CN105879922A - Molybdenum disulfide modified catalytic wet oxidation catalyst and preparation method thereof - Google Patents
Molybdenum disulfide modified catalytic wet oxidation catalyst and preparation method thereof Download PDFInfo
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- CN105879922A CN105879922A CN201610332609.8A CN201610332609A CN105879922A CN 105879922 A CN105879922 A CN 105879922A CN 201610332609 A CN201610332609 A CN 201610332609A CN 105879922 A CN105879922 A CN 105879922A
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- parts
- catalyst
- molybdenum bisuphide
- wet oxidation
- catalytic wet
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 57
- 239000011733 molybdenum Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 37
- 239000012018 catalyst precursor Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000010348 incorporation Methods 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000005562 Glyphosate Substances 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 4
- 229940097068 glyphosate Drugs 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/613—10-100 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a molybdenum disulfide modified catalytic wet oxidation catalyst and a preparation method thereof and belongs to the technical field of catalytic wet oxidation catalysts. The molybdenum disulfide modified catalytic wet oxidation catalyst is prepared from the following components in parts by weight: 70-95 parts of titanium dioxide, 5-15 parts of molybdenum disulfide, 5-15 parts of an additive, 1-10 parts of an organic binding agent and 0.01-5 parts of active components. The lateral compressive strength of a catalyst finished product can reach 240N/cm; and the stability, strength and toughness are increased and the product is not like to crack. Meanwhile, the molybdenum element is used as a transition element and has the effect of transmitting electrons, and the wet catalytic oxidization efficiency can be effectively improved.
Description
Technical field
The present invention relates to modified catalyst of a kind of molybdenum bisuphide and preparation method thereof, it is more particularly related to catalytic wet oxidation catalyst of a kind of molybdenum bisuphide modification and preparation method thereof, belong to the technical field that catalytic wet oxidation catalyst processes with waste water.
Background technology
CWO (Catalytic Wet Air Oxidation) is increasingly becoming the new technique processing high concentration difficult for biological degradation industrial wastewater in recent years, and the core of this technology is exactly corresponding catalyst with key.Wet Oxidation Process relatively, the addition of catalyst can reduce the pressure needed for its reaction and temperature, improve its treatment effeciency simultaneously.CWO have occupation of land less, applied range, treatment effeciency are high, do not produce the advantages such as secondary waste thing.But corresponding high temperature, reaction under high pressure condition, then to the intensity of catalyst, wear-resistant requirement height, and common carrier titanic oxide shaping is poor at present, intensity is relatively low, and side pressure strength only has about 100N/cm, and wear resistance is the best, easily dry linting slagging, the life-span is the longest.At present for overcoming this shortcoming, proposition is had to add zirconium dioxide, rare earth oxide, make the techniques such as coating of transition metal.
State Intellectual Property Office discloses Publication No. CN101284248 in 2008.10.15, the invention of entitled " titanic oxide shaping carrier of a kind of modified by alkali-free glass fibre and preparation method thereof ", a kind of high hydrothermal stability TiO of this disclosure of the invention2Shaping carrier, described TiO2In shaping carrier, the mass percent of each component is: alkali-free glass fibre is 0.5%～20%, and titanium dioxide is 80%～99.5%, and its specific surface area is 40～150m2/ g, comprcssive strength is 80～160N/cm, and after hydrothermal treatment, the comprcssive strength of carrier reduces below 15%.The invention have the advantage that at TiO2The preparation process of shaping carrier introduces alkali-free glass fibre, significantly improves TiO under high-temperature water thermal environment2The comprcssive strength of shaping carrier, improves its hydrothermal stability.This TiO2Shaping carrier has a extensive future, and during can be used for the catalytic hydrogenation reaction that reaction condition is relatively mild or harsh, is particularly well suited as aqueous phase or the catalyst carrier of other liquid-phase hydrogenatin reaction under High Temperature High Pressure.The preparation method technique of the present invention is simple, and cost is relatively low, production suitable for industrialized.The invention discloses its preparation method.
Above-mentioned prior art use alkali-free glass fibre be modified, although comprcssive strength has obtained certain raising, but or the most relatively low, and still there is mouldability and the best problem of wear resistance.
Summary of the invention
Present invention seek to address that the body formed difference of TiO 2 carrying in existing catalyst, intensity is low, the problem of wear resistance difference, it is proposed that the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, make this catalyst have intensity height, good moldability, anti abrasive characteristic, and then extend service life.
In order to realize foregoing invention purpose, its concrete technical scheme is as follows:
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, it is characterised in that: include following component in parts by weight:
Titanium dioxide
70～95 parts
Molybdenum bisuphide
5～15 parts
Additive
5～15 parts
Organic binder bond
1～10 part
Active component
0.01～5 part.
Preferably, the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, it is characterised in that: include following component in parts by weight:
Titanium dioxide
85～95 parts
Molybdenum bisuphide
5～10 parts
Additive
5～10 parts
Organic binder bond
2～5 parts
Active component
0.5～2 part.
Currently preferred, described additive is the mixture that a kind of or arbitrary proportion in graphite, silicon dioxide, zirconium oxide and cerium oxide is two or more.
Currently preferred, described organic binder bond is methylcellulose, sesbania powder, clay, polyvinyl alcohol, polyacrylamide or glycerol.
Currently preferred, described active component is the combination that a kind of or arbitrary proportion in ruthenium, palladium and platinum is two or more.
In such scheme, used titanium dioxide, silicon dioxide, zirconium oxide, cerium oxide are all nanometer grade powders, and the specific surface area of titanium dioxide and silicon dioxide is all not less than 100m2The specific surface area of/g, zirconium oxide and cerium oxide is 20～50m2/g.Molybdenum bisuphide used is the molybdenum bisuphide of 2000 mesh 98.5% content.Organic binder bond used preferentially selects sesbania powder and methylcellulose.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, it is characterised in that: comprise the following steps that:
A, titanium dioxide, molybdenum bisuphide, additive, organic binder bond are placed in kneader mixing, obtain mixture；
B, being uniformly sprayed at by acid solution in the mixture that step A obtains, mixing, the shape that obtains luming moistens mixture；
C, caking shape step B obtained moisten mixture extruded moulding on extruder, obtain column；
D, column step C obtained are dried through 70～100 DEG C, and through 600～900 DEG C of roastings, obtain catalyst carrier；
E, the soluble-salt of active component is configured to solution；
F, disperseed on a catalyst support by incipient impregnation or excess infusion process solution that step E is obtained, be dried to obtain catalyst precursor；
G, catalyst precursor is carried out reduction obtain catalyst.
In step, described incorporation time is 20～60min to the present invention.
In stepb, described acid solution is mass concentration 5～the inorganic acid solution of 15% to the present invention, or organic acid soln, example hydrochloric acid solution, salpeter solution, lactic acid solution, citric acid solution, acetic acid solution.
In stepb, described acid solution is 0.6～1:1 with the mass ratio of described mixture to the present invention.
In stepb, the time of described mixing is 2～4h to the present invention.
The present invention in step C, a length of the 0.5 of described column～1cm.
The present invention is in step E, and the soluble-salt of described active component is the two or more mixture of a kind of or arbitrary proportion in ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium, Palladous chloride., palladium and chloroplatinic acid.
The present invention is in step E, and the tenor of described solution is 0.5～5g/100mL.
Excessive moisture decompression, in step F, particularly as follows: catalyst carrier is dipped in solution 0.5～3h, is then distilled off, is dried to obtain catalyst precursor then at 70～120 DEG C by the present invention.
The present invention in step G, described in be reduced to reduce catalyst precursor formaldehyde, or under the conditions of 300～600 DEG C, hydrogen reducing obtains catalyst.
The Advantageous Effects that the present invention brings:
1, due to titanium dioxide, there is anatase and two kinds of common crystal formations of rutile, crystal transition slowly can occur under conditions of High Temperature High Pressure, thus cause catalyst that breakage occurs.The present invention solves the body formed difference of TiO 2 carrying in existing catalyst, and intensity is low, the problem of wear resistance difference.By adding the molybdenum bisuphide of specified quantitative, simultaneously with the coordinating of other specified quantitative components, roasting process converts molybdenum oxide, forms bridging with titanium dioxide thus add stability, intensity and toughness, not easily broken.Molybdenum element is as transition metal simultaneously, has the effect of transmission electronics, can be effectively improved wet method catalysis oxidation efficiency.
2, the catalyst activity of the present invention is high, runs off few after using, and uses the time long, does not haves and adds the secondary pollution that soluble transition metal salt causes in homogeneous catalytic oxidation.
3, the catalyst of the present invention is highly suitable for heterogeneous wet oxidation process, it is possible to the oxidation operation in the waste water produced during producing glyphosate is decomposed into CO2With micromolecular compounds such as water, the P elements in organic compound is converted into Phos, inorganic phosphate is recovered by filtration by crystallization further and recycles.Clearance >=98% of COD in waste water, catalyst loss rate≤0.02%.
Detailed description of the invention
Embodiment
1
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
70 parts
Molybdenum bisuphide
5 parts
Additive
5 parts
Organic binder bond
1 part
Active component
0.01 part.
Embodiment
2
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
95 parts
Molybdenum bisuphide
15 parts
Additive
15 parts
Organic binder bond
10 parts
Active component
5 parts.
Embodiment
3
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
82.5 parts
Molybdenum bisuphide
10 parts
Additive
10 parts
Organic binder bond
5.5 part
Active component
2.5 part.
Embodiment
4
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
90 parts
Molybdenum bisuphide
12 parts
Additive
7 parts
Organic binder bond
3 parts
Active component
1 part.
Embodiment
5
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
85 parts
Molybdenum bisuphide
5 parts
Additive
5 parts
Organic binder bond
2 parts
Active component
0.5 part.
Embodiment
6
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
95 parts
Molybdenum bisuphide
10 parts
Additive
10 parts
Organic binder bond
5 parts
Active component
2 parts.
Embodiment
7
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
90 parts
Molybdenum bisuphide
7.5 part
Additive
7.5 part
Organic binder bond
3.5 part
Active component
1.25 part.
Embodiment
8
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, including following component in parts by weight:
Titanium dioxide
86 parts
Molybdenum bisuphide
9 parts
Additive
7 parts
Organic binder bond
3 parts
Active component
1 part.
Embodiment
9
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, comprises the following steps that:
A, titanium dioxide, molybdenum bisuphide, additive, organic binder bond are placed in kneader mixing, obtain mixture；
B, being uniformly sprayed at by acid solution in the mixture that step A obtains, mixing, the shape that obtains luming moistens mixture；
C, caking shape step B obtained moisten mixture extruded moulding on extruder, obtain column；
D, column step C obtained are dried through 70 DEG C, and through 600 DEG C of roastings, obtain catalyst carrier；
E, the soluble-salt of active component is configured to solution；
F, disperseed on a catalyst support by incipient impregnation or excess infusion process solution that step E is obtained, be dried to obtain catalyst precursor；
G, catalyst precursor is carried out reduction obtain catalyst.
Embodiment
10
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, comprises the following steps that:
A, titanium dioxide, molybdenum bisuphide, additive, organic binder bond are placed in kneader mixing, obtain mixture；
B, being uniformly sprayed at by acid solution in the mixture that step A obtains, mixing, the shape that obtains luming moistens mixture；
C, caking shape step B obtained moisten mixture extruded moulding on extruder, obtain column；
D, column step C obtained are dried through 100 DEG C, and through 900 DEG C of roastings, obtain catalyst carrier；
E, the soluble-salt of active component is configured to solution；
F, disperseed on a catalyst support by incipient impregnation or excess infusion process solution that step E is obtained, be dried to obtain catalyst precursor；
G, catalyst precursor is carried out reduction obtain catalyst.
Embodiment
11
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, comprises the following steps that:
A, titanium dioxide, molybdenum bisuphide, additive, organic binder bond are placed in kneader mixing, obtain mixture；
B, being uniformly sprayed at by acid solution in the mixture that step A obtains, mixing, the shape that obtains luming moistens mixture；
C, caking shape step B obtained moisten mixture extruded moulding on extruder, obtain column；
D, column step C obtained are dried through 85 DEG C, and through 750 DEG C of roastings, obtain catalyst carrier；
E, the soluble-salt of active component is configured to solution；
F, disperseed on a catalyst support by incipient impregnation or excess infusion process solution that step E is obtained, be dried to obtain catalyst precursor；
G, catalyst precursor is carried out reduction obtain catalyst.
Embodiment
12
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide is modified, comprises the following steps that:
A, titanium dioxide, molybdenum bisuphide, additive, organic binder bond are placed in kneader mixing, obtain mixture；
B, being uniformly sprayed at by acid solution in the mixture that step A obtains, mixing, the shape that obtains luming moistens mixture；
C, caking shape step B obtained moisten mixture extruded moulding on extruder, obtain column；
D, column step C obtained are dried through 80 DEG C, and through 800 DEG C of roastings, obtain catalyst carrier；
E, the soluble-salt of active component is configured to solution；
F, disperseed on a catalyst support by incipient impregnation or excess infusion process solution that step E is obtained, be dried to obtain catalyst precursor；
G, catalyst precursor is carried out reduction obtain catalyst.
Embodiment
13
On the basis of embodiment 9～12:
Preferably, in step, described incorporation time is 20min.
Preferably, in stepb, described acid solution is 0.6:1 with the mass ratio of described mixture.
Preferably or further, in stepb, the time of described mixing is 2h.
Preferably, in step C, a length of 0.5cm of described column.
Preferably, in step E, the tenor of described solution is 0.5g/100mL.
Preferably, in step F, particularly as follows: catalyst carrier to be dipped in 0.5h in solution, then excessive moisture decompression is distilled off, is dried to obtain catalyst precursor then at 70 DEG C.
Preferably, in step G, described in be reduced to reduce catalyst precursor formaldehyde, or under the conditions of 300 DEG C, hydrogen reducing obtains catalyst.
Embodiment
14
On the basis of embodiment 9～12:
Preferably, in step, described incorporation time is 60min.
Preferably, in stepb, described acid solution is 1:1 with the mass ratio of described mixture.
Preferably or further, in stepb, the time of described mixing is 4h.
Preferably, in step C, a length of 1cm of described column.
Preferably, in step E, the tenor of described solution is 5g/100mL.
Preferably, in step F, particularly as follows: catalyst carrier to be dipped in 3h in solution, then excessive moisture decompression is distilled off, is dried to obtain catalyst precursor then at 120 DEG C.
Preferably, in step G, described in be reduced to reduce catalyst precursor formaldehyde, or under the conditions of 600 DEG C, hydrogen reducing obtains catalyst.
Embodiment
15
On the basis of embodiment 9～12:
Preferably, in step, described incorporation time is 40min.
Preferably, in stepb, described acid solution is 0.8:1 with the mass ratio of described mixture.
Preferably or further, in stepb, the time of described mixing is 3h.
Preferably, in step C, a length of 0.75cm of described column.
Preferably, in step E, the tenor of described solution is 2.75g/100mL.
Preferably, in step F, particularly as follows: catalyst carrier to be dipped in 1.75h in solution, then excessive moisture decompression is distilled off, is dried to obtain catalyst precursor then at 95 DEG C.
Preferably, in step G, described in be reduced to reduce catalyst precursor formaldehyde, or under the conditions of 450 DEG C, hydrogen reducing obtains catalyst.
Embodiment
16
On the basis of embodiment 9～12:
Preferably, in step, described incorporation time is 25min.
Preferably, in stepb, described acid solution is 0.9:1 with the mass ratio of described mixture.
Preferably or further, in stepb, the time of described mixing is 3.5h.
Preferably, in step C, a length of 0.6cm of described column.
Preferably, in step E, the tenor of described solution is 2g/100mL.
Preferably, in step F, particularly as follows: catalyst carrier to be dipped in 2h in solution, then excessive moisture decompression is distilled off, is dried to obtain catalyst precursor then at 115 DEG C.
Preferably, in step G, described in be reduced to reduce catalyst precursor formaldehyde, or under the conditions of 550 DEG C, hydrogen reducing obtains catalyst.
Embodiment
17
Carrier prepares 1
1) weighing a certain amount of titanium dioxide, molybdenum bisuphide, zirconium dioxide, respectively 90 parts, 5 parts, the sesbania powder of 5 parts, and 2 parts, kneader is dry mixed 1h.
2) in kneader, in material, uniform speed slow adds 7% acetic acid solution, until mixture stops adding acetic acid solution after being converted into graininess and bulk by powdery, continues mixing 4h.
3) being transferred in banded extruder by the material mixed, carry out pelletizing while extrusion, extruded velocity is 50r/min, and extrusion pressure is 7MPa, and the specification of resulting vehicle is 4mm, a length of 5mm.
4) cylinder obtained is put into 70 DEG C of dry 12h in drying baker.
5) dried carrier is carried out roasting, 700 DEG C of roasting 4h.
Being tested by the carrier obtained, specific surface area is 33m2/ g, mean intensity is 218N.
Comparative example 1
In addition to without molybdenum bisuphide, it is identical that component, preparation technology, testing procedure all prepare 1 with carrier.But its mean intensity is 141N.
Embodiment
18
Carrier prepares 2
1) weighing a certain amount of titanium dioxide, molybdenum bisuphide, respectively 95 parts and 5 parts, and the methylcellulose of 2 parts, kneader is dry mixed 1h.
2) in kneader, in material, uniform speed slow adds 7% lactic acid solution, until mixture stops adding lactic acid solution after being converted into graininess and bulk by powdery, continues mixing 4h.
3) extruded moulding, is dried all identical with embodiment 17 with roasting.
Being tested by the carrier obtained, specific surface area is 31m2/ g, mean intensity is 220N.
Comparative example 2
In addition to without molybdenum bisuphide, it is identical that component, preparation technology, testing procedure all prepare 2 with carrier.But its mean intensity is 160N.
Embodiment
19
Carrier prepares 3
1) weighing a certain amount of titanium dioxide, molybdenum bisuphide, zirconium dioxide and silicon dioxide and be respectively 85 parts, 5 parts, 5 parts and 5 parts, and the methylcellulose of 5 parts, kneader is dry mixed 1h.
2) in kneader, in material, uniform speed slow adds 7% citric acid solution, until mixture stops adding citric acid solution after being converted into graininess and bulk by powdery, continues mixing 4h.
3) extruded moulding is identical with embodiment 17 with dry.
4) dried carrier is carried out roasting, 750 DEG C of roasting 4h.
Being tested by the carrier obtained, specific surface area is 23m2/ g, mean intensity is 182N.
Embodiment
20
Carrier prepares 4
1) weighing a certain amount of titanium dioxide, molybdenum bisuphide, zirconium dioxide and ceria and be respectively 82 parts, 5 parts, 10 parts and 3 parts, and the sesbania powder of 2 parts, kneader is dry mixed 1h.
2) in kneader, in material, uniform speed slow adds 7% acetic acid solution, until mixture stops adding acetic acid solution after being converted into graininess and bulk by powdery, continues mixing 4h.
3) extruded moulding, be dried identical with embodiment 17 with roasting.
Being tested by the carrier obtained, specific surface area is 30m2/ g, mean intensity is 232N.
Embodiment
21
Carrier prepares 5
1) weighing a certain amount of titanium dioxide, molybdenum bisuphide, respectively 90 parts and 10 parts, and the methylcellulose of 2 parts, kneader is dry mixed 1h.
2) in kneader, in material, uniform speed slow adds 7% lactic acid solution, until mixture stops adding lactic acid solution after being converted into graininess and bulk by powdery, continues mixing 4h.
3) extruded moulding, is dried all identical with embodiment 17 with roasting.
Being tested by the carrier obtained, specific surface area is 30m2/ g, mean intensity is 243N.
Embodiment
22
Catalyst prepares 1
1) weigh and be hydrated ruthenic chloride in right amount, add 27mL deionized water dissolving, be configured to solution for standby.
2) weigh the carrier of 100g embodiment 17, add to 1) solution in, shake simultaneously, make carrier be fully contacted with impregnation liquid, after dipping 1h, be placed at 120 DEG C dry 5h.
3) by 2) prepared 0 DEG C of roasting 2h of carrier 30 as one kind loading ruthenium, obtain finished catalyst 1%Ru/TiO2。
Embodiment
23
Catalyst prepares 2
1) weigh and be hydrated ruthenic chloride in right amount, add 70mL deionized water dissolving, be configured to solution for standby.
2) weighing the carrier of 100g embodiment 20, add to 1) in the solution prepared, solution, by carrier submergence, after being evaporated by excessive moisture, is placed at 120 DEG C and is dried 5h after dipping 1h.
3) by 2) the prepared carrier loading ruthenium, in sodium hydroxide solution, add thermal reduction, about 1h with formaldehyde.At 120 DEG C, it is dried 5h i.e. can get finished catalyst 1%Ru/TiO2。
Embodiment
24
Catalyst prepares 3
1) weigh appropriate hydration ruthenic chloride and Palladous chloride., add 70mL deionized water dissolving, be configured to solution for standby.
2) dipping process is identical with embodiment 23.
3) by 2) the prepared carrier loading ruthenium, in sodium hydroxide solution, add thermal reduction 0.5h with formaldehyde.At 120 DEG C, it is dried 5h i.e. can get finished catalyst 0.5wt%Ru+0.5wt%Pd/TiO2。
Embodiment
25
Catalyst is for the degradation experiment of glyphosate mother solution
1) the catalyst 10g of Example 23 preparation, is placed in 600mL autoclave.
2) to 1) described in add the initial COD of 100mL in autoclave be the glyphosate mother solution of 24860mg/L.
3) in autoclave, compressed air it is filled with to 2.5MPa.
4) design temperature is 245 DEG C, and mixing speed is 100r/min, begins to warm up.
5) start timing after being warming up to 245 DEG C, react 1h.
6) after reaction terminates, close heating and stirring, open cooling water, open cooling water and be down to room temperature, take the supernatant after release and be analyzed.
7) take out catalyst, after making to be washed with deionized totally, weigh after being dried 5h at 120 DEG C.
Post catalyst reaction profile is complete, does not has fragmentation, dry linting phenomenon, and reactant liquor is limpid；Being computed, COD clearance is 98%, and catalyst loss is 0.01%.
Embodiment
26
Catalyst is for the life experiment of glyphosate mother solution
1) the catalyst 10g of Example 22 preparation, is placed in 600mL autoclave.
2) reaction unit, temperature, pressure, post processing equivalent integers 9, the response time extends to 15 days.
Post catalyst reaction profile is complete, does not has fragmentation, dry linting phenomenon, and reactant liquor is limpid, and is not detected by ruthenium element in solution；Being computed, COD clearance is 99%, and catalyst loss is 0.02%, illustrates that catalyst stability is good, and the life-span is high.
Comparative example 3
1) catalyst carrier is prepared with the comparative example 1 in embodiment 17.
2) catalyst is prepared with embodiment 22.
3) catalyst is investigated and is evaluated with embodiment 26.
Post catalyst reaction has part fragmentation, and catalyst loss is 4%, and catalyst stability is poor, and the life-span is short.
Claims (10)
1. the catalytic wet oxidation catalyst that a molybdenum bisuphide is modified, it is characterised in that: include following component in parts by weight:
Titanium dioxide
70～95 parts
Molybdenum bisuphide
5～15 parts
Additive
5～15 parts
Organic binder bond
1～10 part
Active component
0.01～5 part.
The catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 1 is modified, it is characterised in that: include following component in parts by weight:
Titanium dioxide
85～95 parts
Molybdenum bisuphide
5～10 parts
Additive
5～10 parts
Organic binder bond
2～5 parts
Active component
0.5～2 part.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 1 and 2 is modified, it is characterised in that: comprise the following steps that:
A, titanium dioxide, molybdenum bisuphide, additive, organic binder bond are placed in kneader mixing, obtain mixture；
B, being uniformly sprayed at by acid solution in the mixture that step A obtains, mixing, the shape that obtains luming moistens mixture；
C, caking shape step B obtained moisten mixture extruded moulding on extruder, obtain column；
D, column step C obtained are dried through 70～100 DEG C, and through 600～900 DEG C of roastings, obtain catalyst carrier；
E, the soluble-salt of active component is configured to solution；
F, disperseed on a catalyst support by incipient impregnation or excess infusion process solution that step E is obtained, be dried to obtain catalyst precursor；
G, catalyst precursor is carried out reduction obtain catalyst.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 3 is modified, it is characterised in that: in step, described incorporation time is 20～60min.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 3 is modified, it is characterised in that: in stepb, described acid solution is 0.6～1:1 with the mass ratio of described mixture.
6. according to the preparation method of the modified catalytic wet oxidation catalyst of a kind of molybdenum bisuphide described in claim 3 or 5, it is characterised in that: in stepb, the time of described mixing is 2～4h.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 3 is modified, it is characterised in that: in step C, a length of the 0.5 of described column～1cm.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 3 is modified, it is characterised in that: in step E, the tenor of described solution is 0.5～5g/100mL.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 3 is modified, it is characterized in that: in step F, particularly as follows: catalyst carrier to be dipped in solution 0.5～3h, then excessive moisture decompression is distilled off, is dried to obtain catalyst precursor then at 70～120 DEG C.
The preparation method of the catalytic wet oxidation catalyst that a kind of molybdenum bisuphide the most according to claim 3 is modified, it is characterized in that: in step G, catalyst precursor formaldehyde is reduced by described being reduced to, or under the conditions of 300～600 DEG C, hydrogen reducing obtains catalyst.
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| CN201610332609.8A CN105879922A (en) | 2016-05-19 | 2016-05-19 | Molybdenum disulfide modified catalytic wet oxidation catalyst and preparation method thereof |
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|---|---|---|---|
| CN201610332609.8A CN105879922A (en) | 2016-05-19 | 2016-05-19 | Molybdenum disulfide modified catalytic wet oxidation catalyst and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317047A (en) * | 2019-07-10 | 2019-10-11 | 鲁东大学 | A kind of temperature gradient selfreparing multi-layered ceramic cutter |
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| CN102451682A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Zirconia-modified wet oxidation catalyst and preparation method thereof |
| CN102451680A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Composite oxide modified wet oxidation catalyst and preparation method thereof |
| CN102600832A (en) * | 2012-02-28 | 2012-07-25 | 北京化工大学 | Combined catalyst for improving denitration performance and application thereof |
| CN103521222A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet-type oxidation catalyst and preparation method thereof |
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| US5552063A (en) * | 1993-05-12 | 1996-09-03 | Mobil Oil Corporation | Process for treating wastewater containing phenol, ammonia, and cod |
| CN102451682A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Zirconia-modified wet oxidation catalyst and preparation method thereof |
| CN102451680A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Composite oxide modified wet oxidation catalyst and preparation method thereof |
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