CN116694372A - La@Fe 2 O 3 Nanoparticle combustion improver and preparation method and application of dispersion liquid thereof - Google Patents
La@Fe 2 O 3 Nanoparticle combustion improver and preparation method and application of dispersion liquid thereof Download PDFInfo
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- CN116694372A CN116694372A CN202310777975.4A CN202310777975A CN116694372A CN 116694372 A CN116694372 A CN 116694372A CN 202310777975 A CN202310777975 A CN 202310777975A CN 116694372 A CN116694372 A CN 116694372A
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 135
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 124
- 239000006185 dispersion Substances 0.000 title claims abstract description 66
- 239000007788 liquid Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 48
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 239000002737 fuel gas Substances 0.000 claims abstract description 15
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001413 amino acids Chemical class 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 238000003756 stirring Methods 0.000 claims description 75
- 238000001914 filtration Methods 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 150000002603 lanthanum Chemical class 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 14
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- CQBPOPVKDNHISM-UHFFFAOYSA-N propane-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OCC(O)CO CQBPOPVKDNHISM-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- OTFFCAGPSWJBDK-UHFFFAOYSA-N 1h-indazol-7-amine Chemical compound NC1=CC=CC2=C1NN=C2 OTFFCAGPSWJBDK-UHFFFAOYSA-N 0.000 claims 3
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 37
- 239000007789 gas Substances 0.000 description 22
- 239000000919 ceramic Substances 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000446 fuel Substances 0.000 description 9
- 238000004537 pulping Methods 0.000 description 9
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- -1 cerium chloride modified neodymium lanthanum oxide Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BRCNMMGLEUILLG-UHFFFAOYSA-N 4,5,6-trihydroxyhexan-2-one Chemical compound CC(=O)CC(O)C(O)CO BRCNMMGLEUILLG-UHFFFAOYSA-N 0.000 description 1
- IFJOCHBDHXGFAA-UHFFFAOYSA-N CC([CH2-])=O.OCC(O)CO Chemical compound CC([CH2-])=O.OCC(O)CO IFJOCHBDHXGFAA-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/003—Additives for gaseous fuels
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses La@Fe 2 O 3 Nanoparticle combustion improver, dispersion liquid of the combustion improver and preparation method thereof, and Fe after amino acid activation 2 O 3 Reaction of nano-particles with lanthanum ligand solution to prepare La@Fe 2 O 3 And the nano-particle combustion improver is beneficial to promoting the combustion of the fuel gas, so that the combustion efficiency of the fuel gas is improved. La@Fe prepared by adopting the method of the invention 2 O 3 The nano-particle combustion improver can be stably dispersed in methoxy polyvinyl alcohol glycerol ether to form La@Fe with stable property 2 O 3 The nano-particle combustion improver dispersion liquid can be mixed with fuel gas by a dilution spray atomization method under the condition of not damaging the original natural gas boiler combustion system, so that the combustion efficiency of the fuel gas is improved.
Description
Technical Field
The invention relates to La@Fe 2 O 3 A preparation method and application of nanoparticle combustion improver and dispersion liquid thereof belong to the technical field of environmental protection.
Background
A gas boiler is a device that generates heat energy by combustion using gas (e.g., natural gas, liquefied petroleum gas, etc.) as fuel and then transfers the heat energy to a heating system or a hot water system. It is a common heating and water heating device, and is widely used in the fields of home, business and industry. Residential and commercial buildings choose gas boilers as heating devices to provide comfortable indoor warmth. In the industrial field, gas boilers can be used for steam production and heating processes in power plants, chemical plants, textile plants, food processing plants and the like. With the increasing concerns about environmental protection and energy efficiency, the high efficiency and energy saving of gas boilers are becoming a trend in the industry. However, the combustion systems of current gas boilers are not efficient, mainly for several reasons: (1) incomplete combustion of fuel. Some of the fuel may not burn sufficiently during combustion, resulting in reduced combustion efficiency, and possible causes include unreasonable burner design, unstable fuel supply, or uneven airflow during combustion; (2) loss of heat. The gas boiler can generate a large amount of smoke and heat in the combustion process, wherein a part of heat can be lost through smoke emission and the surface of the boiler or is not fully utilized, so that the efficiency of a combustion system is reduced; (3) excess air. Excessive air entering the combustion system can cause heat dilution and heat removal, reducing combustion efficiency; (4) inaccurate combustion control. Inaccurate control of parameters such as temperature, humidity, fuel supply, etc. in the combustion process of the gas boiler may cause a decrease in the efficiency of the combustion system. By adopting advanced burner design and combustion technology, such as a premixed burner, a multistage burner and the like, heat in the flue gas is recycled, so that the combustion efficiency of the gas-fired boiler can be improved, and a more complete combustion process can be realized. However, advanced burner technology, flue gas waste heat recovery devices, intelligent control systems, etc., generally require higher technical and economic costs, limiting the ability of small and medium-sized enterprises to employ these improvements.
At present, research on improving the combustion efficiency of the gas by assisting a catalytic auxiliary agent is widely paid attention to, and a plurality of reports of combustion-supporting patent technologies exist, for example, patent with publication number of CN102690696B discloses a preparation method of a nano rare earth combustion improver of dimethyl ether gas, cerium chloride modified neodymium lanthanum oxide nano particles are prepared by a hydrothermal method to serve as the combustion improver of the dimethyl ether gas, and the combustion improver prepared by the method can improve the combustion efficiency of the gas, but the prepared combustion improver only aims at the dimethyl ether gas and cannot be used for natural gas. Patent publication No. CN106147907B discloses liquefied natural gas combustion improver which is prepared from tung oil, ethanol, n-butanol, cyclopentanol, ethylene glycol monobutyl ether, methyl ethyl ketone, borane tetrahydrofuran and the like, wherein the combustion improver can improve the heat value of fuel gas, but the components of the combustion improver are complex, and the preparation cost is higher.
Disclosure of Invention
The invention aims to provide La@Fe 2 O 3 Nanoparticle combustion improver and preparation method of dispersion liquid thereof, wherein the combustion improver can be stably dispersed in methoxy polyvinyl alcohol glycerol ether to form La@Fe with stable property 2 O 3 The nano-particle combustion improver dispersion liquid can be mixed with fuel gas by a dilution spray atomization method under the condition of not damaging the original boiler combustion system, so that the fuel gas combustion efficiency is improved.
In order to achieve the above purposes, the invention firstly provides a La@Fe alloy 2 O 3 The preparation method of the nanoparticle combustion improver comprises the following steps:
(1)Fe 2 O 3 pretreatment of nanoparticles: fe is added to 2 O 3 Adding nano particles into deionized water, stirring to disperse the nano particles, adding sodium hydroxide aqueous solution into the dispersed solution, stirring to react, filtering, washing and drying after the reaction is finished to obtain pretreated Fe 2 O 3 A nanoparticle;
(2)Fe 2 O 3 activation of nanoparticles: amino acid and pretreated Fe obtained in step (1) 2 O 3 Adding the nano particles into a solvent, stirring to react, filtering, washing and drying after the reaction is finished to obtain activated Fe 2 O 3 Nanoparticles, wherein the amino acid comprises one of 3-aminopropionic acid, phenylalanine and serine;
(3) Preparation of lanthanum ligand solution: adjusting the pH value of the disodium ethylenediamine tetraacetate solution to 8-10 by alkali liquor, dripping lanthanum salt solution into the disodium ethylenediamine tetraacetate solution, stirring to react, and filtering after the reaction is finished, wherein the filtrate is lanthanum ligand solution;
(4)La@Fe 2 O 3 preparation of nanoparticle combustion improver: adding the activated Fe obtained in the step (2) to the lanthanum ligand solution in the step (3) 2 O 3 Stirring the nano particles to react, filtering after the reaction is finished, cleaning filter residues with methanol or acetone, and drying to obtain La@Fe 2 O 3 NanoparticlesAnd (3) a combustion improver.
The invention modifies ferric oxide by using lanthanum ions to synthesize La@Fe 2 O 3 The nanometer particle combustion improver has the interaction between ferric oxide and lanthanum ion to form the defect site of ferric oxide, and during operation, oxygen and fuel molecule are easy to be adsorbed onto the defect site of the combustion improver surface, and lanthanum ion can activate the oxygen and fuel molecule adsorbed onto the combustion improver surface to form active matter, and the active matter reacts to produce combustion product and release energy. The reaction mechanism is shown in the following formula.
CH 4 +Fe 2 O 3 →CH 4 @Fe 2 O 3
O 2 +Fe 2 O 3 →O 2 @Fe 2 O 3
O 2 @Fe 2 O 3 +2La 3+ →2La 2 O 3 +O@Fe 2 O 3
CH 4 @Fe 2 O 3 +O@Fe 2 O 3 →CO 2 +H 2 O
In one embodiment of the present invention, in step (1), fe is added 2 O 3 The mass volume ratio of the nano particles to the deionized water is (1-20) kg:100L, and the Fe 2 O 3 The particle size of the nano particles is 5-20 nm.
In one embodiment of the present invention, in step (1), fe 2 O 3 The stirring speed of the nano particles during dispersion is 200-500 r/min.
In one embodiment of the present invention, in the step (1), the concentration of the aqueous sodium hydroxide solution to be added is 0.5 to 1.5mol/L, the addition rate of the aqueous sodium hydroxide solution is 2 to 10L/min, and the total volume of the aqueous sodium hydroxide solution to be added dropwise is 20 to 70L.
In one embodiment of the present invention, in the step (1), after adding the aqueous sodium hydroxide solution, the stirring speed is 200 to 500r/min, and the reaction time is 8 to 16 hours.
In one embodiment of the invention, in the step (1), the porous ceramic membrane is used for concentration before filtration, a membrane filter press is used for filtration after concentration, and filter residues are dried for 6-12 hours at 50-70 ℃ after washing.
In one embodiment of the present invention, in the step (2), the solvent comprises any one or a mixture of several of methanol, ethanol, tetrahydrofuran and dimethylformamide, and the amino acid is preferably 3-aminopropionic acid.
In one embodiment of the present invention, in the step (2), the mass to volume ratio of the amino acid to the solvent is (3 to 30) kg:100L, and the pretreated Fe 2 O 3 The mass volume ratio of the nano particles to the solvent is (1-4) kg/100L.
In one embodiment of the invention, in the step (2), the stirring reaction time is 8-14 h, the porous ceramic membrane is used for concentration before filtration, a membrane filter press is used for filtration after concentration, and filter residues are dried for 6-12 h under the condition of 50-70 ℃ after washing.
In one embodiment of the present invention, in the step (3), the mass concentration of the disodium edetate solution is 0.05-0.3 kg/L, the alkali solution is an aqueous sodium hydroxide solution, and the concentration of the aqueous sodium hydroxide solution is 0.5-1.5 mol/L.
In one embodiment of the present invention, in the step (3), the lanthanum salt includes lanthanum trichloride or lanthanum nitrate, and the mass concentration of the lanthanum salt in the lanthanum salt solution is 0.025-0.2 kg/L.
In one embodiment of the present invention, in the step (3), the dropping speed of the lanthanum salt solution is 5 to 10L/min, the rotation speed during stirring is 100 to 200r/min, and the stirring reaction time is 4 to 12 hours.
In one embodiment of the present invention, in step (4), the activated Fe 2 O 3 The mass volume ratio of the nano particles to the lanthanum ligand solution is (1-2) g to 10L.
In one embodiment of the present invention, in step (4), the pH of the solution is adjusted to 7 to 9 using hydrochloric acid or sodium hydroxide before the stirring reaction, the rotation speed during the stirring reaction is 100 to 600r/min, the reaction time is 4 to 16 hours, and the reaction temperature is 25 to 90 ℃.
In one embodiment of the present invention, in the step (4), the porous ceramic membrane is used for concentration before filtration, a membrane filter press is used for filtration after concentration, and the filter residue is dried for 6-12 hours at 50-70 ℃ after washing by the solvent.
The invention also provides La@Fe prepared by the preparation method 2 O 3 A nano-particle combustion improver.
The invention also provides La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver dispersion liquid comprises the following steps:
(1) Preparation of chloro polyethylene glycol monomethyl ether: adding polyethylene glycol monomethyl ether and pyridine into an organic solvent, dropwise adding thionyl chloride while stirring, stirring and reacting for 4-8 hours after the dropwise adding is completed, and removing the solvent to obtain chlorinated polyethylene glycol monomethyl ether;
(2) Synthesizing methoxy polyvinyl alcohol glycerol ether: adding the chloropolyethylene glycol monomethyl ether obtained in the step (1) into an organic solvent, simultaneously adding sodium hydroxide and acetone glycerol, stirring to react, regulating the pH of a reaction mixed solution to make the mixed solution acidic, continuing stirring to react, removing the solvent after the reaction is finished, dissolving residues with the organic solvent, filtering, and removing the solvent from the filtrate to obtain methoxy polyvinyl alcohol glycerol ether;
(3)La@Fe 2 O 3 preparing a nanoparticle combustion improver dispersion liquid: la@Fe 2 O 3 Dispersing the nano-particle combustion improver in water, adding the methoxy polyvinyl alcohol glycerol ether obtained in the step (2) into the water, and stirring the mixture for reaction to obtain La@Fe 2 O 3 Nanoparticle combustion improver dispersion.
In one embodiment of the present invention, in step (1), the organic solvent includes at least one of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide.
In one embodiment of the present invention, in the step (1), the molecular weight of the polyethylene glycol monomethyl ether is 600 to 2000, and the mass/volume ratio of the polyethylene glycol monomethyl ether to the organic solvent is (1 to 2) kg/10L.
In one embodiment of the present invention, in the step (1), the mass to volume ratio of the pyridine to the organic solvent is (0.5 to 2): 100L.
In one embodiment of the present invention, in the step (1), the speed of stirring is 200-500 r/min for both times, the volume ratio of the added thionyl chloride to the organic solvent is (2-15): 10, and the dropping speed is 0.5-2L/min.
In one embodiment of the present invention, in the step (1), the solvent is removed by vacuum distillation at a temperature of 50 to 80 ℃.
In one embodiment of the present invention, in the step (2), when the chloropolyethylene glycol monomethyl ether is dissolved in an organic solvent, the organic solvent includes at least one of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide, preferably N, N-dimethylformamide.
In one embodiment of the present invention, in the step (2), the mass-to-volume ratio of the chlorinated polyethylene glycol monomethyl ether to the organic solvent is (1-2) kg:10L, the mass-to-volume ratio of the sodium hydroxide to the organic solvent is (1-5) kg:100L, and the mass-to-volume ratio of the acetonide glycerol to the organic solvent is (8-15) kg:100L.
In one embodiment of the present invention, in the step (2), the rotation speed at the time of the stirring reaction is 200 to 500r/min, and the pH of the reaction mixture is adjusted to 1 to 3 by using hydrochloric acid.
In one embodiment of the present invention, in step (2), when the residue is dissolved using an organic solvent, the organic solvent includes at least one of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide, preferably chloroform.
In one embodiment of the present invention, in step (3), the la@fe 2 O 3 The mass ratio of the nano-particle combustion improver to the water is 1 (0.1-0.4).
In one embodiment of the present invention, after adding methoxy polyvinyl alcohol glyceryl ether in step (3), the methoxy polyvinyl alcohol glyceryl ether concentration is 2-20%.
The invention also provides a method for adopting the methodLa@Fe prepared by the method 2 O 3 Nanoparticle combustion improver dispersion.
The invention also provides La@Fe 2 O 3 The application of the nano-particle combustion improver dispersion liquid in the heating field.
The invention also provides La@Fe 2 O 3 Use method of nanoparticle combustion improver dispersion liquid comprises the steps of adding La@Fe 2 O 3 The nano-particle combustion improver dispersion liquid is atomized in the combustion area of the boiler after being sprayed by a sprayer, and the spraying amount is 0.1-0.5Kg of combustion improver dispersion liquid per cubic fuel gas.
The beneficial effects of the invention are that
(1) The invention prepares La@Fe with enhanced oxygen molecular activity 2 O 3 The nanometer particle combustion improver has defect sites on the surface, and oxygen and fuel molecules are easy to be adsorbed onto the defect sites on the surface of the combustion improver when the combustion improver works, lanthanum ions can activate the oxygen and fuel molecules adsorbed on the surface of the combustion improver to form active substances, and the active substances react to generate combustion products and release energy, so that La@Fe prepared by the method of the invention 2 O 3 The nano-particle combustion improver is beneficial to promoting the combustion of the fuel gas, thereby increasing the combustion efficiency of the fuel gas.
(2) La@Fe 2 O 3 The nano-particle combustion improver reacts with methoxy polyvinyl alcohol glycerol ether to form combustion improver dispersion liquid, the dispersion liquid has strong stability, and the static settlement experimental result shows that the dispersion stability period of the combustion improver dispersion liquid exceeds 6 months, and when the combustion improver dispersion liquid is diluted to 0.1-0.3 percent of weight percentage concentration, la@Fe 2 O 3 The nano-particle combustion improver can pass through a 3 mu m microporous filter membrane (based on the water for preparation), and can effectively prevent La@Fe in the using process 2 O 3 The nanoparticles are blocked.
(3) The invention is realized by mixing La@Fe 2 O 3 The nano-particle combustion improver dispersion liquid is sprayed and atomized to be mixed with fuel gas for combustion, and the combustion improver dispersion liquid can promote combustion reaction, so that the combustion efficiency is improved, and the emission of harmful substances such as nitrogen oxides is reduced.
(4) By mixing La@Fe 2 O 3 The nano-particle combustion improver dispersion liquid is sprayed into a boiler combustion area to form atomization to promote combustion, equipment investment is low, operation is convenient, and La@Fe obtained by adopting the method is low in cost 2 O 3 The nano-particle combustion improver dispersion liquid can increase the combustion efficiency of gas by 8-12%.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fe used in the examples of the present invention 2 O 3 The nano particles are produced by Shanghai, a new material and technology Co., ltd, and the particle size range is 5-20 nm; the 3-aminopropionic acid is a product produced by Henan Baizhang biotechnology Co., ltd; lanthanum trichloride and lanthanum nitrate are products produced by the rare earth materials of the Tiboribukang Co.Ltd; disodium edetate is a product produced by Jiangsu Duoyin Biotech Co., ltd; polyethylene glycol monomethyl ether is a product produced by the sea-safe petrochemical plant in Jiangsu province, and has a molecular weight of 600; pyridine is a product produced by chat access chemical industry limited company; the thionyl chloride is a product produced by the chemical industry Co.Ltd. N, N-dimethylformamide is a product produced by Shandong Maojun chemical technology Co., ltd; the acetonylglycerol is a product produced by Wuhan Hua Xiangke Jietexilate Co. The porous ceramic membrane used in the embodiment of the invention is a product with the model PL-T4 of Anhui pluronic membrane technology limited company, the filtering precision is 30-50nm, and the microporous filter membrane is a product produced by Sanqing filter equipment manufacturing limited company in Xinghua city. The sprayer used in the invention is an FZ-6 product produced by sea force machinery in Qingzhou, shandong.
Standing and settling experiments:
La@Fe to be prepared 2 O 3 Nanometer particleThe dispersion of the granular combustion improver is kept stand for a period of time at room temperature, and the stability of the dispersion is determined by judging whether precipitation is generated in the dispersion.
Example 1
La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver comprises the following steps:
(1)Fe 2 O 3 pretreatment of nanoparticles: 500L deionized water is put into a 1000L stirring kettle, and then 100kg Fe is added 2 O 3 And (3) nanoparticles. 50L of aqueous sodium hydroxide solution having a concentration of 1.5mol/L was added dropwise at a rate of 5L/min under mechanical stirring (200 r/min). After the completion of the dropwise addition, the reaction was continued at room temperature for 8 hours with stirring. After the reaction is finished, concentrating the reaction mixture by a porous ceramic membrane, filtering by a membrane filter press, repeatedly pulping and washing a filter cake for three times, and drying at 70 ℃ for 6 hours to obtain pretreated Fe 2 O 3 A nanoparticle;
(2)Fe 2 O 3 activation of nanoparticles: 500L of methanol was added to a 1000L stirred tank, 100kg of 3-aminopropionic acid and 10kg of the pretreated Fe obtained in the step (1) were added 2 O 3 The nanoparticles were reacted at room temperature with stirring for 8 hours. After the reaction is finished, concentrating the reaction mixture by a porous ceramic membrane, filtering by a membrane filter press, repeatedly pulping and washing a filter cake for three times, and drying at 50 ℃ for 12 hours to obtain activated Fe 2 O 3 A nanoparticle;
(3) Preparation of lanthanum ligand solution: into a 200L stirred tank, 20kg of lanthanum trichloride and 150L of deionized water were added to prepare a lanthanum salt solution. In a 500L stirring kettle, 100L deionized water and 30kg disodium ethylenediamine tetraacetate are put into the stirring kettle, stirred and dissolved, and the pH value of the disodium ethylenediamine tetraacetate solution is adjusted to 8 by using 1mol/L sodium hydroxide aqueous solution. Under the stirring condition (the stirring rotating speed is 100 r/min), the lanthanum salt solution is dripped into the disodium ethylenediamine tetraacetate solution, the dripping speed is controlled to be 5L/min, and the temperature is room temperature. After the completion of the dropwise addition, the reaction was continued at room temperature for 4 hours with stirring. Filtering with porous ceramic membrane after the reaction is finished, and removing residues to obtain lanthanum ligand solution;
(4)La@Fe 2 O 3 nanometer scalePreparing a granular combustion improver: putting 100L of lanthanum ligand solution obtained in the step (3) into a 200L stirring kettle, and simultaneously adding 20kg of activated Fe obtained in the step (2) 2 O 3 The pH of the nanoparticle is adjusted to 9 by using 1mol/L sodium hydroxide solution. The reaction temperature was controlled at 40℃and the reaction was stirred (600 r/min) for 16 hours. After the reaction is finished, concentrating the reaction mixture through a porous ceramic membrane, filtering through a membrane filter press, repeatedly pulping a filter cake, washing the filter cake with methanol and acetone for three times respectively, and drying the washed filter cake at 50 ℃ for 6 hours to obtain La@Fe 2 O 3 A nano-particle combustion improver.
La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver dispersion liquid comprises the following steps:
(1) Preparation of chloro polyethylene glycol monomethyl ether: in a 200L stirred tank, 100L of methylene chloride, 12kg of polyethylene glycol monomethyl ether and 0.5kg of pyridine were placed, 50L of thionyl chloride was added dropwise at a rate of 1.5L/min under stirring (200 r/min), and after the completion of the addition, the mixture was stirred at room temperature (200 r/min) for reaction for 8 hours. At 50 ℃ and 0.133 x 10 -3 And removing the solvent by using a vacuum distillation method under the pressure of kPa to obtain the chloro polyethylene glycol monomethyl ether.
(2) 100L of N, N-dimethylformamide is put into a 200L stirring kettle, 20kg of the chloropolyethylene glycol monomethyl ether obtained in the step (1), 5kg of sodium hydroxide and 8kg of acetone glycerol are added, and stirring (200 r/min) is carried out at 10 ℃ for 10 hours. The pH of the reaction mixture was adjusted to 3 with 1mol/L hydrochloric acid, and the reaction was continued with stirring (200 r/min) for 8 hours. After the reaction was completed, the reaction mixture was heated to 50 ℃ and 0.133 x 10 -5 Vacuum distilling under kPa to remove solvent, dissolving residue with chloroform, filtering with porous ceramic membrane, and collecting filtrate at 50deg.C and 0.133×10 -5 And (3) removing the solvent by vacuum distillation under the pressure of kPa to obtain methoxy polyvinyl alcohol glycerol ether.
(3)La@Fe 2 O 3 Preparing a nanoparticle combustion improver dispersion liquid: in a 200L stirring kettle, 100L of tap water for preparation and La@Fe are put 2 O 3 Nanoparticle, tap water for preparation and La@Fe 2 O 3 The weight ratio of the nano particles is 1:0.3, and the methoxy polyethylene obtained in the step (2) is addedAlcohol glyceryl ether to obtain methoxy polyvinyl alcohol glyceryl ether with concentration of 10%, stirring (500 r/min) at room temperature for 1.0 hr to obtain La@Fe 2 O 3 Nanoparticle combustion improver dispersion.
The static settlement experiment proves that the dispersion stability period exceeds 6 months, and the dispersion can pass through a microporous filter membrane with 3 mu m when the dispersion stability period is diluted to 0.2 percent (based on the water for preparation).
La@Fe 2 O 3 The La@Fe obtained in the embodiment is used as a method for using the nanoparticle combustion improver dispersion liquid 2 O 3 The dispersion liquid of the nano-particle combustion improver is diluted to 0.2 percent of weight concentration, and is sprayed by a sprayer to form atomization in a boiler combustion area, wherein the spraying amount is 0.5kg La@Fe per cubic fuel gas 2 O 3 And (3) nanoparticles. The application site of the combustion improver dispersion liquid is a vertical full-automatic fuel oil (gas) steam boiler of Changzhou Zhong Na chemical industry Co., ltd., model: LHS0.3-0.4 (0.7) -Y (Q), rated evaporation capacity: 0.3t/h, nominal vapor pressure: 0.7Mpa, heated area: 7.32m 2 。
Calculated by average daily gas consumption, la@Fe is sprayed 2 O 3 After the nano-particle combustion improver dispersion liquid is adopted, the gas combustion efficiency is increased by 8 percent.
Example 2
La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver comprises the following steps:
(1)Fe 2 O 3 pretreatment of nanoparticles: 500L deionized water is put into a 1000L stirring kettle, and then 75kg Fe is added 2 O 3 And (3) nanoparticles. 40L of aqueous sodium hydroxide solution having a concentration of 1.0mol/L was added dropwise at a rate of 8L/min under mechanical stirring (500 r/min). After the completion of the dropwise addition, the reaction was continued to be stirred at room temperature for 14 hours. After the reaction is finished, concentrating the reaction mixture by a porous ceramic membrane, filtering by a membrane filter press, repeatedly pulping and washing a filter cake for three times, and drying at 60 ℃ for 10 hours to obtain pretreated Fe 2 O 3 A nanoparticle;
(2)Fe 2 O 3 activation of nanoparticles: 500L of dimethylformamide was added to a 1000L stirred tank, and 100kg of 3 was addedAminopropionic acid and 15kg of pretreated Fe obtained in step (1) 2 O 3 The nanoparticles were reacted at room temperature with stirring for 10 hours. After the reaction is finished, concentrating the reaction mixture by a porous ceramic membrane, filtering by a membrane filter press, repeatedly pulping and washing a filter cake for three times, and drying at 60 ℃ for 10 hours to obtain activated Fe 2 O 3 A nanoparticle;
(3) Preparation of lanthanum ligand solution: into a 200L stirred tank, 12kg lanthanum nitrate and 150L deionized water were added to prepare a lanthanum salt solution. In a 500L stirred tank, 100L deionized water and 25kg disodium ethylenediamine tetraacetate are put into the stirred tank for stirring and dissolution, and the pH value of the disodium ethylenediamine tetraacetate solution is adjusted to 10 by using 1mol/L sodium hydroxide aqueous solution. Under the stirring condition (the stirring rotating speed is 100 r/min), the lanthanum salt solution is dripped into the disodium ethylenediamine tetraacetate solution, the dripping speed is controlled to be 8L/min, and the temperature is room temperature. After the completion of the dropwise addition, the reaction was continued at room temperature for 6 hours with stirring. Filtering with porous ceramic membrane after the reaction is finished, and removing residues to obtain lanthanum ligand solution;
(4)La@Fe 2 O 3 preparation of nanoparticle combustion improver: putting 100L of lanthanum ligand solution obtained in the step (3) into a 200L stirring kettle, and simultaneously adding 13kg of activated Fe obtained in the step (2) 2 O 3 The pH of the nanoparticle is adjusted to 8 by using 1mol/L sodium hydroxide solution. The reaction temperature was controlled at 60℃and the reaction was stirred (400 r/min) for 14 hours. After the reaction is finished, concentrating the reaction mixture through a porous ceramic membrane, filtering through a membrane filter press, repeatedly pulping a filter cake, washing the filter cake with methanol and acetone for three times respectively, and drying the washed filter cake at 55 ℃ for 8 hours to obtain La@Fe 2 O 3 A nano-particle combustion improver.
La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver dispersion liquid comprises the following steps:
(1) Preparation of chloro polyethylene glycol monomethyl ether: 100L of dichloromethane, 15kg of polyethylene glycol monomethyl ether and 1kg of pyridine) are placed in a 200L stirring kettle, 100L of thionyl chloride is dropwise added at a speed of 1.5L/min under stirring (300 r/min), and after the completion of the dropwise addition, the mixture is stirred at room temperature (300 r/min) for reaction for 6 hours. At 60 ℃ and 0.133 x 10 -6 Under pressure of kPa, makeRemoving the solvent by vacuum distillation to obtain the chloro polyethylene glycol monomethyl ether.
(2) 100L of N, N-dimethylformamide is put into a 200L stirring kettle, 15kg of the chloropolyethylene glycol monomethyl ether obtained in the step (1), 5kg of sodium hydroxide and 13kg of acetone glycerol are added, and stirring (300 r/min) is carried out at 20 ℃ for 8 hours. The pH of the reaction mixture was adjusted to 2 with 1mol/L hydrochloric acid, and the reaction was continued with stirring (200 r/min) for 7 hours. After the reaction was completed, the reaction mixture was heated to 50 ℃ and 0.133 x 10 -6 Vacuum distilling under kPa to remove solvent, dissolving residue with chloroform, filtering with porous ceramic membrane, and collecting filtrate at 50deg.C and 0.133×10 -6 And (3) removing the solvent by vacuum distillation under the pressure of kPa to obtain methoxy polyvinyl alcohol glycerol ether.
(3)La@Fe 2 O 3 Preparing a nanoparticle combustion improver dispersion liquid: in a 200L stirring kettle, 100L of tap water for preparation and La@Fe are put 2 O 3 Nanoparticle, tap water for preparation and La@Fe 2 O 3 Adding the methoxy polyvinyl alcohol glyceryl ether obtained in the step (2) to the weight ratio of the nano particles being 1:0.2 so that the concentration of the methoxy polyvinyl alcohol glyceryl ether is 13%, and stirring (500 r/min) for 0.8 hours at room temperature to obtain La@Fe 2 O 3 Nanoparticle combustion improver dispersion.
The static settlement experiment proves that the dispersion stability period exceeds 6 months, and the dispersion can pass through a microporous filter membrane with 3 mu m when the dispersion stability period is diluted to 0.1 percent (based on the water for preparation).
La@Fe 2 O 3 The La@Fe obtained in the embodiment is used as a method for using the nanoparticle combustion improver dispersion liquid 2 O 3 The dispersion liquid of the nano-particle combustion improver is diluted to 0.1 percent of weight concentration, and is sprayed by a sprayer to form atomization in a boiler combustion area, wherein the spraying amount is 0.4kg La@Fe per cubic fuel gas 2 O 3 And (3) nanoparticles. The application site of the combustion improver dispersion liquid is YYL (W) fuel oil (gas) organic carrier boiler manufactured by environmental protection technology Co., ltd., in Suzhou, model: YYL (W) -3500Y (Q), rated heating value: 300kCal, rated vapor pressure: 0.8Mpa, highest working temperature: 320 ℃.
Calculated by average daily gas consumption, la@Fe is sprayed 2 O 3 After the nano-particle combustion improver dispersion liquid is adopted, the gas combustion efficiency is increased by 11.5 percent.
Example 3
La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver comprises the following steps:
(1)Fe 2 O 3 pretreatment of nanoparticles: 500L deionized water is put into a 1000L stirring kettle, and then 100kg Fe is added 2 O 3 And (3) nanoparticles. 60L of aqueous sodium hydroxide solution having a concentration of 1.5mol/L are added dropwise at a rate of 8L/min under mechanical stirring (300 r/min). After the completion of the dropwise addition, the reaction was continued at room temperature for 10 hours with stirring. After the reaction is finished, concentrating the reaction mixture by a porous ceramic membrane, filtering by a membrane filter press, repeatedly pulping and washing a filter cake for three times, and drying at 70 ℃ for 7 hours to obtain pretreated Fe 2 O 3 A nanoparticle;
(2)Fe 2 O 3 activation of nanoparticles: 500L of tetrahydrofuran was added to a 1000L stirred tank, 70kg of 3-aminopropionic acid and 10kg of the pretreated Fe obtained in the step (1) were added 2 O 3 The nanoparticles were reacted at room temperature with stirring for 14 hours. After the reaction is finished, concentrating the reaction mixture by a porous ceramic membrane, filtering by a membrane filter press, repeatedly pulping and washing a filter cake for three times, and drying at 50 ℃ for 10 hours to obtain activated Fe 2 O 3 A nanoparticle;
(3) Preparation of lanthanum ligand solution: 16kg lanthanum nitrate and 200L deionized water were added to a 200L stirred tank to prepare a lanthanum salt solution. In a 500L stirring kettle, 100L deionized water and 15kg disodium ethylenediamine tetraacetate are put into the stirring kettle, stirred and dissolved, and the pH value of the disodium ethylenediamine tetraacetate solution is adjusted to 9 by using 1mol/L sodium hydroxide aqueous solution. Under the stirring condition (the stirring rotating speed is 200 r/min), the lanthanum salt solution is dripped into the disodium ethylenediamine tetraacetate solution, the dripping speed is controlled to be 10L/min, and the temperature is room temperature. After the completion of the dropwise addition, the reaction was continued at room temperature for 10 hours with stirring. Filtering with porous ceramic membrane after the reaction is finished, and removing residues to obtain lanthanum ligand solution;
(4)La@Fe 2 O 3 nanoparticlesPreparation of combustion improver: putting 100L of lanthanum ligand solution obtained in the step (3) into a 200L stirring kettle, and simultaneously adding 16kg of activated Fe obtained in the step (2) 2 O 3 The pH of the nanoparticle is adjusted to 9 by using 1mol/L sodium hydroxide solution. The reaction temperature was controlled at 40℃and the reaction was stirred (300 r/min) for 10 hours. After the reaction is finished, concentrating the reaction mixture through a porous ceramic membrane, filtering through a membrane filter press, repeatedly pulping a filter cake, washing the filter cake with methanol and acetone for three times respectively, and drying the washed filter cake at 70 ℃ for 10 hours to obtain La@Fe 2 O 3 A nano-particle combustion improver.
La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver dispersion liquid comprises the following steps:
(1) Preparation of chloro polyethylene glycol monomethyl ether: in a 200L stirred tank, 100L of methylene chloride, 20kg of polyethylene glycol monomethyl ether and 2kg of pyridine were placed, 150L of thionyl chloride was added dropwise at a rate of 2L/min under stirring (500 r/min), and after completion of the dropwise addition, the mixture was stirred at room temperature (500 r/min) for reaction for 8 hours. At 80 ℃ and 0.133 x 10 -5 And removing the solvent by using a vacuum distillation method under the pressure of kPa to obtain the chloro polyethylene glycol monomethyl ether.
(2) 100L of N, N-dimethylformamide is put into a 200L stirring kettle, 20kg of the chloropolyethylene glycol monomethyl ether obtained in the step (1), 4kg of sodium hydroxide and 15kg of acetone glycerol are added, and stirring (500 r/min) is carried out at 25 ℃ for 6 hours. The pH of the reaction mixture was adjusted to 3 with 1mol/L hydrochloric acid, and the reaction was continued with stirring (500 r/min) for 8 hours. After the reaction was completed, the reaction mixture was heated to 50 ℃ and 0.133 x 10 -5 Vacuum distilling under kPa to remove solvent, dissolving residue with chloroform, filtering with porous ceramic membrane, and collecting filtrate at 50deg.C and 0.133×10 -5 And (3) removing the solvent by vacuum distillation under the pressure of kPa to obtain methoxy polyvinyl alcohol glycerol ether.
(3)La@Fe 2 O 3 Preparing a nanoparticle combustion improver dispersion liquid: in a 200L stirring kettle, 100L of tap water for preparation and La@Fe are put 2 O 3 Nanoparticle, tap water for preparation and La@Fe 2 O 3 The weight ratio of the nano particles is 1:0.4, and the methoxy polyvinyl alcohol glycerol obtained in the step (2) is addedEther to give a methoxy polyvinyl alcohol glyceryl ether concentration of 20%, stirring (500 r/min) at room temperature for 1 hr to obtain La@Fe 2 O 3 Nanoparticle combustion improver dispersion.
The static settlement experiment proves that the dispersion stability period exceeds 6 months, and the dispersion can pass through a microporous filter membrane with 3 mu m when the dispersion stability period is diluted to 0.1 percent (based on the water for preparation).
La@Fe 2 O 3 The La@Fe obtained in the embodiment is used as a method for using the nanoparticle combustion improver dispersion liquid 2 O 3 The dispersion liquid of the nano-particle combustion improver is diluted to 0.1 percent of weight concentration, and is sprayed by a sprayer to form atomization in a boiler combustion area, wherein the spraying amount is 0.5kg La@Fe per cubic fuel gas 2 O 3 And (3) nanoparticles. The application site of the combustion improver dispersion liquid is a horizontal vacuum hot water boiler manufactured by Taian Ming's electro-mechanical technology Co., ltd., model: ZKW 2.1.2, rated heating value: 2.1MW, rated vapor pressure: 1.25Mpa.
Calculated by average daily gas consumption, la@Fe is sprayed 2 O 3 After the nano-particle combustion improver dispersion liquid is adopted, the gas combustion efficiency is increased by 12 percent.
Claims (10)
1. La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver is characterized by comprising the following steps:
(1)Fe 2 O 3 pretreatment of nanoparticles: fe is added to 2 O 3 Adding nano particles into deionized water, stirring to disperse the nano particles, adding sodium hydroxide aqueous solution into the dispersed solution, stirring to react, filtering, washing and drying after the reaction is finished to obtain pretreated Fe 2 O 3 Nanoparticles in which Fe is added 2 O 3 The mass volume ratio of the nano particles to the deionized water is (1-20) kg:100L, and the Fe 2 O 3 The particle size of the nano particles is 5-20 nm, the concentration of the added sodium hydroxide aqueous solution is 0.5-1.5 mol/L, the adding speed of the sodium hydroxide aqueous solution is 2-10L/min, and the total volume of the dropwise added sodium hydroxide aqueous solution is 20-70L;
(2)Fe 2 O 3 activation of nanoparticles: amino acid and pretreated Fe obtained in step (1) 2 O 3 Adding the nano particles into a solvent, stirring to react, filtering, washing and drying after the reaction is finished to obtain activated Fe 2 O 3 Nanoparticles, wherein the amino acid comprises one of 3-aminopropionic acid, phenylalanine and serine;
(3) Preparation of lanthanum ligand solution: adjusting the pH value of the disodium ethylenediamine tetraacetate solution to 8-10 by alkali liquor, dropwise adding a lanthanum salt solution into the disodium ethylenediamine tetraacetate solution, stirring to react, and filtering after the reaction is finished to obtain a filtrate, wherein the mass concentration of the disodium ethylenediamine tetraacetate solution is 0.05-0.3 kg/L, the lanthanum salt comprises lanthanum trichloride or lanthanum nitrate, the mass concentration of the lanthanum salt in the lanthanum salt solution is 0.025-0.2 kg/L, and the dropping speed of the lanthanum salt solution is 5-10L/min;
(4)La@Fe 2 O 3 preparation of nanoparticle combustion improver: adding the activated Fe obtained in the step (2) to the lanthanum ligand solution in the step (3) 2 O 3 Stirring the nano particles to react, filtering after the reaction is finished, cleaning filter residues with methanol and/or acetone, and drying to obtain La@Fe 2 O 3 A nano-particle combustion improver.
2. The method according to claim 1, wherein in the step (2), the solvent comprises any one or a mixture of several of methanol, ethanol, tetrahydrofuran and dimethylformamide, the mass-to-volume ratio of the amino acid to the solvent is (3-30) kg:100L, and the pretreated Fe 2 O 3 The mass volume ratio of the nano particles to the solvent is (1-4) kg:100L, and the amino acid is 3-aminopropionic acid.
3. The method of claim 1, wherein in step (4), the activated Fe 2 O 3 The mass volume ratio of the nano particles to the lanthanum ligand solution is (1-2) g to 10L, hydrochloric acid or sodium hydroxide is used for adjusting the pH value of the solution to 7-9 before stirring reaction,the rotation speed during stirring reaction is 100-600 r/min, the reaction time is 4-16 h, and the reaction temperature is 25-90 ℃.
4. La@fe prepared by the preparation method according to any one of claims 1 to 3 2 O 3 A nano-particle combustion improver.
5. La@Fe 2 O 3 The preparation method of the nanoparticle combustion improver dispersion liquid is characterized by comprising the following steps:
(1) Preparation of chloro polyethylene glycol monomethyl ether: adding polyethylene glycol monomethyl ether and pyridine into an organic solvent, dropwise adding thionyl chloride while stirring, stirring and reacting for 4-8 hours after the dropwise adding is completed, and removing the solvent to obtain chlorinated polyethylene glycol monomethyl ether;
(2) Synthesizing methoxy polyvinyl alcohol glycerol ether: adding the chloropolyethylene glycol monomethyl ether obtained in the step (1) into an organic solvent, simultaneously adding sodium hydroxide and acetone glycerol, stirring to react, regulating the pH of a reaction mixed solution to make the mixed solution acidic, continuing stirring to react, removing the solvent after the reaction is finished, dissolving residues with the organic solvent, filtering, and removing the solvent from the filtrate to obtain methoxy polyvinyl alcohol glycerol ether;
(3)La@Fe 2 O 3 preparing a nanoparticle combustion improver dispersion liquid: la@Fe according to claim 6 2 O 3 Dispersing the nano-particle combustion improver in water, adding the methoxy polyvinyl alcohol glycerol ether obtained in the step (2) into the water, and stirring the mixture for reaction to obtain La@Fe 2 O 3 A nanoparticle combustion improver dispersion;
wherein the organic solvent comprises at least one of dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide, in the step (1), the molecular weight of the polyethylene glycol monomethyl ether is 600-2000, the mass volume ratio of the polyethylene glycol monomethyl ether to the organic solvent is (1-2) kg/10L, and the mass volume ratio of the pyridine to the organic solvent is (0.5-2) 100L.
6. The method according to claim 5, wherein in the step (2), the mass/volume ratio of the chloropolyethylene glycol monomethyl ether to the organic solvent is (1-2) kg/10L, the mass/volume ratio of the sodium hydroxide to the organic solvent is (1-5) kg/100L, the mass/volume ratio of the acetonide to the organic solvent is (8-15) kg/100L, and the pH of the mixture is 1-3.
7. The method according to claim 5, wherein in the step (3), the La@Fe 2 O 3 The mass ratio of the nano particles to water is 1 (0.1-0.4), and after the methoxy polyvinyl alcohol glycerol ether is added, the concentration of the methoxy polyvinyl alcohol glycerol ether is 2-20%.
8. La@Fe prepared by the preparation method according to any one of claims 5 to 7 2 O 3 Nanoparticle combustion improver dispersion.
9. La@fe according to claim 8 2 O 3 The application of the nano-particle combustion improver dispersion liquid in the heating field.
10. La@fe according to claim 8 2 O 3 The using method of the nanoparticle combustion improver dispersion liquid is characterized in that La@Fe is used as a catalyst 2 O 3 The nano-particle combustion improver dispersion liquid is atomized in the combustion area of the boiler after being sprayed by a sprayer, and the spraying amount is 0.1-0.5Kg of combustion improver dispersion liquid per cubic fuel gas.
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