CN110152681A - A kind of preparation method of magnetic solid acid catalyst - Google Patents
A kind of preparation method of magnetic solid acid catalyst Download PDFInfo
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- CN110152681A CN110152681A CN201810283691.9A CN201810283691A CN110152681A CN 110152681 A CN110152681 A CN 110152681A CN 201810283691 A CN201810283691 A CN 201810283691A CN 110152681 A CN110152681 A CN 110152681A
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- manganese
- solid acid
- magnetic
- acid catalyst
- magnetic solid
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- 239000011973 solid acid Substances 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 claims abstract description 21
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 19
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 239000011686 zinc sulphate Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- -1 o-phenanthroline iron ion Chemical class 0.000 claims description 2
- 238000002798 spectrophotometry method Methods 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229940099596 manganese sulfate Drugs 0.000 abstract description 3
- 239000011702 manganese sulphate Substances 0.000 abstract description 3
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000002525 ultrasonication Methods 0.000 abstract 1
- 150000003751 zinc Chemical class 0.000 abstract 1
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 12
- 239000002699 waste material Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000006247 magnetic powder Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 244000144730 Amygdalus persica Species 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 240000001085 Trapa natans Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of magnetic solid acid catalyst, the removal of impurities of Leaching of rhodochrosite ore liquid impurity is required low, process flow is short, mainly include following two step: the first step is will be using low grade rhodochrosite as raw material, through acidleach, the Leaching of manganese sulfate liquid that must be purified after filtering and impurity removing, additional zinc salt, molysite, the magnetic core of magnetic solid acid is prepared using chemical coprecipitation, second step wraps up magnetic core with solid acid, under ultrasonication, manganese-zinc ferrite is dispersed in the aqueous solution of aluminum nitrate, pH is adjusted by ammonium hydroxide, then it is aged, filtering, drying, calcination activation is up to magnetic solid acid catalyst, manganese spar leaching liquid removal of impurities of the present invention is easy to operate, it is easily controllable, foreign ion influences magnetic solid acid performance small, the magnetic solid acid catalyst of preparation is magnetic big, it is active high, it is easily recycled, it is at low cost, it reduces Pollution of the low-grade manganese to environment.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, specially a kind of preparation method of magnetic solid acid catalyst.
Background technique
China is a manganese resource big country, by current, found out in existing 213 Manganese Ore Districts in China, has possessed storage
Amount shares 5.66 hundred million tons, and manganese ore is distributed widely in national 23 provinces, municipalities and autonomous regions, and wherein Guizhou pine peach is most important manganese
Ore resources area, 2.42 hundred million tons of manganese ore reserves, 30% or more of Zhan Quanguo reserves, although Guizhou is that manganese resource is big
State, but Guizhou majority manganese ore is low-grade ore, and in the majority with manganese carbonate ore, wherein general manganese grade is lower than 20%, low-grade manganese
It is largely stacked in mining area, the disposition of enterprise place is not only increased and the expenses such as land acquisition increases enterprise and are produced into, and
And also largely occupy land resource, these waste residues are stored for a long time, some harmful elements can be penetrated by soil layer earth's surface,
It is lauched, also will affect groundwater resources, pollute water environment, endanger the ecosystem, while the valuable element quilt in low-grade manganese
It abandons, causes the waste of manganese resource, so, using the poor manganese spar resource of Guizhou pine peach, probe into inexpensive, environmental-friendly
There is positive realistic meaning to the supply and demand for solving the problems, such as China's manganese series of products with the manganese-zinc ferrite production ways of small investment
With important application prospect；
Acid catalyzed reaction is one of the important reaction type in modern chemical industry, traditional homogeneous catalyst such as sulfuric acid, trichlorine
Change aluminium etc. and be currently widely used for the chemical production process such as esterification, alkene hydration, alkylation, cracking, polymerization, for traditional acid
Catalyst, such as dense H2SO4、H3PO4Deng, although specific cheap, catalytic benefit preferably, the advantages that being widely used, it is lacked
Point is more prominent, is such as difficult to separate with product, recycles difficulty, perishable test apparatus equipment, a large amount of discharging of waste liquid and cause environment
Pollution etc..
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of preparation of magnetic solid acid catalyst
Method, magnetic big, epigranular can be recycled, and performance is excellent, effectively realize the recycling of resource, and protect environment, can be with
Effectively solve the problems in background technique.
To achieve the above object, the invention provides the following technical scheme: a kind of preparation method of magnetic solid acid catalyst,
The following steps are included:
1) it after low-grade (manganese content≤20.0%) manganese spar being sieved with ball mill grinding, is soaked with the sulfuric acid of 18.0%-30.0%
It takes, bath temperature is 75.0-90.0 DEG C, stirring intensity 15.0r/s-40.0r/s, stirs 3.0-5.0h, then filters, and is added
Barium hydroxide pH value is adjusted to 5.2-5.8, leachate is obtained by filtration by excess iron powder, after the removal of impurities of national standard titration measuring
Manganese ion content in filtrate, uses spectrophotometric determination o-phenanthroline iron ion content；
2) manganese spar leaching liquid is synthesized into manganese-zinc ferrite using co-precipitation-hydro-thermal method, the molar ratio according to manganese, zinc, iron is
2.5:1.0:4.0 weighing FeSO4And ZnSO4It is placed in the leachate of purification, then barium hydroxide pH is adjusted to 10.0-11.0,
The dispersing agent of 1.0%-2.0% is added, dispersing agent is p-methyl benzenesulfonic acid, is heated to boiling, and after precipitation 10.0h-20.0h, is removed
It is transferred in reaction kettle after supernatant, 5.0-8.0h is reacted under the conditions of 180.0 DEG C -220.0 DEG C, then filtration washing, 100.0
Dry 2.0h, obtains product manganese-zinc ferrite magnetic medium powder under the conditions of DEG C -105.0 DEG C；
3) ANN aluminium nitrate nonahydrate and manganese-zinc ferrite are weighed according to mass ratio 2.0:1.0, ANN aluminium nitrate nonahydrate is first dissolved in 60.0-
In 80.0 DEG C of water, manganese-zinc ferrite is dispersed under ultrasound condition, barium hydroxide is then slowly added dropwise, adjust the pH of solution to
9.0-11.0 forms precipitating, and then water-bath precipitation 30.0mim-60.0min under the conditions of 75.0 DEG C -80.0 DEG C, is then stirred
30.0min-50.0min stands filtration washing after 12.0h-24.0h, in horse at being 500.0 DEG C -600.0 DEG C in temperature after dry
Not kiln roasting 4.0h-6.0h can be prepared by magnetic solid acid catalyst.
As a preferred technical solution of the present invention, the barium hydroxide is content >=96.0% and crosses 200.0 meshes
Solid powder, iron powder are technical grade.
Compared with prior art, the beneficial effects of the present invention are: the preparation method of this magnetic solid acid catalyst, 1, in water chestnut
With the pH value of solid powder barium hydroxide control reaction system in Leaching Solution of Manganese Ore, wherein barium ions can be with the sulfate radical of leachate
Ion, which is formed, to be precipitated and is removed, and in addition hydroxyl can remove most of foreign ion such as calcium, magnesium as precipitating reagent, thus
The comprehensive utilization for realizing magnesium, ferrous ion maximal efficiency, breaches the traditional handicraft of " first clean and prepare afterwards ", and a step completes preparation
The process of pure manganese sulfate shortens the process for preparing manganese-zinc ferrite in next step；
2, it reduces low-grade manganese to endanger environment bring, realizes the regeneration of waste resource；
3, it keeps also giving the certain magnetism of solid acid catalyst while solid acid catalyst activity, makes it in externally-applied magnetic field
Effect is lower to realize quick separating, reusable；
4, the method for the present invention synthesis technology step is simple, and cost of material is low, and product solid acid economic value is high.
Detailed description of the invention
Fig. 1 is infrared light (IR) spectrogram of the invention；
Fig. 2 is X x ray diffraction (XRD) figure of the invention；
Fig. 3 is scanning electron microscope (SEM) figure of the invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment one
A kind of preparation method of magnetic solid acid catalyst, comprising the following steps:
After low-grade manganese is crushed with ball mill, 200.0 meshes are crossed, are leached with 20.0% sulfuric acid solution, in water-bath 80.0
DEG C, stirring intensity is stirred to react 3.0h and is added after excess iron powder after leachate filtering with 70.0 μm under conditions of being 20.0r/s
Solid barium hydroxide adjusts filtrate pH to 5.2, and filtrate is obtained by filtration；
It is equal to 2.5:1.0:4.0 according to the molar ratio of manganese, zinc, iron, weighs FeSO4And ZnSO4It is placed in the leachate of purification, then
Adjusting pH with barium hydroxide is 10.0, and the p-methyl benzenesulfonic acid for adding 1.0% is dispersing agent, is heated to boiling, after precipitation 10.0h,
It is transferred in reaction kettle after removing supernatant, 6.0h is reacted under the conditions of 180.0 DEG C, filtration washing is dry under the conditions of 102.0 DEG C
2.0h obtains manganese-zinc ferrite magnetic powder；
ANN aluminium nitrate nonahydrate and manganese-zinc ferrite are weighed according to mass ratio 2.0:1.0, ANN aluminium nitrate nonahydrate is first dissolved in 60.0 DEG C
It in water, disperses manganese-zinc ferrite in aluminum nitrate solution under ultrasound condition, the pH that barium hydroxide adjusts solution is slowly added dropwise
To 9.0, water-bath precipitation 30.0mim under the conditions of 75.0 DEG C is stirred for 30.0min, filtration washing after 24.0h is stood, after dry
4.0h is roasted under the conditions of 500 DEG C of temperature, magnetic solid acid catalyst is made.
Magnetic retention acid-catalyzed esterification reaction, octyl acetate yield are 97.1%, recycle solid acid catalyst and repeat
Using three times, octyl acetate yield is respectively 97.0%, 96.7%, 96.9%.
Embodiment two
A kind of preparation method of magnetic solid acid catalyst, comprising the following steps:
After low-grade manganese is crushed with ball mill, 200.0 meshes are crossed, are leached with 23.0% sulfuric acid solution, in water-bath 75.0
DEG C, stirring intensity is stirred to react 3.5h under conditions of being 25r/s, after leachate filtering, use about 74.0 μm after excess iron powder is added
Solid barium hydroxide adjusts filtrate pH to 5.4, filters to get filtrate；
It is equal to 2.5: 1: 4 according to the molar ratio of manganese, zinc, iron, weighs FeSO4And ZnSO4It is placed in the leachate of purification, then
Adjusting pH with barium hydroxide is 10.5, and the p-methyl benzenesulfonic acid for adding 1.5% is dispersing agent, is heated to boiling, after precipitation 15.0h,
It is transferred in reaction kettle after removing supernatant, 7.0h is reacted under the conditions of 190.0 DEG C, filtration washing is dry under the conditions of 105.0 DEG C
2.0h obtains manganese-zinc ferrite magnetic powder；
ANN aluminium nitrate nonahydrate and manganese-zinc ferrite are weighed according to mass ratio 2.0:1.0, ANN aluminium nitrate nonahydrate is first dissolved in 65.0 DEG C
It in water, disperses manganese-zinc ferrite in aluminum nitrate solution under ultrasound condition, the pH that barium hydroxide adjusts solution is slowly added dropwise
To 9.5,75 DEG C of water-bath precipitation 60.0mim, it is stirred for 30.0min, filtration washing after 16.0h is stood, in temperature 550.0 after drying
5.0h is roasted at DEG C, and magnetic solid acid catalyst is made.
Magnetic retention acid-catalyzed esterification reaction, octyl acetate yield are 97.5%, recycle solid acid catalyst and repeat
Using three times, octyl acetate yield is respectively 97.2%, 96.3%, 96.4%.
Embodiment three
A kind of preparation method of magnetic solid acid catalyst, comprising the following steps:
After low-grade manganese is crushed with ball mill, 200.0 meshes are crossed, are leached with 18.0% sulfuric acid solution, in water-bath 85.0
DEG C, stirring intensity is stirred to react 4.0h and is added after excess iron powder after leachate filtering with 65.0 μm under conditions of being 30.0r/s
Solid barium hydroxide adjusts filtrate pH to 5.4, and filtrate is obtained by filtration；
It is equal to 2.5: 1.0:4.0 according to the molar ratio of manganese, zinc, iron, weighs FeSO4And ZnSO4It is placed in the leachate of purification,
Adjusting pH with barium hydroxide again is 11.0, and the p-methyl benzenesulfonic acid for adding 2.0% is dispersing agent, is heated to boiling, precipitation 12.0h
Afterwards, it is transferred in reaction kettle after removing supernatant, 8.0h, filtration washing, under the conditions of 102.0 DEG C is reacted under the conditions of 200.0 DEG C
Dry 2.0h, obtains manganese-zinc ferrite magnetic powder.
ANN aluminium nitrate nonahydrate and manganese-zinc ferrite are weighed according to mass ratio 2.0:1.0, is first dissolved in ANN aluminium nitrate nonahydrate
It in 75.0 DEG C of water, disperses manganese-zinc ferrite in aluminum nitrate solution under ultrasound condition, it is molten that barium hydroxide adjusting is slowly added dropwise
The pH to 11.0 of liquid, 80.0 DEG C of water-bath precipitation 60.0mim, are stirred for 50.0min, stand filtration washing after 24.0h, it is dry after
6.0h is roasted under the conditions of at 500.0 DEG C of temperature, magnetic solid acid catalyst is made.
Magnetic retention acid-catalyzed esterification reaction, octyl acetate yield are 97.9%, recycle solid acid catalyst and repeat
Using three times, octyl acetate yield is respectively 97.5%, 97.7%, 97.4%.
The present invention controls the pH value of reaction system in Leaching of rhodochrosite ore liquid with solid powder barium hydroxide, wherein barium ions
It can be formed with the sulfate ion of leachate and precipitate and be removed, in addition it is big to can remove calcium, magnesium etc. as precipitating reagent for hydroxyl
Partial impurities ion breaches the tradition of " first clean and prepare afterwards " to realize the comprehensive utilization of magnesium, ferrous ion maximal efficiency
Technique, a step are completed to prepare the process of pure manganese sulfate, shorten the process for preparing manganese-zinc ferrite in next step；It reduces low-grade
Manganese ore endangers environment bring, realizes the regeneration of waste resource；It keeps also assigning while solid acid catalyst activity
The certain magnetism of solid acid catalyst makes it under the action of an external magnetic field realize quick separating, reusable；Side of the present invention
Method synthesis technology step is simple, and cost of material is low, and product solid acid economic value is high.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (2)
1. a kind of preparation method of magnetic solid acid catalyst, which comprises the following steps:
1) it after low-grade (manganese content≤20.0%) manganese spar being sieved with ball mill grinding, is soaked with the sulfuric acid of 18.0%-30.0%
It takes, bath temperature is 75.0-90.0 DEG C, stirring intensity 15.0r/s-40.0r/s, stirs 3.0-5.0h, then filters, and is added
Barium hydroxide pH value is adjusted to 5.2-5.8, leachate is obtained by filtration by excess iron powder, after the removal of impurities of national standard titration measuring
Manganese ion content in filtrate, uses spectrophotometric determination o-phenanthroline iron ion content；
2) manganese spar leaching liquid is synthesized into manganese-zinc ferrite using co-precipitation-hydro-thermal method, the molar ratio according to manganese, zinc, iron is
2.5:1.0:4.0 weighing FeSO4And ZnSO4It is placed in the leachate of purification, then barium hydroxide pH is adjusted to 10.0-11.0,
The dispersing agent of 1.0%-2.0% is added, dispersing agent is p-methyl benzenesulfonic acid, is heated to boiling, and after precipitation 10.0h-20.0h, is removed
It is transferred in reaction kettle after supernatant, 5.0-8.0h is reacted under the conditions of 180.0 DEG C -220.0 DEG C, then filtration washing, 100.0
Dry 2.0h, obtains product manganese-zinc ferrite magnetic medium powder under the conditions of DEG C -105.0 DEG C；
3) ANN aluminium nitrate nonahydrate and manganese-zinc ferrite are weighed according to mass ratio 2.0:1.0, ANN aluminium nitrate nonahydrate is first dissolved in 60.0-
In 80.0 DEG C of water, manganese-zinc ferrite is dispersed under ultrasound condition, barium hydroxide is then slowly added dropwise, adjust the pH of solution to
9.0-11.0 forms precipitating, and then water-bath precipitation 30.0mim-60.0min under the conditions of 75.0 DEG C -80.0 DEG C, is then stirred
30.0min-50.0min stands filtration washing after 12.0h-24.0h, in horse at being 500.0 DEG C -600.0 DEG C in temperature after dry
Not kiln roasting 4.0h-6.0h can be prepared by magnetic solid acid catalyst.
2. a kind of preparation method of magnetic solid acid catalyst according to claim 1, it is characterised in that: the hydroxide
Barium is content >=96.0% and the solid powder for crossing 200.0 meshes, and iron powder is technical grade.
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| US20040116284A1 (en) * | 2002-12-12 | 2004-06-17 | Saudi Basic Industries Corporation | Preparation of mixed metal oxide catalysts for catalytic oxidation of olefins to unsaturated aldehydes |
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| CN103447054A (en) * | 2013-09-10 | 2013-12-18 | 重庆大学 | Manganese magnetic solid acid catalyst preparation method and manganese magnetic solid acid catalyst |
| CN107055501A (en) * | 2017-04-28 | 2017-08-18 | 北京科技大学 | A kind of method that hureaulite type manganese phosphate is prepared from low grade rhodochrosite leachate |
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| US20040116284A1 (en) * | 2002-12-12 | 2004-06-17 | Saudi Basic Industries Corporation | Preparation of mixed metal oxide catalysts for catalytic oxidation of olefins to unsaturated aldehydes |
| CN102775138A (en) * | 2012-08-06 | 2012-11-14 | 重庆大学 | Method for preparing manganese-zinc ferrites through carrying out acid dipping on low-grade manganese ores and carrying out ferromanganese remaining and impurity removal |
| CN103447054A (en) * | 2013-09-10 | 2013-12-18 | 重庆大学 | Manganese magnetic solid acid catalyst preparation method and manganese magnetic solid acid catalyst |
| CN107055501A (en) * | 2017-04-28 | 2017-08-18 | 北京科技大学 | A kind of method that hureaulite type manganese phosphate is prepared from low grade rhodochrosite leachate |
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Application publication date: 20190823 |