CN103240126B - Iron ore-containing heavy oil hydrogenation catalyst, and preparation method and application thereof - Google Patents
Iron ore-containing heavy oil hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an iron ore-containing heavy oil hydrogenation catalyst, and a preparation method and an application thereof. The heavy oil hydrogenation catalyst is composed by iron ore-containing powder and a dispersion medium. Based on the catalyst, the mass percentage of the iron ore-containing superfine powder is 5-70%; and the dispersion medium comprises the following components of, based on the dispersion medium, 80-99 wt% of a base oil, 0.05-10 wt% of a surfactant and 0.05-10 wt% of a solid thickening rheological agent, wherein the base oil is a distillate oil with a boiling point ranging from 220 DEG C to 550 DEG C. The heavy oil hydrogenation catalyst obtained by the invention has not only high catalytically active solid content but also good mixed ability with a raw oil of the heavy oil, and has good catalytic effect in heavy oil hydrocracking or hydro-upgrading of a suspended bed or a slurry bed.
Description
Technical field
The present invention relates to a kind of heavy-oil hydrogenation catalyst.More particularly, be a kind of catalyst of the iron-stone powder for heavy-oil hydrogenation, and the preparation method and application of this catalyst.
Background technology
Deficient gradually along with conventional oil resource, especially the ratio of inferior heavy oil in oil total amount is more and more higher for heavy oil, and how Efficient Conversion heavy oil becomes the huge challenge that energy field faces.Indication heavy oil comprises pitch, oil-sand, shale oil, boiling point higher than the residual oil etc. of more than 524 DEG C above.It is characterized in that: asphalitine and carbon residue content high, metallic nickel, content of vanadium are high, and total content is generally not less than 200 μ g/g, and S, N compounds content is high, and under normal temperature and pressure, apparent viscosity is large.Inferior heavy oil in heat treatment or hydroprocessing processes easily because heavy oil component assembles sedimentation blocking pipeline, reactor produce green coke.
Heavy-oil slurry hydro-upgrading, hydrocracking are the important heavy oil Efficient Conversion approach of a class.Compare fixed bed and fluidized bed reactor is the hydrogenation technique of main body, adopt paste state bed reactor to have following advantage: the macromolecular Homogeneous phase mixing of efficient hardening catalyst, hydrogen and heavy oil, improve the accessibility of catalyst active center; Easy control course of reaction temperature and pressure, realizes steady state operation; Reactor types adapts to inferior heavy oil processing, easily through adjustment reaction condition and process control reaction depth.For these reasons, the research adopting paste state bed reactor to carry out heavy-oil hydrogenation upgrading aspect is subject to the attention of various countries researcher, and the catalyst research being applicable to paste state bed reactor becomes an important research direction.
Heavy-oil slurry catalyst comprises oil-soluble catalyst, as organic metal salt or organometallic complexs such as cobalt naphthenate, nickel naphthenate, isooctyl acid molybdenums; Water-soluble catalyst, as one or more mixed inorganic aqueous solution such as ferric nitrate, nickel nitrate, ferrous sulfate, ammonium molybdates; Pressed powder type catalyst, as one or more mixtures of the metal sulfides such as molybdenum, iron, nickel, cobalt or oxide, containing molybdenum ore mine tailing, iron-stone etc., for improving its dispersiveness in heavy oil, generally be prepared into the powder with certain grain size distribution, and used strong mechanical mixture.The use of three kinds of catalyst respectively has pluses and minuses.
Oil-soluble catalyst mixes with heavy oil, and after online sulfuration, catalytic hydrocracking is effective, but the ratio of active metal component as metal molybdenum is low, general lower than 10% of catalyst gross mass, conventional molybdenum naphthenate, the mass ratio of metal molybdenum is only 6.5 ~ 9.0%.As CN 1362492 A proposes a kind of containing the phenylhydroxylamine of Mo, W and the oil-soluble hydrocracking heavy oil catalyst of derivative complex compound thereof.According to this inventive embodiments, in the catalyst that conventional method obtains, molybdenum content is 7.0%.And for example CN 1335367 A discloses a kind of oil-soluble catalyst containing heterocycle sulfo-compounds, and be the organic solid product containing one or more metals such as Cr, Ni, Fe, Co, Mo, W, tenor is lower than 9%.CN101165140A and CN101165141A proposes isooctyl acid molybdenum and molybdenum naphthenate catalyst, is the oily of thickness, metal quality percentage composition higher than 6%, for coal oil refining process.In use, for ensureing the concentration of active metal in feedstock oil, addition is large, improves application cost on the one hand, have impact on feedstock oil nature on the other hand for this type of catalyst.
When using water-soluble catalyst, generally the precursor salt containing active metal to be dissolved in the aqueous solution, for improving the dispersiveness of the aqueous solution in feedstock oil, except improving physical agitation intensity, as described a kind of method of being disperseed online by water-soluble catalyst by multistage shear pump or static mixer in CN 1295112 A; Or need to add dispersant and surface active agent composition, as University of Petroleum proposes two kinds of catalyst lyosol systems in patent CN 101024186 A and CN 101011663 A, difference is that the former is water-in-oil system, the latter is oil-in-water system, be dispersed in sol system by metal sulfide complexings such as Mo, Ni, Fe, Co, tenor is generally lower than 15% of gross mass, and use amount is larger, also moisture will be removed, complicated operation in use procedure.
When using solid powder th-1 catalyst, its advantage is easily to control catalyst concn, and its weak point is, the dispersive property of this catalyst in heavy oil is poor.
Summary of the invention
The object of this invention is to provide a kind of heavy-oil hydrogenation catalyst of iron-stone, preparation method and application, to be solved is in the slurry bed system or suspension bed hydrogenation process process adopting solid powder th-1 catalyst, the technical problem of the stable dispersion performance difference of pressed powder type catalyst in heavy oil feedstock oil.
Described heavy-oil hydrogenation catalyst is made up of iron-stone superfines and decentralized medium, take catalyst as benchmark, and the percent mass ratio of iron-stone superfines is 5 ~ 70%; Described decentralized medium contains following composition: take decentralized medium as benchmark, the base oil of 80 ~ 99 % by weight, the surfactant of 0.05 ~ 10 % by weight, 0.05 ~ 10 % by weight solid thickener rheology agent, described base oil is boiling spread at the distillate of 220 DEG C-550 DEG C.
Described iron-stone superfines is for being selected from one or more ore mixed-powders in bauxite, pyrite, limonite, magnetic iron ore, bloodstone and siderite, and the average grain diameter of iron-stone superfines is less than 80 μm.
Take catalyst as benchmark, the percent mass ratio of iron-stone superfines is 15 ~ 50%; Preferably 20 ~ 45%, the average grain diameter of iron-stone superfines is less than 40 μm, is more preferably less than 3 μm.
Described bauxite is rich nurse stone, and also known as boehmite, aluminium element molecular formula is Al
2o
3.H
2o, wherein ferro element mass fraction is calculated as 10 ~ 25% by iron oxide.Described pyritous main component is FeS
2, sulfide mass fraction is 20 ~ 80%.Described limonite main component chemical formula is nFe
2o
3.mH
2o (n=1 ~ 3, m=1 ~ 4), Fe in ore
2o
3mass fraction is 20 ~ 40%.Described magnetic iron ore main component molecular formula is Fe
3o
4, wherein Fe
3o
4mass fraction is 20 ~ 60%.Described bloodstone main component molecular formula is Fe
2o
3, Fe in ore
2o
3mass fraction is 40 ~ 60%.Described siderite main component molecular formula is FeCO
3, in ore, Fe content is according to Fe
2o
3be calculated as 10 ~ 35%.Described iron-stone powder is directly by mechanical crushing and grinding preparation.
Described base oil is selected from one or more in diesel oil, kerosene, wax oil.
Described surfactant is ionic surfactant and/or nonionic surface active agent, ionic surfactant is selected from one or more in enuatrol, neopelex, petroleum sodium sulfonate and fatty acid quaternary ammonium salt, and nonionic surface active agent is one or more in polyethylene glycol, polyvinyl alcohol or Polyethylene Octylphenol Ether (OP).
The number-average molecular weight of described polyethylene glycol (PEG) is 400-6000, can be PEG400, one or more in PEG600, PEG1000, PEG2000, PEG6000, and polyvinyl alcohol is polyvinyl alcohol with low degree of polymerization.
Take decentralized medium as benchmark, the consumption of described surfactant is 0.1 ~ 5.0 % by weight, preferably 0.3 ~ 2.0 % by weight.
Described solid thickener rheology agent is selected from one or more in amorphous silica, magnesium aluminate, magnesium silicate, organobentonite, and the particle diameter of solid thickener rheology agent is less than 100 μm, is preferably less than 20 μm, is more preferably less than 1 μm.
Take decentralized medium as benchmark, the consumption of described solid thickener rheology agent is 0.1 ~ 5.0 % by weight, is preferably 0.5 ~ 3.0 % by weight.
The preparation method of any one catalyst above-mentioned, comprising:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40 ~ 120 DEG C, process 0.5 ~ 3 hour;
(3) be down to room temperature, add surfactant, be at room temperature stirred to system homogeneous phase, obtain decentralized medium;
(4) iron-stone superfines is added in step (3) gained decentralized medium, and shear dispersion or high-speed stirred dispersion.
Also can contain polar additive in the decentralized medium of catalyst of the present invention, take decentralized medium as benchmark, and the consumption of polar additive is 0.05 ~ 10 % by weight, is preferably 0.1 ~ 5.0 % by weight, is more preferably 0.5 ~ 3.0 % by weight.Described polar additive comprises alcohol component.Described alcohol component is selected from one or more in ethanol, ethylene glycol, propane diols, glycerine, two polyethylene glycol.
Any one preparation method containing the catalyst of polar additive above-mentioned is:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40 ~ 120 DEG C, process 0.5 ~ 3 hour;
(3) be down to room temperature, add surfactant and polar additive, be at room temperature stirred to system homogeneous phase, obtain decentralized medium;
(4) iron-stone superfines is added in step (3) gained decentralized medium, and shear dispersion or high-speed stirred dispersion.
An application for any one catalyst above-mentioned, described catalyst application is in the heavy-oil hydrogenation process of slurry bed system or suspension bed.
The heavy-oil hydrogenation catalyst that the present invention obtains both had had high catalytic activity solids content, and have good mixed with heavy oil feedstock oil again, catalyst dispersive property in feedstock oil is good, embodies good heavy-oil hydrogenation catalytic activity.In the hydrocracking heavy oil or upgrading of suspension bed or slurry bed system, there is good catalytic effect.Although lower than the catalyst system containing molybdenum, nickel on hydrogenation activity, have more economy.
Detailed description of the invention
Further illustrate result of use of the present invention by the following examples.Embodiment 1 ~ 4 illustrates the preparation method of decentralized medium, and embodiment 5 ~ 8 illustrates the preparation method of catalyst, and embodiment 9 ~ 14 illustrates the hydrocracking heavy oil effect of catalyst, and with oil-soluble isooctyl acid molybdenum catalyst, commercially available MoS
2catalyst situation contrasts.
Embodiment 1
Weigh diesel oil 38g, add organobentonite 1.0g (domestic, content of organics 15 ~ 20 % by weight), homogenize with on cutter.Then in 80 DEG C of oil baths, thermal agitation is added 2 hours.The homogeneous miscella obtained is chilled to room temperature, adds 0.5g PEG 600, adds 0.2g neopelex, homogenizes under normal temperature, obtains decentralized medium A.
Embodiment 2
Weigh kerosene 42g, add aerosil 0.8g (particle diameter is less than 1 μm), homogenize with on cutter.Under room temperature, add enuatrol 0.2g, add 0.4g PEG2000, add 1.0g and analyze straight alcohol.Homogenize under normal temperature, obtain decentralized medium B.
Embodiment 3
Weigh diesel oil 30g, white oil 12g, adds organobentonite 1.2g (domestic, content of organics 15 ~ 20 % by weight).Homogenize with on cutter.Under room temperature, add enuatrol 0.2g, add 0.4g OP-7, add 1.0g and analyze straight alcohol.Homogenize under normal temperature, obtain decentralized medium C.
Embodiment 4
Weigh diesel oil 21g, white oil 21g, adds aerosil 0.5g (particle diameter is less than 1 μm).Homogenize with on cutter.Under room temperature, add 0.4g PEG 4000, add 1.5g and analyze pure propane diols.Homogenize under normal temperature, obtain decentralized medium D.
Embodiment 5
Get its average grain diameter of bauxite powder and be less than 40 μm, weigh 3.0g and be placed in test tube.Weigh 5.0g decentralized medium A in same test tube, glass bar stirs and vibrates, and infiltrates evenly, leave standstill 12 hours, occur without obvious sedimentation until powder.Obtain catalyst C1.
Embodiment 6
Get hematite and magnetic iron ore mixed-powder, its average grain diameter is less than 10 μm, weighs 5.0g and is placed in test tube.Weigh 8.0g decentralized medium B in same test tube, glass bar stirs and vibrates, and infiltrates evenly, leave standstill 12 hours, occur without obvious sedimentation until powder.Obtain catalyst C2.
Embodiment 7
Get limonite ore and its average grain diameter of siderite powder is less than 20 μm, weigh 5.0g and be placed in test tube.Weigh 12.0g decentralized medium C in same test tube, glass bar stirs and vibrates, and infiltrates evenly, leave standstill 6 hours, occur without obvious sedimentation until powder.Obtain catalyst C3.
Embodiment 8
Get its average grain diameter of yellow iron powder and be less than 30 μm, weigh 4.0g and be placed in test tube.Weigh 10.0g decentralized medium D in same test tube, glass bar stirs and vibrates, and infiltrates evenly, leave standstill 8 hours, occur without obvious sedimentation until powder.Obtain catalyst C4.
Embodiment 9 ~ 14 and comparative example 1 ~ 2
Catalyst towards heavy oil hydro-upgrading effect of the present invention is as described below.Described feedstock oil is the reduced crude that a kind of asphalitine and tenor are higher, and character is as shown in table 1.
Table 1
| Project | Feedstock property data | Project | Feedstock property data |
| Density (20 DEG C), g/cm 3 | 0.9914 | Elementary analysis, % by weight | |
| Kinematic viscosity, mm 2/s | C | 85.38 | |
| 80℃ | 304.5 | H | 10.77 |
| 100℃ | 102.1 | S | 2.11 |
| Carbon residue, % by weight | 16.6 | N | 0.50 |
| Ash content, % by weight | 0.052 | Metal analysis, μ g/g | |
| Total acid number, mgKOH/g | 0.3 | Ni | 35.9 |
| Saturated hydrocarbons, % by weight | 30.8 | V | 201 |
| Aromatic hydrocarbons, % by weight | 36.2 | Ca | 5.7 |
| Colloid, % by weight | 22.1 | Fe | 15.0 |
| Asphalitine, % by weight | 10.9 |
Evaluate catalysts hydrocracking performance indications comprise: heavy oil transformation rate, liquid product yield, coking yield (toluene insolubles yield) three.Each index definition is as follows:
Constituent mass (containing gas)/feedstock oil quality × 100% below heavy oil transformation rate=524 DEG C;
Liquid product yield=liquid product mass/feedstock oil quality × 100%.
Coking yield=toluene insolubles quality/feedstock oil quality × 100%;
Use reactor to be the HV XLPE power cables of 0.5 liter.Catalyst carries out online sulfuration in reaction temperature-rise period, and namely add sublimed sulfur as vulcanizing agent in reaction system, curing temperature is 300 ~ 350 DEG C.
Reaction condition: reaction temperature 410 ~ 440 DEG C, initial hydrogen partial pressure 5.00 ~ 9.00MPa, reaction pressure 9.50 ~ 17.00MPa, heavy oil feedstock addition is 120g, sublimed sulfur 0.1g, mixing speed 400r/min, reaction time 30 ~ 60min, catalyst charge is as described in Table 2.Its reaction effect and comparative example effect as described in Table 2.
Table 2
*: according to mineral dust Mass Calculation
*: according to metal sulfide M oS
2calculate, commercially available MoS
2be 1000 ~ 1500 orders, average grain diameter is 10 ~ 15 μm.
* *: calculated value after deduction catalyst quality
As can be seen from Table 2, from reaction effect, the result of use of catalyst provided by the present invention and commercially available MoS
2close, as catalyst C4 use yellow iron powder 415 ~ 420 DEG C reaction 40min time, course of reaction coking yield is 1.0 % by weight, and when using other mineral dusts, liquid yield is close to 90%, and coking yield is close to 2 % by weight.Effect is slightly worse than comparative example 1 and 2, but coking yield is far below situation when directly using the comparative example 3 of mineral dust.Consider the catalyst based and MoS of oil-soluble molybdenum
2higher price, economy and the effect of catalyst of the present invention comprehensively have advantage mutually.
Claims (16)
1. a heavy-oil hydrogenation catalyst for iron-stone, is characterized in that, described heavy-oil hydrogenation catalyst is made up of iron-stone superfines and decentralized medium, take catalyst as benchmark, and the percent mass ratio of iron-stone superfines is 5 ~ 70%; Described decentralized medium contains following composition: take decentralized medium as benchmark, the base oil of 80 ~ 99 % by weight, the surfactant of 0.05 ~ 10 % by weight, 0.05 ~ 10 % by weight solid thickener rheology agent, described base oil is boiling spread at the distillate of 220 DEG C-550 DEG C.
2. according to catalyst according to claim 1, it is characterized in that, described iron-stone superfines is for being selected from one or more ore mixed-powders in bauxite, pyrite, limonite, magnetic iron ore, bloodstone and siderite, and the average grain diameter of iron-stone superfines is less than 80 μm.
3. according to catalyst according to claim 1, it is characterized in that, take catalyst as benchmark, and the percent mass ratio of iron-stone superfines is 15 ~ 50%; The average grain diameter of iron-stone superfines is less than 40 μm.
4. according to catalyst according to claim 1, it is characterized in that, described base oil is selected from one or more in diesel oil, kerosene, wax oil.
5. according to catalyst according to claim 1, it is characterized in that, described surfactant is ionic surfactant and/or nonionic surface active agent, ionic surfactant is selected from one or more in enuatrol, neopelex, petroleum sodium sulfonate and fatty acid quaternary ammonium salt, and nonionic surface active agent is one or more in polyethylene glycol, polyvinyl alcohol, Polyethylene Octylphenol Ether.
6. according to catalyst according to claim 5, it is characterized in that, the number-average molecular weight of described polyethylene glycol is 400-6000, and polyvinyl alcohol is polyvinyl alcohol with low degree of polymerization.
7. according to catalyst according to claim 1, it is characterized in that, take decentralized medium as benchmark, and the consumption of described surfactant is 0.1 ~ 5.0 % by weight.
8. according to catalyst according to claim 1, it is characterized in that, described solid thickener rheology agent is selected from one or more in amorphous silica, magnesium aluminate, magnesium silicate, organobentonite, and the particle diameter of solid thickener rheology agent is less than 100 μm.
9. according to catalyst according to claim 8, it is characterized in that, the particle diameter of described solid thickener rheology agent is less than 20 μm.
10. according to catalyst according to claim 1, it is characterized in that, take decentralized medium as benchmark, and the consumption of described solid thickener rheology agent is 0.1 ~ 5.0 % by weight.
11., according to catalyst according to claim 1, is characterized in that, also containing polar additive in decentralized medium, take decentralized medium as benchmark, the consumption of polar additive is 0.05 ~ 10 % by weight, and described polar additive comprises alcohol component.
12., according to catalyst according to claim 11, is characterized in that, described alcohol component is selected from one or more in ethanol, ethylene glycol, propane diols, glycerine, two polyethylene glycol.
13., according to the catalyst described in claim 11 or 12, is characterized in that, take decentralized medium as benchmark, and the consumption of polar additive is 0.1 ~ 5.0 % by weight.
The preparation method of 14. 1 kinds of any one catalyst of claim 1-10, comprising:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40 ~ 120 DEG C, process 0.5 ~ 3 hour;
(3) be down to room temperature, add surfactant, be at room temperature stirred to system homogeneous phase, obtain decentralized medium;
(4) iron-stone superfines is added in step (3) gained decentralized medium, and shear dispersion or high-speed stirred dispersion.
The preparation method of 15. 1 kinds of any one catalyst of claim 11-13, comprising:
(1) base oil mixed with solid thickener rheology agent and homogenize with cutter;
(2) be heated to 40 ~ 120 DEG C, process 0.5 ~ 3 hour;
(3) be down to room temperature, add surfactant and polar additive, be at room temperature stirred to system homogeneous phase, obtain decentralized medium;
(4) iron-stone superfines is added in step (3) gained decentralized medium, and shear dispersion or high-speed stirred dispersion.
The application of 16. 1 kinds of any one catalyst of claim 1-13, described catalyst application is in the heavy-oil hydrogenation process of slurry bed system or suspension bed.
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| CN114073984A (en) * | 2020-08-18 | 2022-02-22 | 刘虎 | Oil-soluble molybdenum octoate catalyst, preparation method and application thereof |
| CN112128026B (en) * | 2020-09-24 | 2021-05-14 | 中惠利邦环境技术有限公司 | Porous spherical body capable of realizing fuel saving of fuel-powered vehicle and synergistically reducing emission of exhaust pollutants, and preparation method and application thereof |
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| CN1453346A (en) * | 2002-04-26 | 2003-11-05 | 中国石油化工股份有限公司 | Prepn of extreme pressure antiwear agent for lubricant oil |
| CN1853776A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
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| CN1433692A (en) * | 2003-03-05 | 2003-08-06 | 湖北省林业科学研究院 | Bacillus thuringiensis oil suspension concentrate pesticide |
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