CN108101116B - A kind of preparation method and applications of FeOOH - Google Patents
A kind of preparation method and applications of FeOOH Download PDFInfo
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- CN108101116B CN108101116B CN201711194462.1A CN201711194462A CN108101116B CN 108101116 B CN108101116 B CN 108101116B CN 201711194462 A CN201711194462 A CN 201711194462A CN 108101116 B CN108101116 B CN 108101116B
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- mixed serum
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- 229910002588 FeOOH Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 210000002966 serum Anatomy 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- 230000029087 digestion Effects 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910006299 γ-FeOOH Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 230000005587 bubbling Effects 0.000 abstract description 3
- -1 hydroxy metal oxide Chemical class 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 241001311547 Patina Species 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to hydroxy metal oxide preparation technical fields, and in particular to a kind of preparation method and applications of FeOOH.It is the following steps are included: under the conditions of hypergravity, by Fe2+Metal salt solution and aqueous slkali mixing, meanwhile, it contacts oxygen inversely with reaction solution, obtains reaction mixed serum；The reaction mixed serum is subjected to gas-liquid separation, gained liquid is aged under conditions of stirring and being bubbled oxidation, and the suspension containing FeOOH is made；The suspension is subjected to solid-liquor separation, solid phase is washed, dries, and obtains hydroxyl iron hydroxide.Hypergravity reaction precipitation process is selected in different reactors from bubbling ageing process and carries out by the present invention, and nucleus is generated and nucleus growth process separates.The environment of nucleus growth is controlled by the temperature of adjusting bubbling ageing, time, stirring extent parameter.It is preferably able to that the FeOOH of nanoscale or submicron order is prepared, has the characteristics that small average grain diameter, large specific surface area, particle diameter distribution are uniform.
Description
Technical field
The invention belongs to hydroxy metal oxide preparation technical fields, and in particular to a kind of preparation method of FeOOH
And its application.
Background technique
As a kind of important industrial materials, FeOOH is with a wide range of applications, adsorb in heavy metal particles,
The fields such as organic matter degradation, solid phase/liquid desulfuration, coal liquefaction illustrate very superior application prospect.
It prepares FeOOH powder to prepare frequently with chemical solution (wet process), by controlling certain reaction condition, such as
Reactant concentration, pH value, mixing speed or oxidation rate etc. are made.Such as, Chinese patent CN101070491A discloses one kind
The preparation method of FeOOH, it is characterized in that using Cl is contained-Ion ferrous salt is reacted with alkaline precipitating agent generates interphase, after
FeOOH is formed through oxidizing, or is containing SO4 2-Addition contains Cl in ferrous salt and alkaline precipitating agent reaction system-, contain
HPO4 2-Plasma leads brilliant agent and prepares FeOOH.But the FeOOH specific surface area that is prepared of the above method compared with
It is low, it is not able to satisfy application request.For this purpose, Chinese patent literature CN106185988A, discloses and a kind of prepare high-ratio surface
The technique of FeOOH co-production ammonium sulfate, comprising the following steps: (1) by solid sulphuric acid ferrous iron and solid carbonic acid ammonium and/or
Solid ammonium bicarbonate kneading, and water is added in kneading process to form slurry, control the pH value of slurry described in kneading process
It is 6.5~7, and the pH value of the slurry is 7~8 at the end of kneading；(2) solid-liquid is carried out to the slurry that step (1) obtains
Solid phase and liquid phase are collected in separation respectively, and the liquid phase is evaporated up to ammonium sulfate；(3) solid phase is made by slurries using water,
Hydrogen peroxide is added into the slurries oxidation reaction occurs, to filter after reaction, filter cake is FeOOH.The party
Case obtains the amorphous FeOOH of large specific surface area and oxidability by force by selecting hydrogen peroxide as oxidant.But
It is in above-mentioned document, chemical reaction precipitating process is usually carried out in agitator tank or kneading machine using intermittent mode, cannot
Serialization large-scale production exists simultaneously the microcosmic product particle for mixing poor, uncontrollable product quality, different processing batches
The disadvantages of there are great differences for particle diameter distribution, and grain diameter is big, shape is difficult to control, in addition, specific surface area is also up for into one
Step improves.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming the preparation process of hydroxyl iron hydroxide in the prior art not
Energy continuous production, the defects such as Granularity Distribution is uneven, grain diameter is big, and specific surface area is low, to provide a kind of serialization
Produce the preparation method and applications of high-specific surface area hydroxyl iron hydroxide.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of preparation method of FeOOH, comprising the following steps:
(1) under the conditions of hypergravity, by Fe2+Metal salt solution and aqueous slkali mixing, meanwhile, make oxygen-containing gas and reaction solution
It is inversely contacted, obtains reaction mixed serum；
(2) the reaction mixed serum is subjected to gas-liquid separation, gained liquid is old under conditions of stirring and being bubbled oxidation
Change, the suspension containing FeOOH is made；
(3) suspension is subjected to solid-liquor separation, solid phase is washed, dries, and obtains hydroxyl iron hydroxide.
Further, the pH of rate-determining steps (1) the reaction mixed serum is 6.0-14.0, preferably 7.0-12.0.pH
It is measured by acidometer.
Further, described to contain Fe2+Metal salt solution is in frerrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate
One or more.
Further, wherein containing Fe2+The concentration of solution is 0.1-3mol/L, preferably 0.2-2mol/L.
Further, the aqueous slkali is sodium carbonate, sodium bicarbonate, ammonium hydrogen carbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide
One or more of, when selecting a variety of alkali, proportion is not specially required.
Further, the concentration of the aqueous slkali is 0.5-15mol/L, preferably 1-10mol/L.
Further, the step (1) selects rotary packed bed supergravity reactor, and the filler that can be used includes, but
It is not limited to metal material and nonmetallic materials, such as silk screen, porous plate.The revolving speed of the rotary packed bed supergravity reactor is
100-10000rpm, preferably 300-5000rpm.
Further, step (2) selects the aging tank for having blender, digestion time 10-300min, preferably 30-
180min.Slurries are pumped into the aging tank with blender via sampling pump, are aged pot bottom and side arrangement heating tube, are bubbled
Pipe, slurries are aged in the case where heat preservation, oxygen-containing gas are bubbled oxidation.
Further, the temperature of the ageing is 20-90 DEG C, preferably 30-80 DEG C.
Further, the FeOOH is Alpha-hydroxy iron oxide, beta-hydroxy iron oxide, γ-FeOOH, δ-hydroxyl
One of base iron oxide and amorphous FeOOH.
A kind of application of the FeOOH that above-mentioned preparation method is prepared in hydrocracking reaction.
Further, the FeOOH is directly used as catalyst, or with used after shaping assistant kneading and compacting.Such as
With binder, cosolvent, forming agent etc. together kneading and compacting, different shape, such as spherical, cylindrical, cloverleaf pattern, work is made
It for fixed bed catalyst, can also directly be used with powder, as slurry bubble bed, ebullated bed, suspension bed catalyst.
Technical solution of the present invention has the advantages that
1. the preparation method of hydroxyl iron hydroxide provided by the invention, high-gravity technology is applied preparing hydroxyl oxygen for the first time
Change in iron process.Supergravity reactor is a kind of reactor for being greatly strengthened microcosmic mixing and mass transfer.With oxygen-containing gas
It is reverse to contact, Fe (OH) in system2In part Fe (II) reacted with the oxygen in oxygen-containing gas, be oxidized to Fe (III), formed
" patina " (green rusts), patina are a kind of transition state compounds for containing Fe (II) and Fe (III), and hypergravity reaction condition adds
Speed oxygen and Fe2+Reaction rate, a large amount of patina nucleus can be generated with moment.Compared with customary preparation methods, hypergravity is anti-
It answers the device microcosmic uniformly mixedization used time shorter, thus shortens the time of contact of metal salt and precipitating reagent, nucleation process is made to exist
It is quickly carried out in microcosmic, uniform environment, and the growth of nucleus can be inhibited while forming high concentration nucleus, prepared
Lesser crystal grain out.
2. the preparation method of FeOOH provided by the invention by hypergravity reaction precipitation process and is bubbled ageing process
It is carried out in different reactors, nucleus is generated and the process of nucleus growth separates.By adjust be bubbled ageing temperature, when
Between, the parameters such as stirring extent control the environment of nucleus growth.It is preferably able to that the hydroxyl of nanoscale or submicron order is prepared
Iron oxide has the characteristics that small average grain diameter, large specific surface area, particle diameter distribution are uniform.
3. the preparation method of hydroxyl iron hydroxide provided by the invention, may be implemented continuous industrial production.Hypergravity is anti-
Device outlet slurry is answered to be pumped directly into bubble tower ageing, the slurries after ageing are directly entered the device units systems such as separation, washing, drying
Obtain FeOOH.Customary preparation methods are overcome using stirred tank or bubble tower intermittently operated and bring mass transfer rate it is slow,
Production efficiency is low, poor repeatability, unstable quality and the problem of be unable to continuous production between batch.
4. the FeOOH that the present invention is prepared is used as heavy oil hydrocracking catalyst, add hydrogen living with excellent
Property, gas recovery ratio reduction, the raising of fraction oil yield, conversion ratio is 92% or more.
Specific embodiment
The specific detailed operating procedure of FeOOH preparation method provided by the invention are as follows: in two storage tanks respectively
Configuration contains Fe2+Metal salt solution, aqueous slkali；Two kinds of solution are pumped into rotating packed bed reactor via metering pump, are passed through
Liquid distribution trough sprays into revolving bed, and two kinds of solution contact in supergravity reactor, carries out liquid-liquid reactions；Oxygen-containing gas is from anti-
It answers device bottom to spray into revolving bed by gas distributor, is inversely contacted with reaction solution, carry out gas-liquid reaction；It is thrown away through revolving bed
Slurries leave supergravity reactor through liquid outlet, gas is escaped from gas vent after gas-liquid separation；Slurries are via sample introduction
It is pumped into concatenated aging tank and is bubbled the operations such as oxidation, stirring, heating, the suspension containing FeOOH is made；It is suspended
Liquid obtains FeOOH powder through routine operations such as solid-liquor separation, washing, drying.It is carried out below by specific embodiment
Explanation.
Embodiment 1
Configure the FeCl of 0.5mol/L2The NaOH solution of solution and 2.0mol/L.Silk screen is used to fill for the rotation of filler
Bed supergravity reactor, revolving speed are 1000 rpms.Oxygen-containing gas, which is sprayed into from reactor bottom by gas distributor, to be rotated
Bed.It adjusts and contains Fe2+Solution and lye relative discharge make reactor outlet slurries pH 9.0.Outlet slurry is pumped into via sampling pump
Aging tank.Aging tank heating temperature is 20 DEG C, and stirring, oxygen-containing gas are bubbled oxidation, and digestion time is 30 minutes.It is aged rear slurry
Sample A is made in the routine operations such as separating, washing, drying.
Embodiment 2
Configure the FeSO of 1.0mol/L4The NaCO of solution and 2.8mol/L3And NaHCO3Mixed ammonium/alkali solutions, wherein NaCO3With
NaHCO3Molar ratio be 1:1.Use silk screen for the rotary packed bed supergravity reactor of filler, revolving speed is 1500 revolutions per minute
Clock.Oxygen-containing gas sprays into revolving bed by gas distributor from reactor bottom.It adjusts and contains Fe2+Solution and lye relative discharge,
Make reactor outlet slurries pH 8.0.Outlet slurry is pumped into aging tank via sampling pump.Aging tank heating temperature is 40 DEG C, is stirred
It mixes, oxygen-containing gas bubbling oxidation, digestion time is 10 minutes.The routine operations such as rear slurry separating, washing, drying are aged to be made
Sample B.
Embodiment 3
Configure the Fe (NO of 1.5mol/L3)2The NH of solution and 3.4mol/L4OH and NH4HCO3Mixed ammonium/alkali solutions.Using silk screen
For the rotary packed bed supergravity reactor of filler, revolving speed is 2000 rpms.Oxygen-containing gas passes through gas from reactor bottom
Body distributor sprays into revolving bed.It adjusts and contains Fe2+Solution and lye relative discharge make reactor outlet slurries pH 7.Outlet slurry
Aging tank is pumped into via sampling pump.Aging tank heating temperature is 45 DEG C, and stirring, oxygen-containing gas are bubbled oxidation, digestion time 90
Minute.It is aged the routine operations such as rear slurry separating, washing, drying and sample C is made.
Embodiment 4
Configure the FeSO of 1.8mol/L4The KOH aqueous slkali of solution and 4.0mol/L.Orifice plate is used to fill for the rotation of filler
Bed supergravity reactor, revolving speed are 2500 rpms.Oxygen-containing gas, which is sprayed into from reactor bottom by gas distributor, to be rotated
Bed.It adjusts and contains Fe2+Solution and lye relative discharge make reactor outlet slurries pH 7.5.Outlet slurry is pumped into via sampling pump
Aging tank.Aging tank heating temperature is 90 DEG C, and stirring, oxygen-containing gas are bubbled oxidation, and digestion time is 120 minutes.It is starched after ageing
Sample D is made in the routine operations such as liquid separating, washing, drying.
Embodiment 5
Configure the FeCl of 2.0mol/L2The NaCO of solution and 4.6mol/L3And NaHCO3Mixed ammonium/alkali solutions.Use orifice plate for
The rotary packed bed supergravity reactor of filler, revolving speed are 3000 rpms.Oxygen-containing gas passes through gas from reactor bottom
Distributor sprays into revolving bed.It adjusts and contains Fe2+Solution and lye relative discharge make reactor outlet slurries pH 6.Outlet slurry warp
Aging tank is pumped by sampling pump.Aging tank heating temperature is 40 DEG C, and stirring, oxygen-containing gas are bubbled oxidation, and digestion time is 300 points
Clock.It is aged the routine operations such as rear slurry separating, washing, drying and sample E is made.
Comparative example 1
Configure the FeCl of 1.2mol/L2The NH of solution and 3.0mol/L4OH and NH4HCO3Mixed ammonium/alkali solutions are heavy using cocurrent
Shallow lake method, stirring, 40 DEG C of heating and thermal insulation.The relative discharge for adjusting two kinds of solution makes pH value of solution 8.0 after mixing.Precipitating terminates
It is aged 120 minutes afterwards.It is aged the routine operations such as rear slurry separating, washing, drying and sample F is made.
Comparative example 2
Configure the FeCl of 1.2mol/L2The NH of solution and 3.0mol/L4OH and NH4HCO3Mixed ammonium/alkali solutions, use will contain Fe2 +Solution is added drop-wise to the method in lye, stirring, 40 DEG C of heating and thermal insulation.PH value of solution is 8.0 after adjusting mixing.It is old after precipitating
Change 120 minutes.It is aged the routine operations such as rear slurry separating, washing, drying and sample G is made.
Experimental example
1. the specific surface and pore structure of sample are tested
The measurement of the specific surface area and pore structure of the FeOOH sample prepared in the present embodiment and comparative example is in the U.S.
It is carried out in the full-automatic specific surface of Micrometric company ASAP 2020M type and micropore size distribution instrument.Before test, first by sample
It vacuumizes at 100 DEG C (less than 10-5Torr it) pre-processes within 2 hours, then carries out the measurement of nitrogen adsorption desorption under the conditions of liquid nitrogen.Surface
Product is calculated according to Berrett-Emmett-Teller (BET) method, pore volume and pore-size distribution according to desorption branch according to
Berret-Joyner-Halenda (BJH) model calculates.The grain size of sample uses Debye-Scherrer equation calculation: D
=k λ/β cos θ, wherein D is grain size (nm)；K is Scherrer constant, takes K=0.9；λ is X-ray wavelength；β is diffraction
Peak width degree (FWHM)；θ is Bragg angle of diffraction.
FeOOH sample in embodiment 1-5 and comparative example is tested, experimental result see the table below:
The specific surface and pore structure test result of 1 sample of table
2. sample hydrocracking reaction performance test
The present invention is split using the FeOOH sample of supergravity reactor serialization preparation in mink cell focus floating bed hydrogenation
Change the application in reaction:
Evaluation condition: in autoclave reaction system, using Kelamayi high calcium super-viscous oil as feedstock oil, supergravity reactor
The FeOOH and vulcanizing agent of preparation are added in autoclave together.First replaced with nitrogen, then be passed through hydrogen, in certain temperature and
Vulcanized and reacted under pressure, finally collects gaseous product and product liquid.Specific reaction condition are as follows: in 300ml reaction kettle
In, initial pressure 12.0MPa, sulfidation is divided to two sections, and respectively temperature is 250 DEG C, 30 minutes and 350 DEG C, 30 minutes；Instead
Answering temperature is 440 DEG C.Reaction pressure can be fluctuated in the case where initial pressure is certain in a small range.So keeping initial pressure
Power is identical.Feedstock oil conversion ratio and fraction oil yield are calculated according to the following formula, the evaluation index as reaction effect:
Conversion ratio=520 DEG C following components quality (containing gas)/raw material oil quality × 100%
Gas recovery ratio=(feedstock oil-product liquid quality)/raw material oil quality × 100%
Fraction oil yield=520 DEG C or less liquid component quality/raw material oil quality × 100%
2 sample hydrocracking reaction the performance test results of table
| Gas recovery ratio/% | Fraction oil yield/% | Conversion ratio/% | |
| A | 9.7 | 83.1 | 92.8 |
| B | 8.9 | 83.8 | 92.7 |
| C | 9.5 | 82.9 | 92.4 |
| D | 9.1 | 84.1 | 93.2 |
| E | 9.1 | 83.4 | 92.5 |
| F | 15.4 | 65.7 | 81.1 |
| G | 14.7 | 68.1 | 82.8 |
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (16)
1. a kind of preparation method of FeOOH, which comprises the following steps:
Under the conditions of hypergravity, by Fe2+Salting liquid and aqueous slkali mixing, meanwhile, connect oxygen-containing gas inversely with reaction solution
Touching, obtains reaction mixed serum；
The reaction mixed serum is subjected to gas-liquid separation, gained liquid is aged under conditions of stirring and being bubbled oxidation, is made
Suspension containing FeOOH；
The suspension is subjected to solid-liquor separation, solid phase is washed, dries, and obtains hydroxyl iron hydroxide.
2. the preparation method of FeOOH according to claim 1, which is characterized in that rate-determining steps (1) described reaction
The pH of mixed serum is 6.0-14.0.
3. the preparation method of FeOOH according to claim 2, which is characterized in that rate-determining steps (1) described reaction
The pH of mixed serum is 7.0-12.0.
4. the preparation method of FeOOH according to claim 1, which is characterized in that described to contain Fe2+Metal salt solution
For one or more of frerrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate.
5. the preparation method of FeOOH according to claim 1, which is characterized in that wherein contain Fe2+The concentration of solution
For 0.1-3mol/L.
6. the preparation method of FeOOH according to claim 5, which is characterized in that wherein contain Fe2+The concentration of solution
For 0.2-2mol/L.
7. the preparation method of FeOOH according to claim 1, which is characterized in that the aqueous slkali be sodium carbonate,
One or more of sodium bicarbonate, ammonium hydrogen carbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide.
8. the preparation method of FeOOH according to claim 1, which is characterized in that the concentration of the aqueous slkali is
0.5-15mol/L。
9. the preparation method of FeOOH according to claim 8, which is characterized in that the concentration of the aqueous slkali is 1-
10mol/L。
10. the preparation method of FeOOH according to claim 1, which is characterized in that the step (1) selects rotation
Packed bed supergravity reactor, the revolving speed of the rotary packed bed supergravity reactor are 100-10000rpm.
11. the preparation method of FeOOH according to claim 10, which is characterized in that preferably 300-5000rpm.
12. the preparation method of FeOOH according to claim 1, which is characterized in that step (2) is selected with stirring
The aging tank of device, digestion time 10-300min.
13. the preparation method of FeOOH according to claim 12, which is characterized in that step (2) is selected to have and be stirred
Mix the aging tank of device, digestion time 30-180min.
14. the preparation method of FeOOH according to claim 1, which is characterized in that the temperature of the ageing is 20-
90℃。
15. the preparation method of FeOOH according to claim 14, which is characterized in that the temperature of the ageing is
30-80℃。
16. the preparation method of -15 described in any item FeOOHs according to claim 1, which is characterized in that the hydroxyl oxygen
Change iron is Alpha-hydroxy iron oxide, beta-hydroxy iron oxide, γ-FeOOH, δ-FeOOH or amorphous FeOOH
One of.
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| CN108946820B (en) * | 2018-08-06 | 2021-06-08 | 武汉轻工大学 | Carbonate patina and preparation method thereof |
| CN109351357B (en) * | 2018-10-16 | 2020-09-22 | 华中科技大学 | Universal method for effectively improving catalytic performance of perovskite catalyst |
| CN109437321B (en) * | 2019-01-18 | 2021-04-06 | 广西雅照钛白有限公司 | Method for producing iron oxide red by using titanium dioxide byproduct ferrous sulfate heptahydrate |
| CN110422885A (en) * | 2019-08-23 | 2019-11-08 | 上海新禹固废处理有限公司 | A kind of preparation method of compound hydrated ferric oxide |
| CN111686731B (en) * | 2020-06-05 | 2023-06-16 | 中北大学 | Preparation method of alpha-FeOOH/GAC catalyst and application of alpha-FeOOH/GAC catalyst in degrading nitrobenzene wastewater in hypergravity field |
| CN112110491B (en) * | 2020-08-18 | 2022-10-04 | 江苏宇星科技有限公司 | Preparation method of iron oxyhydroxide for biological fermentation desulfurization |
| CN113828310A (en) * | 2021-10-13 | 2021-12-24 | 太原科技大学 | FeOOH/Cu2O composite microsphere photocatalyst and preparation method thereof |
| CN114045179B (en) * | 2021-11-30 | 2023-04-11 | 陕西延长石油（集团）有限责任公司 | Multiphase flow residual oil hydro-upgrading and catalytic cracking combined process and system |
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| CN116212625B (en) * | 2023-05-09 | 2023-09-05 | 明硕环境科技集团股份有限公司 | High-strength ferric hydroxide desulfurizing agent and preparation method thereof |
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