CN104531119A - Method for preparing supported metallic catalyst based on Fe3O4 - Google Patents

Method for preparing supported metallic catalyst based on Fe3O4 Download PDF

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CN104531119A
CN104531119A CN201510012311.4A CN201510012311A CN104531119A CN 104531119 A CN104531119 A CN 104531119A CN 201510012311 A CN201510012311 A CN 201510012311A CN 104531119 A CN104531119 A CN 104531119A
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oleic acid
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volume ratio
supported catalyst
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陈磊
郭喜明
程树康
郭斌
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
    • B01J2531/002—Materials
    • B01J2531/005—Catalytic metals

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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a method for preparing a supported metallic catalyst based on Fe3O4. The method solves the problems that in the existing hydrothermal catalytic viscosity reduction technology, the catalyzing temperature and cost are high, and a catalyst is high in pollution. The method comprises the steps that firstly, Fe3O4 magnetic nanoparticles are prepared; secondly, Fe3O4 nanoparticles provided with hydrophobic surfaces and wrapped by monolayer oleic acid; thirdly, composite nanoparticles are prepared; fourthly, the composite nanoparticles and a polyvinylpyrrolidone water solution are mixed, and then the supported metallic catalyst based on Fe3O4 is obtained.

Description

A kind of preparation method based on Z 250 metal supported catalyst
Technical field
The present invention relates to the preparation method of metal catalyst.
Background technology
Along with the scarcity of world energy sources is more and more serious, cause many countries to drop into huge fund development novel energy, and the raising of original ancient energy utilization degree be also result in the attention of many decision maker and scientists.Crude oil is energy goods and materials important in national economy.Along with increasing rapidly of global crude oil consumption, conventional oil resource reduces day by day, and viscous crude is as a kind of unconventional resource had a high potential, and its exploitation more and more causes the attention of people.The part crude oil that China produces particularly northeast and North China crude oil all belong to high glutinous, the viscous crude of Gao Ning, this type of viscous crude viscous crude molecular structure is complicated, and heavy components content is high, makes its viscosity higher, and its exploitation is still world-famous puzzle so far.Viscosity Reducing Technologies for Recovery of Viscous Crude Oils is one of focus of Oil & Gas Storage circle scientific research always.
Traditional fall modal in sticking method to be heating method, during the method process, a large amount of oil fuel and power will to be consumed.What other were traditional fall, and sticking method such as chemical pour-point depression is carried method, pour point depression to carry method, is mixed lightweight oil conveying method, water-mixing transportation method and hydraulic pump oil recovery conveying method etc., also there is the drawbacks such as investment is large, destruction oil, contaminate environment, limit respective applying.Therefore, the new and effective viscosity reduction for heavy oils of development research is most important.
Fall glutinous and hydro-thermal catalytic cracking at the oil soluble viscosity reducer fallen in sticking method of at present research to fall glutinous technology and there is many advantages, but there is very scabrous bottleneck problem equally, oil soluble viscosity reducer falls that glutinous to be that the one that grows up on the basis of pour point depressant technology is novel fall glutinous technology.By dispersion in visbreaking agent molecule, osmosis enters between colloid and bitum sheet molecule, part breaks the aggregate structure that plane overlap is piled up, formation sheet molecule is random to be piled up, structure fluffs loose, and reduce the colloid comprised in aggregate, asphaltene molecules number, reduce crude oil force of cohesion, play and fall glutinous effect, it is utilize the aquathermolysis occurred between viscous crude and water vapor that glutinous technology falls in hydro-thermal catalytic cracking, make viscous crude under the effect of catalyzer, make the viscous crude generating portion cracking of high carbon number and become lightweight oil, irreversibly reduce thick oil viscosity, improve oil product grade. in addition, the H produced in aquathermolysis process 2, down-hole hydrogenation reaction can be there is, improve the quality of viscous crude.Thick oil hydrothermal catalytic visbreaking technology is also faced with many practical problemss urgently to be resolved hurrily.First, in the exploitation of catalyzer, current hydro-thermal catalytic reforming falls that glutinous catalyst body ties up to catalytic activity, environmental compatibility aspect will be strengthened further, and cost then will reduce further.Secondly, catalytic temperature should be reduced as far as possible, take the type of heating of environmental protection more economically, reduce energy consumption and the pollution of catalytic visbreaking process.Finally, the metal ingredient fallen in glutinous rear residual catalyzer is also a noticeable aspect on the impact of viscous crude deep processing afterwards.Therefore, with other fall sticking method with the use of, develop compound, integrated-type and fall glutinous technique, playing multiple synergy of falling glutinous means, is that one of developing direction of glutinous catalyzer falls in hydro-thermal catalytic reforming.
When the action of a magnetic field is in crude oil, magnetization can make crude oil produce induction magnetic distance, suppress wax crystalline substance formed and coalescent, wax crystalline substance is made to be present in crude oil with small particles form, the diamagnetic substance such as paraffin, colloid, bituminous matter simultaneously in viscous crude can carry out short-range order arrangement, enhance mobility, reduce former oil viscosity.Electric field is combined with magnetic field, can produce polarized action and electrocaloric effect, have magnetization effect again, can reach good thinning effect to crude oil.Therefore electromagnetic field is fallen glutinous method and is widely used.Be magnetic fluid technique on the other hand, magnetic fluid (magnetic fluid) is the colloid merged by the magnetically permeable material of 0.1nm ~ 100nm, dispersion agent and carrier.
Summary of the invention
The present invention will solve the problem that in existing hydro-thermal catalytic visbreaking technology, catalytic temperature is high, cost is high and catalyst contamination is large, and provides a kind of original position to prepare the method for Z 250/charcoal/graphite nanosheets nano composite material.
Based on a preparation method for Z 250 metal supported catalyst, specifically carry out according to following steps:
One, first by FeCl 36H 2o is mixed with the FeCl that concentration is 0.01mol/L ~ 1mol/L 3solution, by FeSO 44H 2o is mixed with the FeSO that concentration is 0.01mol/L ~ 1mol/L 4concentration, then under nitrogen protection and agitation condition, is the FeCl of 0.01mol/L ~ 1mol/L by solution 3solution and concentration are the FeSO of 0.01mol/L ~ 1mol/L 4solution mixes, then in mixed solution, add concentration be hydrochloric acid to the pH value of mixed solution of 0.1mol/L ~ 5mol/L is 5 ~ 7, is then drip the NH that mass percent is 10% ~ 40% in the mixed solution of 5 ~ 7 to pH value 4oH solution, until there is black precipitate, then low whipping speed is under the condition of 500rpm ~ 2000rpm, stirs 1h, obtain black precipitate liquid, under additional the action of a magnetic field, remove black precipitate liquid upper strata waste liquid, obtain black precipitate, then by black precipitate deionized water wash, obtain Fe 3o 4magnetic nano-particle;
Described concentration is the FeCl of 0.01mol/L ~ 1mol/L 3fe in solution 3+be the FeSO of 0.01mol/L ~ 1mol/L with concentration 4fe in solution 2+mol ratio be 1:(0.2 ~ 10);
Two, by Fe 3o 4magnetic nano-particle joins in oleic acid ethanolic soln, and reaction 0.5h ~ 2h, obtains the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle, then by the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle washes of absolute alcohol 2 times ~ 10 times, then clean 2 times ~ 10 times with distilled water, obtain the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle;
Described oleic acid ethanolic soln is that to join ethanol by oleic acid formulated, and described oleic acid and the volume ratio of ethanol are 1:(0.2 ~ 10); Described Fe 3o 4the quality of magnetic nano-particle and the volume ratio of oleic acid ethanolic soln are 1g:(0.2 ~ 10) mL;
Three, by the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle joins in ethanol, obtains the Fe that concentration is the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4then concentration be the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L by nano-particle solution 3o 4nano-particle solution and concentration are that the chloroplatinic acid aqueous solution of 0.01mol/L ~ 1mol/L joins in deionized water, stir, then hydrazine hydrate solution is instilled, and be ultrasonic under the condition of 10kHz ~ 100kHz in ultrasonic frequency, until reaction soln becomes atrament and the generation of adjoint bubble, after reaction terminates, permanent magnet is utilized to be isolated from solution by magnetic nanoparticle, and by washed with de-ionized water 2 times ~ 10 times, obtain composite nanoparticle;
Described concentration is the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4the volume ratio of nano-particle solution and deionized water is 1:(0.2 ~ 10); Described concentration is the chloroplatinic acid aqueous solution of 0.01mol/L ~ 1mol/L and the volume ratio of deionized water is 1:(0.2 ~ 10); Described hydrazine hydrate solution and concentration are the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4the volume ratio of nano-particle solution is 1:(0.2 ~ 10);
Four, polyvinylpyrrolidone is joined in distilled water, under temperature is 80 DEG C ~ 90 DEG C and agitation condition, be stirred to polyvinylpyrrolidone to dissolve, obtain aqueous povidone solution, then join in aqueous povidone solution by composite nanoparticle, low whipping speed is under the condition of 500rpm ~ 2000rpm, stirs 5min ~ 100min, finally carry out Magneto separate, obtain based on Z 250 metal supported catalyst;
The quality of described polyvinylpyrrolidone and the volume ratio of distilled water are 1g:(0.2 ~ 10) mL; Described composite nanoparticle and the mass ratio of polyvinylpyrrolidone are 1:(0.2 ~ 10).
The invention has the beneficial effects as follows: a kind of magnetic fluid loaded with nano of the present invention catalyzer composite nano materials, this composite nanoparticle is coated by lipophilicity temperature sensing material, effectively can solve the stability of nanoparticle in crude oil and dispersiveness, utilize the uniformity of temperature profile that the heat transfer characteristic of magnetic fluid can make in crude oil, thus better can activate the catalyst activity of load, thus effectively heighten and fall glutinous efficiency.
Quasi-step matrix oil soluble viscosity reducer of the present invention falls glutinous and hydro-thermal catalytic cracking and falls glutinous technology, the characteristic of the advantage in sticking and magnetic fluid thereof falls in magnetic field, the composite nanoparticle utilizing synthesis lipophilicity magnetic nano-particle supported catalyst is proposed, this composite nanoparticle is by between dispersion, the osmosis colloid that enters viscous crude and bitum sheet molecule, effectively can be dispersed in the aggregate structure piled up of plane overlap, thus may form that sheet molecule is random to be piled up.Prepared by the present invention low based on Z 250 metal supported catalyst catalytic temperature, lower 10 DEG C than catalytic temperature in existing hydro-thermal catalytic visbreaking technology ~ 20 DEG C, cost is low and catalyst contamination is little.
The present invention is used for a kind of preparation method based on Z 250 metal supported catalyst.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph based on Z 250 metal supported catalyst prepared by embodiment;
Fig. 2 is the powder X-ray RD based on Z 250 metal supported catalyst prepared by embodiment;
Fig. 3 is the FT-IR based on Z 250 metal supported catalyst prepared by embodiment;
Fig. 4 is the magnetzation curve based on Z 250 metal supported catalyst prepared by embodiment;
Fig. 5 is viscosity-temperature curve; 1 is the viscosity-temperature curve of crude oil, 2 viscosity-temperature curves based on the oil after the process of Z 250 metal supported catalyst catalytic visbreaking prepared for embodiment.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of preparation method based on Z 250 metal supported catalyst described in present embodiment, specifically carry out according to following steps:
One, first by FeCl 36H 2o is mixed with the FeCl that concentration is 0.01mol/L ~ 1mol/L 3solution, by FeSO 44H 2o is mixed with the FeSO that concentration is 0.01mol/L ~ 1mol/L 4concentration, then under nitrogen protection and agitation condition, is the FeCl of 0.01mol/L ~ 1mol/L by solution 3solution and concentration are the FeSO of 0.01mol/L ~ 1mol/L 4solution mixes, then in mixed solution, add concentration be hydrochloric acid to the pH value of mixed solution of 0.1mol/L ~ 5mol/L is 5 ~ 7, is then drip the NH that mass percent is 10% ~ 40% in the mixed solution of 5 ~ 7 to pH value 4oH solution, until there is black precipitate, then low whipping speed is under the condition of 500rpm ~ 2000rpm, stirs 1h, obtain black precipitate liquid, under additional the action of a magnetic field, remove black precipitate liquid upper strata waste liquid, obtain black precipitate, then by black precipitate deionized water wash, obtain Fe 3o 4magnetic nano-particle;
Described concentration is the FeCl of 0.01mol/L ~ 1mol/L 3fe in solution 3+be the FeSO of 0.01mol/L ~ 1mol/L with concentration 4fe in solution 2+mol ratio be 1:(0.2 ~ 10);
Two, by Fe 3o 4magnetic nano-particle joins in oleic acid ethanolic soln, and reaction 0.5h ~ 2h, obtains the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle, then by the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle washes of absolute alcohol 2 times ~ 10 times, then clean 2 times ~ 10 times with distilled water, obtain the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle;
Described oleic acid ethanolic soln is that to join ethanol by oleic acid formulated, and described oleic acid and the volume ratio of ethanol are 1:(0.2 ~ 10); Described Fe 3o 4the quality of magnetic nano-particle and the volume ratio of oleic acid ethanolic soln are 1g:(0.2 ~ 10) mL;
Three, by the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle joins in ethanol, obtains the Fe that concentration is the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4then concentration be the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L by nano-particle solution 3o 4nano-particle solution and concentration are that the chloroplatinic acid aqueous solution of 0.01mol/L ~ 1mol/L joins in deionized water, stir, then hydrazine hydrate solution is instilled, and be ultrasonic under the condition of 10kHz ~ 100kHz in ultrasonic frequency, until reaction soln becomes atrament and the generation of adjoint bubble, after reaction terminates, permanent magnet is utilized to be isolated from solution by magnetic nanoparticle, and by washed with de-ionized water 2 times ~ 10 times, obtain composite nanoparticle;
Described concentration is the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4the volume ratio of nano-particle solution and deionized water is 1:(0.2 ~ 10); Described concentration is the chloroplatinic acid aqueous solution of 0.01mol/L ~ 1mol/L and the volume ratio of deionized water is 1:(0.2 ~ 10); Described hydrazine hydrate solution and concentration are the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4the volume ratio of nano-particle solution is 1:(0.2 ~ 10);
Four, polyvinylpyrrolidone is joined in distilled water, under temperature is 80 DEG C ~ 90 DEG C and agitation condition, be stirred to polyvinylpyrrolidone to dissolve, obtain aqueous povidone solution, then join in aqueous povidone solution by composite nanoparticle, low whipping speed is under the condition of 500rpm ~ 2000rpm, stirs 5min ~ 100min, finally carry out Magneto separate, obtain based on Z 250 metal supported catalyst;
The quality of described polyvinylpyrrolidone and the volume ratio of distilled water are 1g:(0.2 ~ 10) mL; Described composite nanoparticle and the mass ratio of polyvinylpyrrolidone are 1:(0.2 ~ 10).
The Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity prepared by this embodiment step 2 3o 4nanoparticle, is dispersed in the NaCl aqueous solution of 0.4mol/L for subsequent use, now Fe 3o 4the negative electricity of magnetic nano particle subband trace, its zeta current potential is-4.32mV.
The beneficial effect of present embodiment is: a kind of magnetic fluid loaded with nano of present embodiment catalyzer composite nano materials, this composite nanoparticle is coated by lipophilicity temperature sensing material, effectively can solve the stability of nanoparticle in crude oil and dispersiveness, utilize the uniformity of temperature profile that the heat transfer characteristic of magnetic fluid can make in crude oil, thus better can activate the catalyst activity of load, thus effectively heighten and fall glutinous efficiency.
Present embodiment quasi-step matrix oil soluble viscosity reducer falls glutinous and hydro-thermal catalytic cracking and falls glutinous technology, the characteristic of the advantage in sticking and magnetic fluid thereof falls in magnetic field, the composite nanoparticle utilizing synthesis lipophilicity magnetic nano-particle supported catalyst is proposed, this composite nanoparticle is by between dispersion, the osmosis colloid that enters viscous crude and bitum sheet molecule, effectively can be dispersed in the aggregate structure piled up of plane overlap, thus may form that sheet molecule is random to be piled up.Prepared by present embodiment low based on Z 250 metal supported catalyst catalytic temperature, lower 10 DEG C than catalytic temperature in existing hydro-thermal catalytic visbreaking technology ~ 20 DEG C, cost is low and catalyst contamination is little.
Embodiment two: present embodiment and embodiment one unlike: the concentration described in step one is the FeCl of 0.01mol/L ~ 1mol/L 3fe in solution 3+be the FeSO of 0.01mol/L ~ 1mol/L with concentration 4fe in solution 2+mol ratio be 2:1.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two are that to join ethanol by oleic acid formulated unlike: the oleic acid ethanolic soln described in step 2, and described oleic acid and the volume ratio of ethanol are 1:(0.5 ~ 5).Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike Fe described in step 2 3o 4the quality of magnetic nano-particle and the volume ratio of oleic acid ethanolic soln are 1g:(0.5 ~ 5) mL.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the concentration described in step 3 is the Fe of the Coated with Oleic Acid of 7.5g/L 3o 4the volume ratio of nano-particle solution and deionized water is 1:(0.5 ~ 5).Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the concentration described in step 3 is the chloroplatinic acid aqueous solution of 0.05-0.5mol/L and the volume ratio of deionized water is 1:(0.5 ~ 5).Other is identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the hydrazine hydrate solution described in step 3 and concentration are the Fe of the Coated with Oleic Acid of 2-8g/L 3o 4the volume ratio of nano-particle solution is 1:(0.5 ~ 5).Other is identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the quality of the polyvinylpyrrolidone described in step 4 and the volume ratio of distilled water are 1g:(0.5 ~ 5) mL.Other is identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the mass ratio of the composite nanoparticle described in step 4 and polyvinylpyrrolidone is 1:(0.5 ~ 5).Other is identical with embodiment one to eight.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment:
A kind of preparation method based on Z 250 metal supported catalyst described in the present embodiment, specifically carries out according to following steps:
One, first by FeCl 36H 2o is mixed with the FeCl that concentration is 0.1mol/L 3solution, by FeSO 44H 2o is mixed with the FeSO that concentration is 0.1mol/L 4solution, then under nitrogen protection and agitation condition, by FeCl 3solution and FeSO 4solution mixes, then in mixed solution, add concentration be hydrochloric acid to the pH value of mixed solution of 1mol/L is 5, is then drip the NH that mass percent is 25% in the mixed solution of 5 to pH value 4oH solution, until there is black precipitate, then low whipping speed is under the condition of 1500rpm, stirs 1h, obtain black precipitate liquid, under additional the action of a magnetic field, remove black precipitate liquid upper strata waste liquid, obtain black precipitate, then by black precipitate deionized water wash, obtain Fe 3o 4magnetic nano-particle;
Described FeCl 3fe in solution 3+with FeSO 4fe in solution 2+mol ratio be 2:1;
Two, by Fe 3o 4magnetic nano-particle joins in oleic acid ethanolic soln, and reaction 1h, obtains the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle, then by the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle washes of absolute alcohol 5 times, then clean 5 times with distilled water, obtain the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle;
Described oleic acid ethanolic soln is that to join ethanol by oleic acid formulated, and described oleic acid and the volume ratio of ethanol are 1:2; Described Fe 3o 4the quality of magnetic nano-particle and the volume ratio of oleic acid ethanolic soln are 1g:5mL;
Three, by the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle joins in ethanol, obtains the Fe that concentration is the Coated with Oleic Acid of 7.5g/L 3o 4then concentration be the Fe of the Coated with Oleic Acid of 7.5g/L by nano-particle solution 3o 4nano-particle solution and concentration are that the chloroplatinic acid aqueous solution of 0.1mol/L joins in deionized water, stir, then hydrazine hydrate solution is instilled, and be ultrasonic under the condition of 80kHz in ultrasonic frequency, until reaction soln becomes atrament and the generation of adjoint bubble, after reaction terminates, permanent magnet is utilized to be isolated from solution by magnetic nanoparticle, and by washed with de-ionized water 3 times, obtain composite nanoparticle;
Described concentration is the Fe of the Coated with Oleic Acid of 7.5g/L 3o 4the volume ratio of nano-particle solution and deionized water is 1:5; Described concentration is the chloroplatinic acid aqueous solution of 0.1mol/L and the volume ratio of deionized water is 1:5; Described hydrazine hydrate solution and concentration are the Fe of the Coated with Oleic Acid of 7.5g/L 3o 4the volume ratio of nano-particle solution is 1:5;
Four, polyvinylpyrrolidone is joined in distilled water, under temperature is 85 DEG C and agitation condition, be stirred to polyvinylpyrrolidone to dissolve, obtain aqueous povidone solution, then join in aqueous povidone solution by composite nanoparticle prepared by step 3, low whipping speed is under the condition of 500rpm, stirs 30min, finally carry out Magneto separate, obtain based on Z 250 metal supported catalyst;
The quality of described polyvinylpyrrolidone and the volume ratio of distilled water are 1g:5mL; Described composite nanoparticle and the mass ratio of polyvinylpyrrolidone are 1:5.
Fig. 1 is the electromicroscopic photograph based on Z 250 metal supported catalyst prepared by the present embodiment; As seen from the figure, characterize pattern and the size of particle, yardstick is approximately distributed in 10nm, and distribution is more even.
Fig. 2 is the powder X-ray RD based on Z 250 metal supported catalyst prepared by the present embodiment; As seen from the figure, the typical diffraction peak of nano ferriferrous oxide, its 2 θ appears at 35.70 respectively, 30.38,63.00,43.36,57.36,18.50,53.84 and 74.48 correspond to (311), (220), (440), (400), (511), (111), the crystal faces such as (422) (533), this illustrates that the metal carrying catalyst of preparation has face-centered cubic crystal structure.
Fig. 3 is the FT-IR based on Z 250 metal supported catalyst prepared by the present embodiment; As seen from the figure, the typical IR absorption peak of typical ferriferrous oxide nano-particle is shown in figure.
Fig. 4 is the magnetzation curve based on Z 250 metal supported catalyst prepared by the present embodiment; As seen from the figure, what prepared by the present embodiment has Superconducting magnetic based on Z 250 metal supported catalyst.
The 1g prepared by the present embodiment joins in 1000mL crude oil based on Z 250 metal supported catalyst, be 40 DEG C of glutinous 5min that decline at catalytic temperature, then the viscosity-temperature curve of the oil after sticking process falls in testing catalytic, and the viscosity-temperature curve original with crude oil compares.
Fig. 5 is viscosity-temperature curve; 1 is the viscosity-temperature curve of crude oil, 2 viscosity-temperature curves based on the oil after the process of Z 250 metal supported catalyst catalytic visbreaking prepared for embodiment.As seen from the figure, what utilize the present embodiment to prepare falls glutinous oil based on Z 250 metal supported catalyst, is tested by viscosity reducing capability, and recording catalyzer has crude oil and significantly fall glutinous effect.
Add in heavy oil pipeline by a certain amount of catalyzer, the lipophilic material by outermost layer parcel affects, and magnetic fluid meeting self-dispersing, namely can apply magnetic field in the duct.Magnetic fluid particle produces heat under the influence of a magnetic field, and first outer field oleophylic temperature sensing material melted by heat, makes catalyst activation after reaching catalytic temperature, catalytic pyrolysis viscous crude, make its viscosity degradation.Fall after sticking, then with magnetic field, catalyzer is separated from viscous crude, avoid the metal ingredient in catalyzer to affect the characteristic of viscous crude.

Claims (9)

1., based on a preparation method for Z 250 metal supported catalyst, it is characterized in that a kind of preparation method based on Z 250 metal supported catalyst carries out according to following steps:
One, first by FeCl 36H 2o is mixed with the FeCl that concentration is 0.01mol/L ~ 1mol/L 3solution, by FeSO 44H 2o is mixed with the FeSO that concentration is 0.01mol/L ~ 1mol/L 4concentration, then under nitrogen protection and agitation condition, is the FeCl of 0.01mol/L ~ 1mol/L by solution 3solution and concentration are the FeSO of 0.01mol/L ~ 1mol/L 4solution mixes, then in mixed solution, add concentration be hydrochloric acid to the pH value of mixed solution of 0.1mol/L ~ 5mol/L is 5 ~ 7, is then drip the NH that mass percent is 10% ~ 40% in the mixed solution of 5 ~ 7 to pH value 4oH solution, until there is black precipitate, then low whipping speed is under the condition of 500rpm ~ 2000rpm, stirs 1h, obtain black precipitate liquid, under additional the action of a magnetic field, remove black precipitate liquid upper strata waste liquid, obtain black precipitate, then by black precipitate deionized water wash, obtain Fe 3o 4magnetic nano-particle;
Described concentration is the FeCl of 0.01mol/L ~ 1mol/L 3fe in solution 3+be the FeSO of 0.01mol/L ~ 1mol/L with concentration 4fe in solution 2+mol ratio be 1:(0.2 ~ 10);
Two, by Fe 3o 4magnetic nano-particle joins in oleic acid ethanolic soln, and reaction 0.5h ~ 2h, obtains the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle, then by the Fe of double-deck Coated with Oleic Acid 3o 4nanoparticle washes of absolute alcohol 2 times ~ 10 times, then clean 2 times ~ 10 times with distilled water, obtain the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle;
Described oleic acid ethanolic soln is that to join ethanol by oleic acid formulated, and described oleic acid and the volume ratio of ethanol are 1:(0.2 ~ 10); Described Fe 3o 4the quality of magnetic nano-particle and the volume ratio of oleic acid ethanolic soln are 1g:(0.2 ~ 10) mL;
Three, by the Fe of the individual layer Coated with Oleic Acid of surface hydrophobicity 3o 4nanoparticle joins in ethanol, obtains the Fe that concentration is the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4then concentration be the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L by nano-particle solution 3o 4nano-particle solution and concentration are that the chloroplatinic acid aqueous solution of 0.01mol/L ~ 1mol/L joins in deionized water, stir, then hydrazine hydrate solution is instilled, and be ultrasonic under the condition of 10kHz ~ 100kHz in ultrasonic frequency, until reaction soln becomes atrament and the generation of adjoint bubble, after reaction terminates, permanent magnet is utilized to be isolated from solution by magnetic nanoparticle, and by washed with de-ionized water 2 times ~ 10 times, obtain composite nanoparticle;
Described concentration is the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4the volume ratio of nano-particle solution and deionized water is 1:(0.2 ~ 10); Described concentration is the chloroplatinic acid aqueous solution of 0.01mol/L ~ 1mol/L and the volume ratio of deionized water is 1:(0.2 ~ 10); Described hydrazine hydrate solution and concentration are the Fe of the Coated with Oleic Acid of 1g/L ~ 10g/L 3o 4the volume ratio of nano-particle solution is 1:(0.2 ~ 10);
Four, polyvinylpyrrolidone is joined in distilled water, under temperature is 80 DEG C ~ 90 DEG C and agitation condition, be stirred to polyvinylpyrrolidone to dissolve, obtain aqueous povidone solution, then join in aqueous povidone solution by composite nanoparticle, low whipping speed is under the condition of 500rpm ~ 2000rpm, stirs 5min ~ 100min, finally carry out Magneto separate, obtain based on Z 250 metal supported catalyst;
The quality of described polyvinylpyrrolidone and the volume ratio of distilled water are 1g:(0.2 ~ 10) mL; Described composite nanoparticle and the mass ratio of polyvinylpyrrolidone are 1:(0.2 ~ 10).
2. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the concentration described in step one is the FeCl of 0.01mol/L ~ 1mol/L 3fe in solution 3+be the FeSO of 0.01mol/L ~ 1mol/L with concentration 4fe in solution 2+mol ratio be 2:1.
3. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, it is characterized in that the oleic acid ethanolic soln described in step 2 is that to join ethanol by oleic acid formulated, described oleic acid and the volume ratio of ethanol are 1:(0.5 ~ 5).
4. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the Fe described in step 2 3o 4the quality of magnetic nano-particle and the volume ratio of oleic acid ethanolic soln are 1g:(0.5 ~ 5) mL.
5. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the concentration described in step 3 is the Fe of the Coated with Oleic Acid of 7.5g/L 3o 4the volume ratio of nano-particle solution and deionized water is 1:(0.5 ~ 5).
6. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the concentration described in step 3 be the chloroplatinic acid aqueous solution of 0.05-0.5mol/L and the volume ratio of deionized water is 1:(0.5 ~ 5).
7. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the hydrazine hydrate solution described in step 3 and concentration are the Fe of the Coated with Oleic Acid of 2-8g/L 3o 4the volume ratio of nano-particle solution is 1:(0.5 ~ 5).
8. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the quality of the polyvinylpyrrolidone described in step 4 and the volume ratio of distilled water are 1g:(0.5 ~ 5) mL.
9. a kind of preparation method based on Z 250 metal supported catalyst according to claim 1, is characterized in that the mass ratio of the composite nanoparticle described in step 4 and polyvinylpyrrolidone is 1:(0.5 ~ 5).
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