CN114249333A - Microcrystalline molecular sieve for viscosity reduction of thick oil and preparation method and application thereof - Google Patents
Microcrystalline molecular sieve for viscosity reduction of thick oil and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 157
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 69
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 46
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000001603 reducing effect Effects 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000006011 modification reaction Methods 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 82
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000295 fuel oil Substances 0.000 claims description 6
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims description 2
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 claims description 2
- WOMUGKOOLXQCTQ-UHFFFAOYSA-N trichloro-(4-methylphenyl)silane Chemical compound CC1=CC=C([Si](Cl)(Cl)Cl)C=C1 WOMUGKOOLXQCTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002149 hierarchical pore Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- -1 stability Chemical compound 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Abstract
The invention provides a microcrystalline molecular sieve for viscosity reduction of thick oil and a preparation method and application thereof, wherein the method comprises the steps of dispersing the microcrystalline molecular sieve into an organic solvent, adding organosilane containing straight-chain alkyl into an obtained system, carrying out modification reaction, and obtaining the microcrystalline molecular sieve modified by the straight-chain alkyl outside a hole after the reaction is finished; adding the microcrystalline molecular sieve into a mixed solution of hydrofluoric acid aqueous solution and ethanol for reaction, and obtaining the microcrystalline molecular sieve with a macroporous structure and modified by straight-chain alkyl outside the pores after the reaction is finished; dispersing the microcrystalline molecular sieve with the macroporous structure and modified by straight-chain alkyl outside the pores in an organic solvent, adding organosilane containing aromatic groups into the obtained system, and continuing modification reaction to modify the aromatic groups in the pores of the microcrystalline molecular sieve, thus obtaining the microcrystalline molecular sieve for viscosity reduction of the thick oil after the reaction is finished. When the microcrystalline molecular sieve for reducing the viscosity of the thick oil prepared by the invention is used as a thick oil viscosity reducer, the viscosity of the thick oil can be obviously reduced.
Description
Technical Field
The invention relates to a microcrystalline molecular sieve for viscosity reduction of thick oil, and a preparation method and application thereof, and belongs to the technical field of viscosity reduction of thick oil in oil fields.
Background
With the rapid development of global industry, the demand of human beings for energy is increasing year by year. Although new energy has grown year by year as a supplement in energy consumption, crude oil remains one of the important strategic energy sources. With the development of oil and gas resources, the proportion of poor crude oil resources in the total crude oil resource increases, and the economic and efficient development technology of heavy oil (heavy oil) becomes an important key for the future development of the petroleum industry. Due to the characteristics of complex composition, high viscosity, high density and the like of the thickened oil, the exploitation and transportation of the thickened oil are the key points of the research in recent years. In order to realize the economic and efficient development of the thick oil, the key is to reduce the viscosity and improve the fluidity of the thick oil at low temperature.
At present, the viscosity reduction method for thick oil comprises two main types of physics and chemistry. Wherein, the physical viscosity reducing method comprises a dilution viscosity reducing method, a thermal viscosity reducing method and a microwave viscosity reducing method; the chemical viscosity reduction method comprises an emulsification viscosity reduction method, a catalysis viscosity reduction method and the like. The viscosity reducing method for thick oil generally adopted in industry is a thermal viscosity reducing method, and the chemical viscosity reducing method for achieving the viscosity reducing effect of crude oil by adding a chemical viscosity reducer has high selectivity and poor universality on thick oil, so that the method has certain limitation and regionality in the application process. Therefore, the development of a new crude oil viscosity reduction material, which can reduce the viscosity of crude oil at low cost and with universality by adsorbing and isolating asphaltenes, colloids and the like in the crude oil through a simple physical adsorption method, has become a technical problem to be solved in the field.
Porous materials such as mesoporous silica-based materials, hierarchical pore molecular sieves, hollow particles, MOF/ZIF, and the like, are receiving increasing attention due to their excellent adsorption characteristics. Among many porous materials, a hierarchical pore molecular sieve has been widely studied due to its characteristics of simple preparation method, high stability, strong adsorption capacity, and the like. Molecular sieves are widely applied to the aspect of catalytic cracking and viscosity reduction of petroleum, but the molecular sieves are used for modifying crude oil by a chemical method, and the viscosity reduction of thick oil by a physical adsorption method is not reported.
Therefore, the molecular sieve is modified to obtain the multi-level pore functionalized molecular sieve which is used for reducing the viscosity of the thickened oil by the physical adsorption method, and the method has important significance.
Disclosure of Invention
In order to solve the disadvantages and shortcomings, the invention aims to provide a preparation method of a microcrystalline molecular sieve for viscosity reduction of thick oil.
The invention also aims to provide the microcrystalline molecular sieve for reducing the viscosity of the thick oil, which is prepared by the preparation method of the microcrystalline molecular sieve for reducing the viscosity of the thick oil.
The invention also aims to provide the application of the microcrystalline molecular sieve for viscosity reduction of the thick oil as the viscosity reducer of the thick oil.
The invention also aims to provide a method for reducing viscosity of thick oil, which uses the microcrystalline molecular sieve for reducing viscosity of thick oil as a thick oil viscosity reducer.
In order to achieve the above object, in one aspect, the present invention provides a preparation method of a microcrystalline molecular sieve for viscosity reduction of thick oil, wherein the preparation method of the microcrystalline molecular sieve for viscosity reduction of thick oil comprises:
(1) dispersing the microcrystalline molecular sieve into an organic solvent, adding organosilane containing straight-chain alkyl into the obtained system, and then carrying out modification reaction to obtain the microcrystalline molecular sieve modified by the straight-chain alkyl outside the pores after the reaction is finished;
(2) adding the microcrystalline molecular sieve modified by straight-chain alkyl outside the pores into a mixed solution of hydrofluoric acid aqueous solution and ethanol for reaction, and obtaining the microcrystalline molecular sieve modified by straight-chain alkyl outside the pores with a macroporous structure after the reaction is finished;
(3) dispersing the microcrystalline molecular sieve with the macroporous structure and the outside of the pores modified by straight-chain alkyl in an organic solvent, adding organosilane containing aromatic groups into the obtained system, and continuing modification reaction to modify the aromatic groups in the pores of the microcrystalline molecular sieve, and obtaining the microcrystalline molecular sieve for viscosity reduction of the thick oil after the reaction is finished.
In the preparation method, the microcrystalline molecular sieve is a material with a microporous structure and is relatively compact, so when organosilane containing linear alkyl is used for modifying the microcrystalline molecular sieve in the step (1), the linear alkyl cannot enter micropores, and only the surface of the microcrystalline molecular sieve can be modified; in the step (2), after the microcrystalline molecular sieve modified by the straight-chain alkyl outside the hole is added into the mixed solution of hydrofluoric acid aqueous solution and ethanol, the microcrystalline molecular sieve is etched by hydrofluoric acid, so that the microcrystalline molecular sieve has a macroporous structure, the intermediate product is still the microcrystalline molecular sieve modified by the straight-chain alkyl outside the hole, and no modification group is modified in the hole; because the active sites outside the pores of the microcrystalline molecular sieve are occupied by the linear alkyl groups, in the step (3), the aromatic groups can only react at the active sites inside the pores to modify the aromatic groups inside the pores of the microcrystalline molecular sieve, so that the microcrystalline molecular sieve which is modified by the linear alkyl groups outside the pores and modified by the aromatic groups inside the pores is obtained, namely the microcrystalline molecular sieve for reducing the viscosity of the heavy oil.
In the above-described production method, preferably, the size of the microcrystalline molecular sieve is 13 to 35 μm.
In the above preparation method, the microcrystalline molecular sieve (ZSM-5 micron-sized molecular sieve crystals) may be a conventional microcrystalline molecular sieve commercially available in the art, or a microcrystalline molecular sieve prepared by a method conventional in the art (such as the method in the documents Microporous and Mesoporous Materials 1999,28, 241-259) and optimizing the synthesis conditions based on the method).
In the above-described production method, preferably, in the step (1), the mass of the organic solvent is 25 to 75 times that of the microcrystalline molecular sieve, and the mass of the organosilane containing a linear alkyl group is 0.5 to 4.5 times that of the microcrystalline molecular sieve.
In the preparation method described above, preferably, in step (1), the organic solvent includes one or a combination of several of toluene, benzene and xylene.
In the above-mentioned preparation method, preferably, in the step (1), the modification reaction is carried out at 40 to 120 ℃ for 2 to 15 hours.
In the above-described production method, preferably, in the step (1), the structural formula of the organosilane containing a linear alkyl group is shown in the following formula 1):
in formula 1), X is a hydrolyzable group;
Rais a straight chain alkyl group;
Rband RcIs a hydrolyzable group or a straight-chain alkyl group which is the same as or different from X, Ra.
In the above-described production method, preferably, the hydrolyzable group includes halogen or alkoxy.
In the above-mentioned preparation method, preferably, the organosilane containing a linear alkyl group includes one or more of ethyltrimethoxysilane, n-hexadecyltriethoxysilane, n-hexyltrichlorosilane, and n-butyltrimethoxysilane.
In the above-described production method, preferably, in the step (2), the volume ratio of the hydrofluoric acid aqueous solution to the ethanol in the mixed solution of the hydrofluoric acid aqueous solution and the ethanol is 1:0.5 to 1: 15.
In the above preparation method, preferably, in the step (2), the concentration of the hydrofluoric acid aqueous solution is 0.1mL/10mL to 1.5mL/10mL (i.e., 0.1mL to 1.5mL of hydrofluoric acid is contained in each 10mL of the hydrofluoric acid aqueous solution).
In the above-described production method, preferably, the ethanol has a volume concentration of 90 to 99%.
In the above-described preparation method, preferably, in the step (2), the mass ratio between the microcrystalline molecular sieve modified by straight-chain alkyl outside the pores and the mixed solution (etching solution) of hydrofluoric acid aqueous solution and ethanol is 1:10 to 1: 120.
In the above-mentioned production method, preferably, in the step (2), the reaction is carried out at 55 to 130 ℃ for 18 to 48 hours.
In the above-described production method, preferably, in the step (3), the mass of the organic solvent is 25 to 75 times that of the microcrystalline molecular sieve modified with straight-chain alkyl groups outside the pores, and the mass of the aromatic group-containing organosilane is 0.5 to 4.5 times that of the microcrystalline molecular sieve modified with straight-chain alkyl groups outside the pores.
In the preparation method described above, preferably, in the step (3), the organic solvent includes one or a combination of several of toluene, benzene and xylene.
In the above-mentioned preparation method, preferably, in the step (3), the modification reaction is performed at 50 to 130 ℃ for 2 to 20 hours.
In the above-described production method, preferably, in the step (3), the structural formula of the aromatic group-containing organosilane is represented by the following formula 2):
in formula 2), X is a hydrolyzable group;
R′ais an aromatic group;
R′band R'cIs X, R'aThe same or different hydrolyzable or aromatic groups, and alkyl groups. The aromatic group and the alkyl group in the formula 2) are not particularly required, and those skilled in the art can select an appropriate aromatic group and an appropriate alkyl group by routine, as long as the purpose of the invention can be achieved.
In the above-described production method, preferably, the hydrolyzable group includes halogen or alkoxy.
In the above preparation method, preferably, the organosilane containing an aromatic group includes one or more of phenylmethyldiethoxysilane, p-tolyltrichlorosilane, and triphenylchlorosilane.
On the other hand, the invention also provides the microcrystalline molecular sieve for reducing the viscosity of the thick oil, which is prepared by the preparation method of the microcrystalline molecular sieve for reducing the viscosity of the thick oil, wherein the microcrystalline molecular sieve for reducing the viscosity of the thick oil is a multi-stage pore functionalized microcrystalline molecular sieve, the outside of the pores of the microcrystalline molecular sieve is modified by linear alkyl groups, and the inside of the pores of the microcrystalline molecular sieve is modified by aromatic groups.
In another aspect, the invention also provides the application of the microcrystalline molecular sieve for viscosity reduction of thick oil as a viscosity reducer of thick oil.
On the other hand, the invention also provides a thick oil viscosity reduction method, wherein the thick oil viscosity reduction method comprises the steps of adding the microcrystalline molecular sieve for viscosity reduction of thick oil into a mixed solution of thick oil and an organic solvent, and carrying out viscosity reduction treatment at 60-90 ℃;
wherein the organic solvent comprises C5-C16Linear alkanes of (1).
In the above-described thick oil viscosity reduction method, the organic solvent may be, for example, n-heptane.
In application, the microcrystalline molecular sieve for viscosity reduction of the thick oil can be directly used as a thick oil viscosity reduction material or used as a viscosity reduction additive.
In application, the viscosity of the thick oil is reducedThe straight-chain alkyl modified outside the sieve pores of the crystal molecules is beneficial to the organic solvent (C)5-C16The linear alkane), and the aromatic groups modified in the microcrystalline molecular sieve pores are beneficial to adsorbing components such as asphaltene and the like which have great influence on the viscosity of the thick oil in the thick oil, so that the viscosity reduction of the thick oil is realized.
The preparation method of the microcrystalline molecular sieve for reducing the viscosity of the thick oil, provided by the invention, has the advantages of simple process flow, low production cost, mild synthesis conditions and easiness in industrial production; the preparation method can be used for preparing the multi-stage pore functionalized microcrystalline molecular sieve with the inside and the outside of the pores modified by different groups, namely the microcrystalline molecular sieve with the outside of the pores modified by straight chain alkyl groups and the inside of the pores modified by aromatic groups.
The microcrystalline molecular sieve (the hierarchical pore functionalized microcrystalline molecular sieve) for viscosity reduction of the thick oil, which is prepared by the invention, still has the characteristic peak of an MFI type molecular sieve, and has the micropore pore passage and characteristics of the microcrystalline molecular sieve, such as stability, strong adsorbability and the like.
Because the inside and the outside of the pores of the hierarchical pore functionalized microcrystal molecular sieve are modified by different groups, when the hierarchical pore functionalized microcrystal molecular sieve is used as the viscosity reducer of the thick oil, the viscosity of the thick oil can be obviously reduced; and the viscosity reduction efficiency of the hierarchical pore functionalized microcrystalline molecular sieve material modified by different groups can be adjusted by changing the types of functional groups modified inside and outside the pores of the microcrystalline molecular sieve with the hierarchical pore structure.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a microcrystalline molecular sieve for viscosity reduction of thick oil prepared in example 1 of the present invention.
FIG. 2 is an infrared spectrum of the microcrystalline molecular sieve, the microcrystalline molecular sieve with outside pores modified by linear alkyl group, and the microcrystalline molecular sieve for viscosity reduction of heavy oil in example 1 of the present invention.
FIG. 3 is a wide-angle XRD spectrum of the microcrystalline molecular sieve for reducing viscosity of thick oil prepared in example 2 of the present invention.
FIG. 4 is a scanning electron microscope image of the microcrystalline molecular sieve for reducing viscosity of thick oil prepared in example 3 of the present invention.
FIG. 5 is a viscosity reduction curve of a thick oil viscosity reduction microcrystalline molecular sieve prepared in example 2 of the present invention when used as a thick oil viscosity reducer.
FIG. 6 is a viscosity reduction curve of a viscous oil viscosity reducer using the microcrystalline molecular sieve for viscosity reduction prepared in example 3 of the present invention.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
The embodiment provides a preparation method of a microcrystalline molecular sieve for reducing viscosity of thick oil, wherein the preparation method comprises the following specific steps:
fully stirring 3.0g of tetrapropylammonium bromide, 27.5g of deionized water, 1.75g of ammonium fluoride, 0.4g of aluminum source (aluminum sulfate) and 3.5g of silicon source (white carbon black), and reacting for 24 hours under hydrothermal conditions (140-; centrifuging, washing, drying and sintering (550-650 ℃) to obtain the ZSM-5 microcrystalline molecular sieve with the size of 13-35 mu m;
dispersing 1.0g of microcrystalline molecular sieve in 75mL of toluene, adding 1.2mL of n-hexadecyl triethoxy silane, carrying out water bath at 75 ℃ for 5h, and carrying out centrifugal drying to obtain the microcrystalline molecular sieve with the outside of the pores modified by straight chain alkyl;
adding 1.0g of microcrystalline molecular sieve modified by straight chain alkyl outside the pores into a mixed solution of 30g of hydrofluoric acid aqueous solution (0.3mL/10mL) and ethanol (99%), wherein the volume ratio of the hydrofluoric acid aqueous solution to the ethanol is 1:5, reacting for 36h at 80 ℃, and drying after centrifugal washing treatment by deionized water to obtain the microcrystalline molecular sieve modified by straight chain alkyl outside the pores with a macroporous structure;
dispersing the microcrystalline molecular sieve with the macroporous structure and modified by straight-chain alkyl outside the pores into 75mL of toluene, adding 1.2mL of phenyl methyl diethoxysilane, carrying out water bath at 80 ℃ for 6h, and carrying out centrifugal drying to obtain the microcrystalline molecular sieve with the inside and the outside of the pores modified by different groups, namely the microcrystalline molecular sieve with the outside of the pores modified by straight-chain alkyl and the inside of the pores modified by aromatic groups.
The microcrystalline molecular sieve for viscosity reduction of thick oil prepared in this example was scanned by a Hitachi JSM-6700F field emission scanning electron microscope at an accelerating voltage of 50kV, and before the experiment, the microcrystalline molecular sieve for viscosity reduction of thick oil was subjected to metal spraying for 60s to increase the conductivity of the sample, and the scanning electron microscope image obtained by scanning is shown in fig. 1. The microcrystalline molecular sieve for reducing the viscosity of the thick oil finally obtained in the embodiment is a micron-scale crystal with a macroporous-microporous structure, and the pore size is 100nm-150 nm.
An infrared spectrometer is adopted to perform infrared spectrum characterization on the microcrystalline molecular sieve, the microcrystalline molecular sieve modified by the straight chain alkyl outside the pores and the microcrystalline molecular sieve for viscosity reduction of thick oil in the embodiment respectively, and the obtained infrared spectrogram is shown in fig. 2, wherein in fig. 2, a is the microcrystalline molecular sieve, B is the microcrystalline molecular sieve modified by the straight chain alkyl outside the pores, and C is the microcrystalline molecular sieve for viscosity reduction of thick oil.
Example 2
The embodiment provides a preparation method of a microcrystalline molecular sieve for reducing viscosity of thick oil, wherein the preparation method comprises the following specific steps:
fully stirring 3.0g of tetrapropylammonium bromide, 27.5g of deionized water, 1.75g of ammonium fluoride, 0.4g of aluminum source (aluminum sulfate) and 3.5g of silicon source (white carbon black), and reacting for 24 hours under hydrothermal conditions (140-; centrifuging, washing, drying and sintering (550-650 ℃) to obtain the ZSM-5 microcrystalline molecular sieve with the size of 13-35 mu m;
dispersing 1.0g of microcrystalline molecular sieve in 85mL of toluene, adding 1.0mL of n-hexadecyl triethoxy silane, carrying out water bath at 75 ℃ for 5h, and carrying out centrifugal drying to obtain the microcrystalline molecular sieve with the outside of the pores modified by straight chain alkyl;
adding 1.0g of microcrystalline molecular sieve modified by straight chain alkyl outside the pores into a mixed solution of 30g of hydrofluoric acid aqueous solution (0.3mL/10mL) and ethanol (99%), wherein the volume ratio of the hydrofluoric acid aqueous solution to the ethanol is 1:5, reacting for 36h at 80 ℃, and drying after centrifugal washing treatment by deionized water to obtain the microcrystalline molecular sieve modified by straight chain alkyl outside the pores with a macroporous structure;
dispersing the microcrystalline molecular sieve with the macroporous structure and modified by straight-chain alkyl outside the pores into 75mL of toluene, adding 1.2mL of phenyl methyl diethoxysilane, carrying out water bath at 80 ℃ for 6h, and carrying out centrifugal drying to obtain the microcrystalline molecular sieve with the inside and the outside of the pores modified by different groups, namely the microcrystalline molecular sieve with the outside of the pores modified by straight-chain alkyl and the inside of the pores modified by aromatic groups.
In order to better illustrate the structure of the microcrystalline molecular sieve for reducing the viscosity of the thick oil prepared in the embodiment, a Rigaku D/Max-2550 type ray diffractometer is used for testing the microcrystalline molecular sieve for reducing the viscosity of the thick oil, an obtained wide-angle XRD spectrogram is shown in fig. 3, and as can be seen from fig. 3, a diffraction peak of a sample of the microcrystalline molecular sieve for reducing the viscosity of the thick oil is completely consistent with a characteristic peak of an MFI type molecular sieve.
Example 3
The embodiment provides a preparation method of a microcrystalline molecular sieve for reducing viscosity of thick oil, wherein the preparation method comprises the following specific steps:
fully stirring 3.0g of tetrapropylammonium bromide, 27.5g of deionized water, 1.75g of ammonium fluoride, 0.4g of aluminum source (aluminum sulfate) and 3.5g of silicon source (white carbon black), and reacting for 24 hours under hydrothermal conditions (140-; centrifuging, washing, drying and sintering (550-650 ℃) to obtain the ZSM-5 microcrystalline molecular sieve with the size of 13-35 mu m;
dispersing 1.0g of microcrystalline molecular sieve in 85mL of toluene, adding 1.0mL of n-hexadecyl triethoxy silane, carrying out water bath at 75 ℃ for 5h, and carrying out centrifugal drying to obtain the microcrystalline molecular sieve with the outside of the pores modified by straight chain alkyl;
adding 1.0g of microcrystalline molecular sieve modified by straight chain alkyl outside the pores into a mixed solution of 30g of hydrofluoric acid aqueous solution (0.3mL/10mL) and ethanol (99%), wherein the volume ratio of the hydrofluoric acid aqueous solution to the ethanol is 1:5, reacting for 36h at 80 ℃, and drying after centrifugal washing treatment by deionized water to obtain the microcrystalline molecular sieve modified by straight chain alkyl outside the pores with a macroporous structure;
dispersing the microcrystalline molecular sieve with the macroporous structure and modified by straight-chain alkyl outside the pores into 75mL of toluene, adding 1.2mL of p-toluene trichlorosilane, carrying out water bath at 80 ℃ for 6h, and carrying out centrifugal drying to obtain the microcrystalline molecular sieve with the inside and the outside of the pores modified by different groups, namely the microcrystalline molecular sieve with the outside of the pores modified by straight-chain alkyl and the inside of the pores modified by aromatic groups.
The microcrystalline molecular sieve for viscosity reduction of thick oil prepared in this example was scanned by a Hitachi JSM-6700F field emission scanning electron microscope at an accelerating voltage of 50kV, and before the experiment, the microcrystalline molecular sieve for viscosity reduction of thick oil was subjected to metal spraying for 60s to increase the conductivity of the sample, and the scanning electron microscope image obtained by scanning is shown in fig. 4. The microcrystalline molecular sieve for reducing the viscosity of the thick oil prepared by the embodiment is a macroporous-microporous hierarchical pore molecular sieve, and after the modification of different groups inside and outside the pores, the particle size of the hierarchical pore molecular sieve is not changed, and the size of the hierarchical pore molecular sieve is still 13-35 mu m.
Application example 1
The application example provides a viscosity reducing method for thick oil, wherein the used viscosity reducer is the microcrystalline molecular sieve for viscosity reduction of the thick oil prepared in example 2, and the method comprises the following steps:
1.0g of the microcrystalline molecular sieve for reducing the viscosity of the thick oil prepared in example 2 is added into a system of 60mL of crude oil and 10mL of n-heptane, viscosity test is carried out at 80 ℃, the viscosity reduction curve is shown in FIG. 5, as can be clearly seen from FIG. 5, after the microcrystalline molecular sieve for reducing the viscosity of the thick oil prepared in example 2 of the present invention is added, the viscosity of the crude oil can be reduced from about 12100 mPa.s to 1400 mPa.s, and the viscosity reduction effect is significant.
Application example 2
The application example provides a method for reducing viscosity of thick oil, wherein the used viscosity reducer is the microcrystalline molecular sieve for reducing viscosity of thick oil prepared in example 3, and the method comprises the following steps:
1.0g of the microcrystalline molecular sieve for reducing the viscosity of the thickened oil prepared in the example 3 is added into a system of 60mL of crude oil and 10mL of n-heptane, viscosity test is carried out at 80 ℃, the obtained viscosity reduction curve is shown in FIG. 6, as can be clearly seen from FIG. 6, after the microcrystalline molecular sieve for reducing the viscosity of the thickened oil prepared in the example 3 is added, the viscosity of the crude oil can be reduced to 5400mPa · s, and the viscosity reduction effect is obvious. By carrying out comprehensive analysis by combining the experimental results in application example 1, the viscosity reduction efficiency of the microcrystalline molecular sieve material for viscosity reduction of thick oil modified by different groups as the viscosity reducer of thick oil can be adjusted by changing the types of the functional groups modified inside and outside the microcrystalline molecular sieve pores with the hierarchical pore structure.
The above description is only exemplary of the invention and should not be taken as limiting the scope of the invention, so that the invention is intended to cover all modifications and equivalents of the embodiments described herein. In addition, the technical features and the technical inventions of the present invention, the technical features and the technical inventions, and the technical inventions can be freely combined and used.
Claims (20)
1. The preparation method of the microcrystalline molecular sieve for reducing the viscosity of the thick oil is characterized by comprising the following steps of:
(1) dispersing the microcrystalline molecular sieve into an organic solvent, adding organosilane containing straight-chain alkyl into the obtained system, and then carrying out modification reaction to obtain the microcrystalline molecular sieve modified by the straight-chain alkyl outside the pores after the reaction is finished;
(2) adding the microcrystalline molecular sieve modified by straight-chain alkyl outside the pores into a mixed solution of hydrofluoric acid aqueous solution and ethanol for reaction, and obtaining the microcrystalline molecular sieve modified by straight-chain alkyl outside the pores with a macroporous structure after the reaction is finished;
(3) dispersing the microcrystalline molecular sieve with the macroporous structure and the outside of the pores modified by straight-chain alkyl in an organic solvent, adding organosilane containing aromatic groups into the obtained system, and continuing modification reaction to modify the aromatic groups in the pores of the microcrystalline molecular sieve, and obtaining the microcrystalline molecular sieve for viscosity reduction of the thick oil after the reaction is finished.
2. The method of claim 1, wherein the microcrystalline molecular sieve has a size of 13-35 μm.
3. The method according to claim 1, wherein in step (1), the mass of the organic solvent is 25 to 75 times that of the microcrystalline molecular sieve, and the mass of the organosilane containing a linear alkyl group is 0.5 to 4.5 times that of the microcrystalline molecular sieve;
preferably, the organic solvent comprises one or more of toluene, benzene and xylene.
4. The method according to claim 1, wherein the modification reaction in step (1) is carried out at 40 to 120 ℃ for 2 to 15 hours.
5. The method according to any one of claims 1 to 4, wherein in the step (1), the organosilane containing a linear alkyl group has a structural formula shown in the following formula 1):
in formula 1), X is a hydrolyzable group;
Rais a straight chain alkyl group;
Rband RcIs and X, RaThe same or different hydrolyzable or straight chain alkyl groups.
6. The method of claim 5, wherein the hydrolyzable group includes a halogen or an alkoxy group.
7. The method according to claim 5 or 6, wherein the organosilane containing a linear alkyl group comprises one or more of ethyltrimethoxysilane, n-hexadecyltriethoxysilane, n-hexyltrichlorosilane, and n-butyltrimethoxysilane.
8. The method according to claim 1, wherein in the step (2), the volume ratio of the hydrofluoric acid aqueous solution to the ethanol in the mixed solution of the hydrofluoric acid aqueous solution and the ethanol is 1:0.5 to 1: 15.
9. The method according to claim 8, wherein the concentration of the aqueous hydrofluoric acid solution in the step (2) is 0.1mL/10mL-1.5mL/10 mL.
10. The method according to claim 8, wherein the ethanol is present at a concentration of 90 to 99% by volume.
11. The method according to any one of claims 1 and 8 to 10, wherein in the step (2), the reaction is carried out at 55 to 130 ℃ for 18 to 48 hours.
12. The preparation method according to any one of claims 1 and 8 to 10, wherein in the step (2), the mass ratio between the microcrystalline molecular sieve modified by linear alkyl outside the pores and the mixed solution of hydrofluoric acid aqueous solution and ethanol is 1:10 to 1: 120.
13. The preparation method according to claim 1, wherein in the step (3), the mass of the organic solvent is 25 to 75 times of the mass of the microcrystalline molecular sieve modified by the straight chain alkyl outside the pores, and the mass of the organosilane containing the aromatic group is 0.5 to 4.5 times of the mass of the microcrystalline molecular sieve modified by the straight chain alkyl outside the pores;
preferably, the organic solvent comprises one or more of toluene, benzene and xylene.
14. The method according to claim 1, wherein in the step (3), the modification reaction is carried out at 50 to 130 ℃ for 2 to 20 hours.
15. The method according to any one of claims 1 and 13 to 14, wherein in the step (3), the aromatic group-containing organosilane has a structure represented by the following formula 2):
in formula 2), X is a hydrolyzable group;
r' a is an aromatic group;
R′band R 'c is a hydrolyzable or aromatic group, which may be the same as or different from X, R' a, and an alkyl group.
16. The method of claim 15, wherein the hydrolyzable group includes a halogen or an alkoxy group.
17. The method according to claim 15 or 16, wherein the organosilane containing an aromatic group comprises one or more of phenylmethyldiethoxysilane, p-tolyltrichlorosilane, and triphenylchlorosilane.
18. The microcrystalline molecular sieve for reducing the viscosity of the heavy oil, which is prepared by the preparation method of the microcrystalline molecular sieve for reducing the viscosity of the heavy oil, according to any one of claims 1 to 17, is a multi-level pore functionalized microcrystalline molecular sieve, and the outside of the pores of the microcrystalline molecular sieve is modified by straight-chain alkyl groups, and the inside of the pores of the microcrystalline molecular sieve is modified by aromatic groups.
19. The use of the microcrystalline molecular sieve for viscosity reduction of thick oil according to claim 18 as a viscosity reducer for thick oil.
20. A method for reducing viscosity of thick oil, which is characterized by comprising the steps of adding the microcrystalline molecular sieve for reducing viscosity of thick oil disclosed by claim 18 into a mixed solution of thick oil and an organic solvent, and carrying out viscosity reduction treatment at 60-90 ℃;
wherein the organic solvent comprises C5-C16Linear alkanes of (1).
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