hydrothermal cracking reaction; The solid product of step (3) further can also be separated, purifies, obtain the transient metal complex shown in formula I, then use it for catalysis thick oil hydrothermal cracking reaction.
A kind of transient metal complex has the structure shown in formula I,
In formula I, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, M is the metal of VB, VIB, VIIB or VIII family, and A is end group, and m is 3～28 integer, and n is 1～3 integer.
Under preferable case, R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
M is preferably 13～18 integer.
M is preferably the metal of VIB, VIIB or VIII family, more preferably iron, cobalt, nickel, chromium or manganese.
Those skilled in the art know that the scope of end group A of the present invention, when it refers to prepare APEO, introduced the group of the polyethers end of the chain by initiator.Described end group A is preferably the alkoxyl of C12～C25 or the phenol oxygen base of C8～C20.
The present invention also provides a kind of part, has the structure of formula III,
In formula III, A is end group, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, m is 3～28 integer.
Under preferable case, R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
M is preferably 13～18 integer.
Those skilled in the art know that the scope of end group A of the present invention, when it refers to prepare APEO, introduced the group of the polyethers end of the chain by initiator.Described end group A is preferably the alkoxyl of C12～C25 or the phenol oxygen base of C8～C20.
Researches on Aquathermolysis Catalysts for Heavy Crude Oils of the present invention can be used for the tertiary oil recovery in thickened oil recovery and oilfield exploitation later stage.
Compare with existing Researches on Aquathermolysis Catalysts for Heavy Crude Oils, catalyst of the present invention has higher catalytic efficiency, can reduce reaction temperature, reduce the reaction time, and viscosity of thickened oil is reduced reach 90%, the light component increase reaches 8%.Catalyst of the present invention has amphiphilic structure, soluble in water and oily, in use can be made under aqueous solution Injection Well, in case contact with oil, amphiphilic structure wherein disperses the viscous crude particle by emulsification, guaranteed that catalyst mixes with fully contacting with good of viscous crude, the coordination metal end that has simultaneously catalytic activity enters oil phase, catalysis viscous crude molecule carries out aquathermolysis under the effect of Re Heshui, can realize high viscosity break ratio within a short period of time, reaches irreversible reduction viscosity of thickened oil, improves the purpose of viscous crude quality.
The specific embodiment
In embodiment, after reaction finished, then standing minute water in the slow cooling process measured the rear viscosity of thickened oil of dehydration; By four component contents before and after family's component analysis method (SY/T5119-2008) assaying reaction, defining light component content is the content sum of saturated part and fragrance part.
Viscosity break ratio calculates with following formula.
Light component recruitment calculates with following formula.
Embodiment 1
In the present embodiment, get the 0.1g hydrothermal cracking catalyst and be dissolved in 30g water, it is joined in the reactor that fills the 70g viscous crude, be warming up to 160 ℃ after sealing, isothermal reaction 10 hours is reacted complete, slowly be down to room temperature, standing minute water, measuring the dewatered oil viscosity break ratio is 92%, light component mass penalty 7%.
Viscous crude in the present embodiment is Tahe Heavy Crude, and the hydrothermal cracking catalyst preparation process is as follows:
2.5g dodecyl alcohol polyoxyethylene (6) ether and 1g thionyl chloride are mixed, stir 3h under 80 ℃ of conditions, decompression removes the complete solvent of unreacted and obtains chlorinated dodecane base alcohol polyoxyethylene (6) ether, need not purifying, and is standby.The 3g potassium tert-butoxide is joined in acetylacetone,2,4-pentanedione, and then back flow reaction 2h adds chlorinated dodecane base alcohol polyoxyethylene (6) ether, continues backflow 3h, namely obtains the amphiphilic organic ligand.The 1.5g Nickel dichloride hexahydrate is dissolved in the 120g absolute ethyl alcohol, adds amphiphilic organic ligand obtained above, the 6h that refluxes under condition of heating and stirring, desolvation is drying to obtain hydrothermal cracking catalyst.Characterize by nucleus magnetic hydrogen spectrum, data are as follows, 1H NMR (CDCl3) δ: 3.30～3.61,24H; 3.21,1H; 2.21～2.41,6H; 1.89～2.01,2H; 1.25～1.50,20H; 0.71～0.92,3H.
Embodiment 2
In the present embodiment, get the 0.08g hydrothermal cracking catalyst and be dissolved in 35g water, it is joined in the reactor that fills the 65g viscous crude, be warming up to 180 ℃ after sealing, isothermal reaction 8 hours is reacted complete, slowly be down to room temperature, standing minute water, measuring the dewatered oil viscosity break ratio is 84%, light component mass penalty 5%.
Viscous crude in the present embodiment is triumph Dan Jia temple-56-13-19 viscous crude, the hydrothermal cracking catalyst preparation process is with embodiment 1, wherein APEO is for being that phosphorus trichloride, organic ligand are 1-phenyl-1 to cetyl phenol polyethenoxy (12) ether, halogenating agent, and 3-diacetyl, transition metal salt are that Hexaaquachromium chloride, alkali are sodium hydride.Hydrothermal cracking catalyst in the present embodiment characterizes by nucleus magnetic hydrogen spectrum, and data are as follows, 1H NMR (CDCl3) δ: 6.80～7.92,9H; 4.31,2H; 3.85,1H; 3.30～3.81,44H; 2.62,2H; 2.21～2.41,3H; 1.89～2.01,2H; 1.25～1.50,28H; 0.71～0.92,3H.
Embodiment 3
In the present embodiment, get the 0.15g hydrothermal cracking catalyst and be dissolved in 40g water, it is joined in the reactor that fills the 60g viscous crude, be warming up to 180 ℃ after sealing, isothermal reaction 8 hours is reacted complete, slowly be down to room temperature, standing minute water, measuring the dewatered oil viscosity break ratio is 90%, light component mass penalty 6%.
Viscous crude in the present embodiment is Tahe TH12510 viscous crude, the hydrothermal cracking catalyst preparation process is with embodiment 1, wherein APEO is that eicosanol polyoxyethylene (18) ether, halogenating agent are that phosphorus pentachloride, organic ligand are 1,4-diphenyl-1,3-diacetyl, transition metal salt are that four hydration manganese acetates, alkali are sodium metal.Hydrothermal cracking catalyst in the present embodiment characterizes by nucleus magnetic hydrogen spectrum, and data are as follows, 1HNMR (CDCl3) δ: 7.32～7.95,10H; 3.85,1H; 3.30～3.75,74H; 1.89～2.01,2H; 1.25～1.50,36H; 0.71～0.92,3H.
Embodiment 4
In the present embodiment, get the 0.1g hydrothermal cracking catalyst and be dissolved in 30g water, it is joined in the reactor that fills the 70g viscous crude, be warming up to 200 ℃ after sealing, isothermal reaction 8 hours is reacted complete, slowly be down to room temperature, standing minute water, measuring the dewatered oil viscosity break ratio is 94%, light component mass penalty 8%.
Viscous crude in the present embodiment is triumph Dan Jia temple 56-19-11 viscous crude, the hydrothermal cracking catalyst preparation process is with embodiment 1, and wherein APEO is that n nonylphenol polyoxyethylene (24) ether, halogenating agent are that hydrogen chloride, organic ligand are that acetylacetone,2,4-pentanedione, transition metal salt are that Nickel dichloride hexahydrate, alkali are sodium hydride.Hydrothermal cracking catalyst in the present embodiment characterizes by nucleus magnetic hydrogen spectrum, and data are as follows, 1H NMR (CDCl
3) δ: 6.75～7.23,4H; 4.31,2H; 3.28～3.85,92H; 3.21,1H; 2.62,2H; 2.21～2.41,6H; 1.89～2.01,2H; 1.25～1.50,16H; 0.71～0.92,3H.
Embodiment 5
Two weeks and one month, tested viscosity are preserved in the sealing of the viscous crude processed in above embodiment.Result shows, viscosity changes in ± 5%.
By IR Characterization, the part in embodiment 1～4 is without the hydroxyl absworption peak, and at 1630cm
-1Near strong absworption peak is all arranged, be the characteristic absorption peak of beta-diketon; After making corresponding hydrothermal cracking catalyst, 1630cm
-1Near strong absworption peak all disappears, at 1500cm
-1Near the new strong absworption peak of appearance is beta-diketon and metal-complexing absworption peak afterwards.
In the cited embodiment of the present invention, value up and down, the interval value of each raw material and technological parameter all can be realized effect set forth in the present invention, do not enumerate embodiment at this.
Claims (28)
1. a Researches on Aquathermolysis Catalysts for Heavy Crude Oils, contain the transient metal complex shown in formula I,
In formula I, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, M is the metal of VB, VIB, VIIB or VIII family, and A is end group, and m is 3～28 integer, and n is 1～3 integer.
2. according to catalyst claimed in claim 1, it is characterized in that R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
3. according to catalyst claimed in claim 1, it is characterized in that, m is 13～18 integer.
4. according to catalyst claimed in claim 1, it is characterized in that, M is iron, cobalt, nickel, chromium or manganese.
5. according to catalyst claimed in claim 1, it is characterized in that the phenol oxygen base of the alkoxyl that described end group A is C12～C25 or C8～C20.
6. the preparation method of a Researches on Aquathermolysis Catalysts for Heavy Crude Oils comprises:
(1) with APEO and halogenating agent reaction, obtain the halo APEO;
(2) with the halo APEO of step (1) preparation and the formula II compound reaction of alkali treatment, obtain the compound shown in formula III;
(3) in solvent, formula III compound and transition metal reactant salt that step (2) is made;
In formula II and formula III, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, A is end group, and m is 3～28 integer, and transition metal salt is the slaine of VB, VIB, VIIB or VIII family.
7. in accordance with the method for claim 6, it is characterized in that, m is 13～18 integer.
8. in accordance with the method for claim 6, it is characterized in that, the end group of described APEO is the alkoxyl of C12～C25 or the phenol oxygen base of C8～C20.
9. in accordance with the method for claim 6, it is characterized in that, described halogenating agent is thionyl chloride, phosphorus trichloride, phosphorus pentachloride or hydrogen chloride.
10. in accordance with the method for claim 6, it is characterized in that, described alkali is alkali metal alcoholates, alkali metal hydride or alkali metal.
11. in accordance with the method for claim 6, it is characterized in that R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
12. in accordance with the method for claim 6, it is characterized in that, M is molysite, cobalt salt, nickel salt, chromic salts or manganese salt.
13. in accordance with the method for claim 6, it is characterized in that, described solvent is one or more in C1～C6 alcohol.
14. in accordance with the method for claim 6, it is characterized in that, the reaction time of step (1) is 3～24 hours.
15. in accordance with the method for claim 6, it is characterized in that, the reaction temperature of step (1) is-10～120 ℃.
16. in accordance with the method for claim 6, it is characterized in that, the reaction time of step (2) is 2～10 hours.
17. in accordance with the method for claim 6, it is characterized in that, the reaction temperature of step (2) is 60～160 ℃.
18. in accordance with the method for claim 6, it is characterized in that, the reaction time of step (3) is 2～12 hours.
19. in accordance with the method for claim 6, it is characterized in that, the reaction temperature of step (3) is 20～120 ℃.
20. a transient metal complex has the structure shown in formula I,
In formula I, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, M is the metal of VB, VIB, VIIB or VIII family, and A is end group, and m is 3～28 integer, and n is 1～3 integer.
21. according to the described complex of claim 20, it is characterized in that R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
22. according to the described complex of claim 20, it is characterized in that, m is 13～18 integer.
23. according to the described complex of claim 20, it is characterized in that, M is iron, cobalt, nickel, chromium or manganese.
24. according to the described complex of claim 20, it is characterized in that the phenol oxygen base of the alkoxyl that described end group A is C12～C25 or C8～C20.
25. a part has the structure of formula III,
In formula III, A is end group, R
1, R
2Be C1～C6 alkyl or C6～C10 aryl independently of one another, m is 3～28 integer.
26. according to the described part of claim 20, it is characterized in that R
1, R
2Be C1～C3 alkyl or C6～C8 aryl independently of one another.
27. according to the described part of claim 20, it is characterized in that, m is 13～18 integer.
28. according to the described part of claim 20, it is characterized in that the phenol oxygen base of the alkoxyl that described end group A is C12～C25 or C8～C20.
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| CN201110364603.6A CN103111327B (en) | 2011-11-17 | 2011-11-17 | Researches on Aquathermolysis Catalysts for Heavy Crude Oils and preparation method thereof and transition metal complex and part |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558352A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Block polymer and preparation method therefore, application of block polymer in hydrothermal catalytic viscosity reduction of thickened oil and hydrothermal catalytic viscosity reduction method of thickened oil |
| CN104830305A (en) * | 2015-04-03 | 2015-08-12 | 长江大学 | Active catalytic viscosity reducer for viscous oil recovery, and preparation method and application thereof |
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| CN1944572A (en) * | 2006-10-13 | 2007-04-11 | 中国地质大学（武汉） | Process for preparing thick oil hydrothermally catalytic cracking viscosity reducer containing amphiphilic structure |
| CN1948349A (en) * | 2006-11-09 | 2007-04-18 | 西南石油大学 | Preparation method of acetyl acetone cyclodextrin inclusion compound and its application in reducing thick oil viscosity |
| CN101007286A (en) * | 2007-01-22 | 2007-08-01 | 西南石油大学 | Preparation method of molybdenum acetylacetonate catalyst coated by surfactants and its application |
| CN102019205A (en) * | 2009-09-15 | 2011-04-20 | 中国石油天然气股份有限公司 | Complex catalyst for viscosity reduction of thick oil by hydrothermal catalytic cracking and preparation and application thereof |
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2011
- 2011-11-17 CN CN201110364603.6A patent/CN103111327B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944572A (en) * | 2006-10-13 | 2007-04-11 | 中国地质大学（武汉） | Process for preparing thick oil hydrothermally catalytic cracking viscosity reducer containing amphiphilic structure |
| CN1948349A (en) * | 2006-11-09 | 2007-04-18 | 西南石油大学 | Preparation method of acetyl acetone cyclodextrin inclusion compound and its application in reducing thick oil viscosity |
| CN101007286A (en) * | 2007-01-22 | 2007-08-01 | 西南石油大学 | Preparation method of molybdenum acetylacetonate catalyst coated by surfactants and its application |
| CN102019205A (en) * | 2009-09-15 | 2011-04-20 | 中国石油天然气股份有限公司 | Complex catalyst for viscosity reduction of thick oil by hydrothermal catalytic cracking and preparation and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558352A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Block polymer and preparation method therefore, application of block polymer in hydrothermal catalytic viscosity reduction of thickened oil and hydrothermal catalytic viscosity reduction method of thickened oil |
| CN104558352B (en) * | 2013-10-28 | 2018-02-23 | 中国石油化工股份有限公司 | Block polymer and preparation method thereof and the application in thick oil hydrothermal catalytic visbreaking and the method for thick oil hydrothermal catalytic visbreaking |
| CN104830305A (en) * | 2015-04-03 | 2015-08-12 | 长江大学 | Active catalytic viscosity reducer for viscous oil recovery, and preparation method and application 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 |
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