CN114602468A - Catalyst, device and method for treating aerospace propellant production sewage through catalytic reduction - Google Patents
Catalyst, device and method for treating aerospace propellant production sewage through catalytic reduction Download PDFInfo
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- CN114602468A CN114602468A CN202210123910.3A CN202210123910A CN114602468A CN 114602468 A CN114602468 A CN 114602468A CN 202210123910 A CN202210123910 A CN 202210123910A CN 114602468 A CN114602468 A CN 114602468A
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- 239000010865 sewage Substances 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000003380 propellant Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 30
- 230000004048 modification Effects 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 201
- 229910052742 iron Inorganic materials 0.000 claims description 95
- 239000000463 material Substances 0.000 claims description 57
- 239000010949 copper Substances 0.000 claims description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 229910052802 copper Inorganic materials 0.000 claims description 53
- 150000001879 copper Chemical class 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 241001424392 Lucia limbaria Species 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- -1 meta-hydrazone Chemical compound 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- PRGCYUAJTPIADR-WAYWQWQTSA-N n-[(z)-dimethylaminodiazenyl]-n-methylmethanamine Chemical compound CN(C)\N=N/N(C)C PRGCYUAJTPIADR-WAYWQWQTSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- B01J23/70—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00548—Flow
- B01J2208/00557—Flow controlling the residence time inside the reactor vessel
Abstract
The invention discloses a catalyst, a device and a method for treating aerospace propellant production sewage by catalytic reduction. The device comprises a filter bed reactor, a catalyst filled in the filter bed reactor, a water pump for lifting sewage to the filter bed reactor, and a circulating water pump for circularly lifting the sewage in the filter bed reactor. The method uses the device to carry out reduction treatment on the aerospace propellant production sewage. The iron-copper composite catalytic reduction system is formed by chemical plating and oxidation modification, has large contact area, strong adhesive force, small copper consumption, simple equipment, convenient operation and management, no other energy consumption except the power consumption of a water pump, higher catalytic activity, high reduction reaction rate and no secondary pollution, and is very suitable for treating the production sewage of the space propellant.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a catalyst, a device and a method for treating aerospace propellant production sewage by catalytic reduction.
Background
The sewage produced by the aerospace propellant belongs to one of industrial sewage difficult to degrade, is complex in component, contains a large amount of toxic and harmful pollutants, is difficult to degrade biochemically, contains a series of organic matters such as unsym-dimethylhydrazine, meta-hydrazone, dimethylamine, nitroso-dimethylamine, tetramethyl-tetrazene and the like, wherein most of the organic matters belong to high-toxicity substances, have the effects of teratogenesis, carcinogenesis, mutagenesis and the like, and have great influence on the ecological environment and the health safety of personnel. The traditional biological treatment technology is difficult to solve due to poor biodegradability, and meanwhile, the oxidation technology in the physicochemical treatment technology has extremely poor treatment effect on substances such as metahydrazone and the like, so that the technology is not suitable for the treatment, wherein the technologies comprise an ozone oxidation method, a Fenton oxidation method, a wet catalytic oxidation method and the like, the treatment mechanism of the technologies is complex and the price is high, and the technologies are not suitable for treating the sewage produced by the aerospace propellant; the catalytic reduction method can reduce substances such as metahydrazone, nitrosodimethylamine and the like into aerospace propellants such as metadimethylhydrazine, dimethylamine and the like or propellant production raw materials, and can recycle useful substances while degrading sewage.
In recent years, many researches on reduction treatment of organic matters in water by zero-valent metal have been carried out, for example, the organic matters can be subjected to reduction reaction by using elementary iron, zinc, aluminum and the like, and particularly, the elementary iron is utilized for catalytic reduction treatment. Zero-valent iron has attracted interest to many researchers because of its low cost, lack of toxicity and contamination. However, the simple substance iron is used alone to catalyze and reduce the organic matters, the reduction reaction rate is very slow, and propellant pollutants in the water body cannot be completely reduced. In the research, a binary metal system is generally used for improving the reaction rate, and the research proves that the reaction rate can be obviously improved by adding another metal as a catalyst into an elemental iron reduction system. However, the raw materials adopted in the research are all reduced iron powder with very fine particle size, oxides are generally removed by acid washing before use, and iron oxides or hydroxides are easily generated in the using process to cause passivation, so that a reactor is easily blocked, and the engineering application is not facilitated. And in part, the research uses expensive noble metals, so that the treatment cost is increased sharply.
Therefore, a catalytic reduction method which is simple and convenient to operate and can realize industrial sewage treatment is needed to be provided, and technical support is provided for the sewage treatment in the aerospace propellant production.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a catalyst, a device and a method for treating aerospace propellant production sewage by catalytic reduction.
The technical scheme adopted by the invention for realizing the technical effects is as follows:
a catalyst for treating sewage generated in the production of aerospace propellant by catalytic reduction, which comprises:
an iron base material having a surface from which an oxide film is removed;
the metal copper particles are deposited on the surface of the iron base material based on chemical plating, and the mass ratio of copper to iron is 1: 100-1: 10;
wherein, the iron base material and the metal copper particles on the surface of the iron base material are subjected to surface modification, and the part of the iron base material and the metal copper particles is in an oxidation state.
Preferably, in the catalyst for treating the sewage generated in the production of the space propellant by catalytic reduction, the iron substrate is in the form of iron shavings, iron filings or thin iron sheets.
Preferably, in the catalyst for treating the sewage generated in the production of the space propellant by catalytic reduction, the catalyst is prepared by the following steps:
s1, pretreating a material, namely cleaning an iron base material by using a concentrated sodium hydroxide solution, dilute hydrochloric acid and clear water respectively to remove an oxide film on the surface of the iron base material, then placing the iron base material in the clear water, and heating the water to 30 ℃;
s2, copper plating modification, namely placing the iron base material subjected to washing treatment in a copper salt solution at a certain temperature, converting copper ions in the copper salt solution into a copper simple substance through a chemical displacement reaction through chemical plating, and depositing the copper simple substance on the surface of the iron base material in a particle form;
s3, oxidizing modification, namely drying the iron base material with the surface plated with copper for modification in inert gas, and then oxidizing modification to partially oxidize the iron simple substance and the copper simple substance on the surface of the iron base material into metal oxide.
Preferably, in the catalyst for treating the aerospace propellant production wastewater through catalytic reduction, the mass concentration of the copper salt solution is 1-10%.
Preferably, in the above catalyst for treating sewage from production of propellant for space flight by catalytic reduction, the copper salt in the copper salt solution is a soluble copper salt, including one or more of copper sulfate, copper nitrate, copper chloride and basic copper carbonate.
Preferably, in the catalyst for treating the spacecraft propellant production wastewater through catalytic reduction, in the step S3, the iron substrate with the copper-plated modified surface is dried and then oxidized for a certain time in oxidizing gas or sprayed with an oxidizing solvent for oxidation modification.
Preferably, in the above catalyst for treating sewage from the production of space propellant by catalytic reduction, the oxidizing gas is oxygen, 50% oxygen or a mixed gas of oxygen and air, and the oxidizing solvent is hydrogen peroxide solvent or sodium hypochlorite solvent.
The device for treating the aerospace propellant production sewage through catalytic reduction comprises a filter bed reactor, a catalyst serving as a filter material and filled in the filter bed reactor, a water pump for lifting the aerospace propellant production sewage to the filter bed reactor, and a circulating water pump for circularly lifting the sewage entering the filter bed reactor, wherein the catalyst is the catalyst in any one of claims 1 to 7.
Preferably, in the device for treating the production sewage of the space propellant by catalytic reduction, the bulk density of the catalyst is 0.1-2.0 x 103kg/m3。
The method for treating the sewage produced by the aerospace propellant by catalytic reduction comprises the following steps:
introducing a certain volume of the aerospace propellant production sewage into a filter bed reactor, closing a water inlet, and heating the sewage to 30 ℃ by using a heating rod;
reacting the heated sewage in a continuous flow filtering bed reactor from top to bottom or in a advection mode, wherein the retention time of the sewage in a filtering bed of a catalytic reduction system is 30-300 minutes;
and discharging the reacted sewage, and pumping the sewage into the next volume of the aerospace propellant production sewage for next circulation treatment.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst of the invention deposits metal copper on the surface of iron by utilizing the reaction of iron and a copper salt solution in a chemical plating mode to form an iron-copper composite catalytic reduction system, thereby increasing the reduction capability and the reaction rate of iron. Copper is fixed on the surface of iron in the form of tiny particles, the contact area is large, the adhesive force is strong, the copper is not easy to fall off, the catalytic activity is higher, and the reduction reaction rate can be improved by 3-18 times;
2. the catalyst is cheap and easy to obtain, the catalytic reaction rate and the reduction capacity can be improved, the using amount of copper is very small, the mass ratio of copper to iron is 1: 100-1: 10, the catalytic efficiency is improved, and the water treatment operation cost is effectively saved;
3. according to the invention, the reaction activity of the iron surface is improved in an oxidation modification mode, the reduction reaction speed of organic matters in sewage on the iron surface is improved, and the reduction reaction speed is improved by 3-7 times after the oxidation modification; in addition, the oxidant adopted by the method of the invention can not generate secondary pollution;
4. the device and the method have the advantages of simple equipment, convenient operation and management, no other energy consumption except the power consumption of the water pump, obviously reduced operation energy consumption and contribution to engineering application.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples which are set forth in part by way of illustration:
in the description of the present invention, it should be noted that unless otherwise specifically stated or limited, the terms "disposed," "mounted," "connected," and "connected" are used broadly and can be, for example, fixedly connected, detachably connected, or integrally connected, mechanically connected, electrically connected, directly connected, or connected through an intermediate medium, and can be used to connect two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The embodiment of the invention provides a catalyst for treating aerospace propellant production sewage by catalytic reduction, which comprises the following components in percentage by weight:
an iron base material having a surface from which an oxide film is removed;
the metal copper particles are deposited on the surface of the iron base material based on chemical plating, and the mass ratio of copper to iron is 1: 100-1: 10;
wherein, the iron base material and the metal copper particles on the surface of the iron base material are subjected to surface modification, and the part of the iron base material and the metal copper particles is in an oxidation state.
Further, in a preferred embodiment of the present invention, the iron base material is in the form of iron shavings, iron filings, or thin iron pieces.
Specifically, the catalyst is prepared by the following steps:
s1, pretreating a material, namely cleaning an iron base material by using a concentrated sodium hydroxide solution, dilute hydrochloric acid and clear water respectively to remove an oxide film on the surface of the iron base material, then placing the iron base material in the clear water, and heating the water to 30 ℃;
s2, copper plating modification, namely placing the iron base material subjected to washing treatment in a copper salt solution at a certain temperature, converting copper ions in the copper salt solution into a copper simple substance through a chemical displacement reaction through chemical plating, and depositing the copper simple substance on the surface of the iron base material in a particle form;
s3, oxidizing modification, namely drying the iron base material with the surface plated with copper for modification in inert gas, and then oxidizing modification to partially oxidize the iron simple substance and the copper simple substance on the surface of the iron base material into metal oxide.
In a preferred embodiment of the present invention, the mass concentration of the copper salt solution is 1% to 10%. The copper salt in the copper salt solution is soluble copper salt, and comprises one or more of copper sulfate, copper nitrate, copper chloride and basic copper carbonate. In step S3, the surface copper-plated modified iron base material is dried and oxidized in an oxidizing gas for a certain time or subjected to oxidation modification by spraying an oxidizing solvent. In a preferred embodiment of the present invention, the oxidizing gas is oxygen, 50% oxygen, or a mixed gas of oxygen and air, and the oxidizing solvent is a hydrogen peroxide solvent or a sodium hypochlorite solvent.
In step S2, a copper salt aqueous solution with a mass concentration of 1% to 10% is prepared, and the copper salt is a soluble copper salt, such as one or more of copper sulfate, copper nitrate, copper chloride, and basic copper carbonate. And then soaking the iron base material in the form of iron shavings, iron filings or thin iron sheets in a copper salt aqueous solution at a certain temperature, reacting for a period of time, and taking out the iron base material. Cu in copper salt solution2+Will be converted into Cu by chemical replacement reaction0The copper is adsorbed on the surface of the iron base material, and countless micro particles are formed on the surface of the iron base material, so that the copper on the surface of the iron base material can be firmly combined with iron, the contact surface area of the copper and the iron is very large, and the copper on the surface of the iron base material is newly generated, so that the copper has high catalytic activity and can greatly improve the reduction speed of the iron. The mass of the copper adsorbed on the surface of the iron base material is 1-10% of the total mass of the iron, so that the using amount of the copper is greatly reduced, and the cost is reduced.
In the step S3, to increase Fe0The reducing capability of the propellant pollutants is improved, the speed of reduction reaction of organic matters on the surface of the iron base material is increased, and the surface of the iron base material is modified. The Fe on the surface of the iron base material is oxidized in oxidizing gas for a certain time or in a mode of spraying an oxidizing solvent after the iron base material after being plated with copper is dried0And Cu0Oxidizing to realize the function of modifying the surface of the iron base material, thus greatly improving the speed of reducing and converting organic matters in the sewage by the iron.
On the other hand, the embodiment of the invention also provides a device for treating the spacecraft propellant production sewage through catalytic reduction, which comprises a filter bed reactor, a catalyst serving as a filter material and filled in the filter bed reactor, a water pump used for lifting the spacecraft propellant production sewage to the filter bed reactor, and a circulating water pump used for circularly lifting the sewage entering the filter bed reactor, wherein the catalyst is the catalyst for treating the spacecraft propellant production sewage through catalytic reduction provided by the embodiment.
Further, in a preferred embodiment of the present invention, the catalyst in the apparatus has a bulk density of 0.1 to 2.0X 103kg/m3. The placing height of the catalyst is 0.1-5 m, the catalyst can be arranged into one layer or a multilayer structure according to different actual requirements, and when the catalyst is arranged into the multilayer structure, the height of 0.1m can be filled between every two layers of catalyst through Raschig rings, polytetrafluoroethylene fillers and the like, so that the stacking density is ensured, and water flow is uniformly distributed.
On the other hand, the embodiment of the invention also provides a method for treating the production sewage of the space propellant by catalytic reduction, which comprises the following steps:
introducing a certain volume of the aerospace propellant production sewage into a filter bed reactor, closing a water inlet, and heating the sewage to 30 ℃ by using a heating rod;
reacting the heated sewage in a continuous flow filtering bed reactor from top to bottom or in a advection mode, wherein the retention time of the sewage in a filtering bed of a catalytic reduction system is 30-300 minutes;
and discharging the reacted sewage, and pumping the sewage into the next volume of the aerospace propellant production sewage for next circulation treatment.
In the preferred embodiment of the invention, the temperature rise in the filter bed reactor is beneficial to the reaction, and the reaction is generally controlled to be carried out under the conditions of normal temperature plus 5-40 ℃ and normal pressure. The pH value of the sewage is not required to be adjusted generally, but when the pH value of the sewage is within the range of 3-5, the water treatment effect is optimal.
For a better understanding of the present invention, the following description of the present invention is given in terms of a specific embodiment and various process embodiments.
Example 1:
a method for treating sewage generated in production of space propellant by catalytic reduction uses a catalyst and a device which are composed of the following parts: copper-plated zero-valent iron with the mass of 1.0 multiplied by 103kg; filter bed reactor, volume 1m3(ii) a Water pump with head of 30m and flow rate of 1m3H; pool, 2m3(ii) a The oxidant is hydrogen peroxide with the concentration of 10 percent; the electroless copper plating reagent is CuNO3。
Preparation of zero-valent iron-based catalyst:
1) preparing materials: loading the iron shavings into a filter bed reactor, washing with concentrated sodium hydroxide solution, dilute hydrochloric acid and clear water, and standing at 2m3In the water pool, the water pool is filled with clear water, and the water is heated to 30 ℃;
2) chemical copper plating: 80kg of copper nitrate (CuNO) was weighed3) Introducing the filter bed into a water tank filled with the cleaned iron shavings, reacting for 2 hours, taking the filter bed reactor and the iron shavings out of the water surface by using a crane when the surface color of the iron shavings is slightly changed, and drying the surface by using nitrogen;
3) oxidation modification: pumping 2/3% industrial hydrogen peroxide out of a barrel, adding 2 times of water to obtain 10% hydrogen peroxide, inserting one end of a water pump into the barrel, and connecting the other end of the water pump with a micron-sized atomizing nozzle; spreading the catalyst after copper plating on the ground, uniformly spraying atomized hydrogen peroxide on the surface of the catalyst, turning over after reacting for 1 minute, spraying again, and washing with a large amount of clear water after 1 minute.
Preparation of catalytic reaction device:
1) filling a catalyst: the catalyst after oxidation modification is filled in a filter bed reactor, the placement height of the catalyst is 1.0m, and the bulk density is 1.0 multiplied by 103kg/m3. Every time the catalyst with the height of 0.2m is filled, Raschig rings, polytetrafluoroethylene fillers and the like are used for filling the catalyst with the height of 0.1m so as to ensure the bulk density and ensure the uniform water flow distribution;
2) on the basis of the step 1), introducing the aerospace propellant production sewage into a filter bed reactor of a catalytic reduction system by using a water pump, heating the sewage to 30 ℃ by using a heating rod, closing a water inlet, enabling the sewage to flow into the filter bed reactor from top to bottom continuously by using a circulating water pump, and discharging the sewage after reacting for 60 minutes.
Treatment example 1: comparison of treatment effects of the method of the invention with other zero-valent iron reduction methods
The catalyst was prepared as described above in example 1.
Weighing four parts of iron shavings with the same weight and one part of reduced iron powder with the same weight, wherein one part of the four parts of iron shavings is chemically plated with 1% of copper, and filling the parts into a 1L filter bed reactor (A reaction system); after one part of copper is chemically plated by 1%, oxidizing and modifying by using 10% hydrogen peroxide, and filling the product into a 1L filter bed reactor (a reaction system B); one part of the copper sheet is uniformly mixed with the copper sheet with the same mass and is put into a filter bed reactor (C reaction system) of 1L; the remaining one portion was charged into a 1L filter bed reactor without any treatment (D reaction system); the bulk density and the bulk height of the catalyst were the same in each reaction system. The remaining part of reduced iron powder was also charged into a 1L filter bed reactor (E reaction system) without any treatment.
The 5 reactors are all filled with simulated aerospace propellant production sewage with COD concentration of 1000mg/L, main pollutants in the sewage are metahydrazone (with the concentration of 100mg/L) and unsym-dimethylhydrazine (with the concentration of 125mg/L), and the concentration of the metahydrazone is taken as a judgment standard. The peristaltic pump is used as sewage circulation power, so that sewage flows through the catalyst from top to bottom, the reaction is carried out under the conditions of normal temperature and normal pressure, the pH value of the sewage is not regulated, and the reaction time is 60 minutes.
The metahydrazone concentration in the treated simulated sewage is measured, and the specific result is shown in table 1:
TABLE 1 measurement results of metahydrazone content in wastewater
The reaction system B in Table 1 is the result after the treatment by the method of the present invention, and the comparison shows that the surface of iron is chemically plated with copper and is oxidized and modified to obviously increase the catalytic reduction reaction rate. Although the reduced iron powder has a large specific surface area, a large speed difference does not exist in sewage treatment, and the reaction speed of the reduced iron powder is not large and only reaches about 16 percent because the sewage reacts with the iron powder to block partial micropores and reduce the reaction activity in the treatment process. The mechanical copper mixing ratio of copper sheets is much less efficient than electroless copper plating, and although the mechanical copper-iron mixing ratio is 1:1, the electroless copper plating copper-iron mixing ratio is 1:100, the reaction rate is about 1 times slower than the electroless copper plating iron shaving. These show that the process of the invention has a strong acceleration capacity.
Treatment example 2: the method of the invention is used for treating the actual aerospace propellant production sewage
The catalyst was prepared according to the method of example 1.
Selecting actual aerospace propellant production sewage, and the treatment method comprises the following steps: the prepared catalyst was placed in a 1L filter bed reactor with a bulk density of 1.0X 103kg/m3The stacking height is 0.2m, a peristaltic pump is used as sewage circulation power, so that sewage flows through the catalyst from top to bottom, the initial pH value of the sewage is 12.3, the pH value is adjusted to 5.0, the reaction is carried out at the temperature of 30 ℃, and the reaction time is 300 minutes.
After the reaction is finished, the organic matter concentration, COD value and other parameters in the actual processed aerospace propellant production sewage are measured, and the specific results are shown in Table 2:
TABLE 2 test results of the content index of each pollutant in the wastewater
Therefore, the catalyst, the device and the method can efficiently treat the production sewage of the aerospace propellant, and can enable the propellant and upstream and downstream organic matters in the water body to quickly react in the sewage treatment process.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. The catalyst for treating the sewage generated in the production of the space propellant by catalytic reduction is characterized by comprising the following components in percentage by weight:
an iron base material having a surface from which an oxide film is removed;
the metal copper particles are deposited on the surface of the iron base material based on chemical plating, and the mass ratio of copper to iron is 1: 100-1: 10;
wherein, the iron base material and the metal copper particles on the surface of the iron base material are subjected to surface modification, and the part of the iron base material and the metal copper particles is in an oxidation state.
2. The catalyst for treating the sewage generated in the production of the aerospace propellant by the catalytic reduction according to claim 1, wherein the iron substrate is in the form of iron shavings, iron filings or thin iron sheets.
3. The catalyst for treating the aerospace propellant production wastewater through catalytic reduction according to claim 1, wherein the catalyst is prepared by adopting the following steps:
s1, pretreating a material, namely cleaning an iron base material by using a concentrated sodium hydroxide solution, dilute hydrochloric acid and clear water respectively to remove an oxide film on the surface of the iron base material, then placing the iron base material in the clear water, and heating the water to 30 ℃;
s2, copper plating modification, namely placing the iron base material subjected to washing treatment in a copper salt solution at a certain temperature, converting copper ions in the copper salt solution into a copper simple substance through a chemical displacement reaction through chemical plating, and depositing the copper simple substance on the surface of the iron base material in a particle form;
s3, oxidizing modification, namely drying the iron base material with the surface plated with copper for modification in inert gas, and then oxidizing modification to partially oxidize the iron simple substance and the copper simple substance on the surface of the iron base material into metal oxide.
4. The catalyst for treating the sewage generated in the production of the space propellant by catalytic reduction according to claim 3, wherein the mass concentration of the copper salt solution is 1-10%.
5. The catalyst for catalytic reduction treatment of spacecraft propellant production wastewater of claim 3, wherein the copper salt in the copper salt solution is a soluble copper salt, and comprises one or more of copper sulfate, copper nitrate, copper chloride and basic copper carbonate.
6. The catalyst for treating sewage generated in propellant production of space flight through catalytic reduction according to claim 3, wherein in step S3, the iron substrate with copper-plated modified surface is dried and then oxidized in oxidizing gas for a certain time or sprayed with an oxidizing solvent for oxidation modification.
7. The catalyst for catalytic reduction treatment of spacecraft propellant production wastewater according to claim 6, wherein the oxidizing gas is oxygen, 50% oxygen or a mixed gas of oxygen and air, and the oxidizing solvent is hydrogen peroxide solvent or sodium hypochlorite solvent.
8. The device for treating the sewage generated in the production of the space propellant through catalytic reduction is characterized by comprising a filter bed reactor, a catalyst serving as a filter material and filled in the filter bed reactor, a water pump for lifting the sewage generated in the production of the space propellant to the filter bed reactor, and a circulating water pump for circularly lifting the sewage entering the filter bed reactor, wherein the catalyst is the catalyst in any one of claims 1 to 7.
9. The device for treating the sewage generated in the production of the space propellant by the catalytic reduction according to claim 8, wherein the bulk density of the catalyst is 0.1-2.0 x 103kg/m3。
10. The method for treating the sewage produced by the aerospace propellant through catalytic reduction is characterized by comprising the following steps:
introducing a certain volume of the aerospace propellant production sewage into a filter bed reactor, closing a water inlet, and heating the sewage to 30 ℃ by using a heating rod;
reacting the heated sewage in a continuous flow filtering bed reactor from top to bottom or in a advection mode, wherein the retention time of the sewage in a filtering bed of a catalytic reduction system is 30-300 minutes;
and discharging the reacted sewage, and pumping the sewage into the next volume of the aerospace propellant production sewage for next circulation treatment.
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