CN117701049A - Composite crystallization film slurry for inner wall of ethylene cracking furnace tube - Google Patents
Composite crystallization film slurry for inner wall of ethylene cracking furnace tube Download PDFInfo
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- CN117701049A CN117701049A CN202410161617.5A CN202410161617A CN117701049A CN 117701049 A CN117701049 A CN 117701049A CN 202410161617 A CN202410161617 A CN 202410161617A CN 117701049 A CN117701049 A CN 117701049A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000002002 slurry Substances 0.000 title claims abstract description 40
- 238000005336 cracking Methods 0.000 title claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000005977 Ethylene Substances 0.000 title claims abstract description 22
- 238000002425 crystallisation Methods 0.000 title claims abstract description 20
- 230000008025 crystallization Effects 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 239000002270 dispersing agent Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical class S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000280 densification Methods 0.000 claims abstract description 18
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
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- -1 polydimethylsiloxane Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical group CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 32
- 230000005764 inhibitory process Effects 0.000 abstract description 3
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- 239000000463 material Substances 0.000 description 41
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- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101150049811 SEC6 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102100030552 Synaptosomal-associated protein 25 Human genes 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses composite crystallization film slurry used on the inner wall of a furnace tube of an ethylene cracking furnace. The slurry is prepared by mixing the following components: 20-40 parts of aluminum dihydrogen phosphate, 10-20 parts of zirconium dioxide, 10-20 parts of silicon dioxide micro powder, 5-20 parts of silica sol, 5-15 parts of magnesium oxide, 2-6 parts of modified molybdenum disulfide, 0.5-2 parts of boron carbide, 0.1-0.5 part of carbon black, 1-5 parts of stabilizer, 0.1-0.5 part of densification agent, 0.1-0.5 part of dispersing agent, 1-5 parts of curing agent, 1-5 parts of solvent and 1-3 parts of auxiliary agent. The composite crystallization film used on the inner wall of the furnace tube of the ethylene cracking furnace has the performances of coking inhibition, carburization, high temperature resistance and high density; the composite crystallization film is used on the inner wall of the furnace tube, so that the burning period can be effectively prolonged, the ethylene yield can be improved, and the burning cost can be reduced.
Description
Technical Field
The invention belongs to the technical field of functional coating, and particularly relates to composite crystalline film slurry used for the inner wall of an ethylene cracking furnace tube.
Background
In the ethylene production process, an ethylene cracking furnace is the most important device, and the inside of a radiant section furnace tube of the cracking furnace is a key area for cracking materials. Therefore, the use effect and stability of the radiant section furnace tube of the cracking furnace are key to influencing the operation of the cracking furnace.
The common problems of ethylene cracking furnace tubes are coking and carburization of the inner walls of the furnace tubes. When the cracking furnace is operated, the temperature of the furnace tube is 900-1150 ℃, materials are easy to coke on the inner wall of the furnace tube at high temperature, and coking increases the heat resistance and fuel consumption of the wall of the furnace tube, thereby influencing the yield of ethylene. The coking can cause the furnace tube to have local high temperature, thereby aggravating carburization of the furnace tube and greatly reducing the service life of the furnace tube. At present, the cracking furnace generally runs continuously for 2-4 months, the furnace must be shut down for burning, and the service life of the furnace tube is only about 5-10 years (the material components and specific working conditions have great influence on the service life of the furnace tube). The coking mechanism of the inner wall of the furnace tube mainly comprises three mechanisms: catalytic coking, condensation coking, and free radical coking. Related studies have been carried out for many years, and the solutions currently existing are:
1. adding an inhibitor into the material: the surface of the furnace tube is passivated, the catalytic reaction of the tube wall on materials is inhibited, and coking is reduced, wherein the inhibitor mainly comprises sulfur-containing compounds, phosphorus-containing compounds, metal salts, metal oxides, boron-containing compounds and polysiloxane compounds. However, when the inner wall of the furnace tube is passivated, some inhibitors damage the furnace tube, the service life of the furnace tube is reduced, and leakage is easy to occur at a welding line, so that safety accidents are caused;
2. changing the structure of the furnace tube: the developed furnace tubes with the novel structure comprise an internal spiral plum blossom type furnace tube, a longitudinal fin furnace tube, a MERT furnace tube, a twisted furnace tube and the like. The furnace tube with the new structure has high cost, and the cost performance is continuously demonstrated by application;
3. coating technology: the surface coating technology with good effect is currently applied in many foreign countries, and mainly comprises the technologies of surfacing, ceramic coating, heat treatment and coating, and has the advantages of higher material cost and higher construction difficulty.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide composite crystallization film slurry for the inner wall of a furnace tube of an ethylene cracking furnace.
The key points and the technical difficulties of the invention are as follows:
1. the composite crystallization film slurry component does not produce catalysis effect on materials and does not promote coking reaction;
2. the composite crystalline film needs to have the functions of coking prevention and carburization prevention under working conditions;
3. the composite crystalline film needs to have high bonding strength with the substrate at high temperature, and to remain free from falling off and cracking in severe thermal shock environments.
The invention designs the composite crystallization membrane slurry used for the ethylene cracking furnace tube through researching the coking mechanism, coking components, coking forms and the like of the inner wall of the furnace tube.
The composite crystallization film slurry for the inner wall of the furnace tube of the ethylene cracking furnace is prepared by mixing the following components: 20-40 parts of aluminum dihydrogen phosphate, 10-20 parts of zirconium dioxide, 10-20 parts of silicon dioxide micro powder, 5-20 parts of silica sol, 5-15 parts of magnesium oxide, 2-6 parts of modified molybdenum disulfide, 0.5-2 parts of boron carbide, 0.1-0.5 part of carbon black, 1-5 parts of stabilizer, 0.1-0.5 part of densification agent, 0.1-0.5 part of dispersing agent, 1-5 parts of curing agent, 1-5 parts of solvent and 1-3 parts of auxiliary agent.
In specific cases, the modified nano molybdenum disulfide is prepared by the following steps: adding modifier into absolute ethanol, mixing uniformly, adding nanometer MoS 2 Stirring or ball milling the fine powder for 2-4h, filtering, drying, and pulverizing to obtain modifier and nanometer MoS 2 The mass ratio of the fine powder is 2:1, the mass/volume ratio of the modifier to the absolute ethyl alcohol is 1:4-6, and the modifier is one or a combination of a silane coupling agent and an emulsifier OP-10.
In specific cases, the stabilizer is nano yttrium oxide and is prepared by the following steps: taking yttrium nitrate as mother liquor, taking urea as precipitant, adding PEG-2000 for dispersing, adjusting pH to 8 by ammonia water, mixing and stirring in water bath, filtering out precipitate, adding a proper amount of n-butanol into a filter cake for fully stirring, distilling to obtain a precursor, and finally calcining in a muffle furnace at 700 ℃ for 5 hours to obtain the nano yttrium oxide powder.
In particular, the aluminum dihydrogen phosphate is white powder, wherein Al (H) 2 PO 4 ) 3 The content is more than 98 percent, fe 2 O 3 Less than 0.01%.
In specific cases, the mass fraction of silicon dioxide in the silica sol is more than 30 percent, na 2 O is less than 0.5%, and the diameter of the silicon dioxide particles is 3-50nm.
In particular, the silicaMicro powder SiO 2 The content is more than 99.5%, and the granularity is 1-50 μm.
In particular, zrO in the zirconium dioxide 2 The content is more than 95 percent, and the grain diameter is 1-50 mu m.
In particular, the MgO content in the magnesium oxide is more than 98 percent, and the granularity is 0.3-1 mu m.
In particular, B in the boron carbide 4 The content of C is more than 95%, and the granularity is 1-10 μm.
In particular, the C content in the carbon black is more than 99 percent, and the granularity is 0.03-0.1 mu m.
In specific cases, the densification agent is metal aluminum powder, the Al content is more than 99%, and the granularity is 0.5-10 mu m.
In specific cases, the curing agent is alumina micropowder, and Al in the alumina micropowder 2 O 3 The content is more than 99%, and the granularity is 0.3-1 μm.
In specific cases, the solvent is ethyl orthosilicate; the dispersing agent is a mixture of an inorganic dispersing agent and an organic dispersing agent, wherein the inorganic dispersing agent is sodium tripolyphosphate or sodium hexametaphosphate, the organic dispersing agent is triethylhexyl phosphoric acid or polyvinylpyrrolidone, and the weight ratio of the inorganic dispersing agent to the organic dispersing agent is 1:2.
specifically, the auxiliary agent consists of a leveling agent and a defoaming agent, wherein the leveling agent is at least one of fluorine modified acrylic ester copolymer and acrylic ester copolymer, the defoaming agent is polydimethylsiloxane, and the ratio of the leveling agent to the defoaming agent is 1:1 by weight.
The production of the composite crystallization film comprises the steps of firstly putting silica sol and aluminum dihydrogen phosphate into a high-speed dispersing machine according to a designed proportion, adding a proper amount of deionized water for uniform mixing, then adding powder materials into the dispersing machine one by one, filtering, packaging and sealing after full uniformity, and obtaining composite crystallization film slurry used on the inner wall of a furnace tube of an ethylene cracking furnace, wherein the application implementation steps of the composite crystallization film slurry are as follows:
(1) Carrying out acid washing, water washing, high-pressure flushing and drying treatment on the inner wall of the furnace tube;
(2) At normal temperature, protecting the outer wall of the furnace tube, and uniformly coating the composite crystalline film slurry on the inner wall of the furnace tube by using a dip coating method, wherein the thickness is 60-90 micrometers;
(3) Removing water by natural drying;
(4) And baking to form a film through a special baking system, and then putting the film into use.
The performance test shows that: the composite crystallization film used on the inner wall of the furnace tube of the ethylene cracking furnace has the performances of coking inhibition, carburization, high temperature resistance and high density, and is realized by the following technical principles:
(1) The transition metal element is easy to carry out electron pairing with the hydrocarbon free radical intermediate rich in electrons, can promote the generation of unstable carbide, and finally forms a large amount of coking. The components of the composite crystalline film of the invention reduce the use of transition metal elements as much as possible. Elemental components such as zinc, copper, chromium, titanium, etc. commonly used in phosphate coating materials;
(2) In-situ generation of microcrystals and solid solution strengthening and toughening technology: according to the invention, magnesia and alumina micropowder are added, the generation temperature of the aluminum magnesium spinel can be reduced under the action of yttria, the aluminum magnesium spinel starts to be generated in situ at 900 ℃, and the generation of the spinel is accompanied with volume expansion, so that the density and strength of the composite crystalline film are improved. When the temperature of the furnace tube exceeds 1000 ℃, the silicon dioxide and alumina micropowder in the composite crystal film can gradually generate mullite phase solid solution, so that the high-temperature thermal shock performance and the compactness of the coating are enhanced. Aluminum dihydrogen phosphate and magnesium oxide can gradually form amorphous cordierite structure solid solution at the temperature, so that the high strength and good thermal shock performance of the composite crystalline film at high temperature are further ensured;
(3) By adding the rare earth material yttrium oxide, the crystal formation temperature can be reduced, and the compactness, toughness and regularity of the composite crystalline film are improved. The dispersed microcrystalline ceramic phase makes the structure of the composite crystalline film tend to be uniform, and corrosive elements cannot permeate the composite crystalline film, so that the furnace tube is isolated from the outside. The regular composite crystallization film has low surface energy, and coke scale can not adhere to the surface of the film, so that the adhesion of coke quality is reduced. In addition, at high temperatures, micron-sized yttrium oxide and zirconium oxide begin to form ZrO 2 -Y 2 O 3 Solid solution is formed intoThe yttrium stabilizes the zirconium oxide, so that the mechanical strength of the composite crystalline film is improved;
(4) The volume type deformation of spinel and solid solution generated in situ is utilized, the thermal expansion coefficient of the composite crystalline film can be regulated to be basically synchronous with the base material at high temperature, the internal stress of the composite crystalline film is reduced, and the thermal shock performance of the material is improved;
(5) The modified molybdenum disulfide is a layered structure material, so that a labyrinth effect can be formed on microcosmic scale, and a penetrating hole structure can not appear in the material; the densification agent metallic aluminum can generate a dense alumina film on the surface in an oxygen-containing environment, and the dense alumina film plays a role in closing pores along with volume expansion. In addition, unoxidized aluminum metal can melt at high temperature to further block pores, and the combined action of the aluminum metal and the pore can play a role in reducing micropores of the composite crystalline film. The labyrinth effect and the plugging of micropores together prevent corrosive elements and material components from penetrating the composite crystalline film.
The invention has the technical advantages that:
1. the composite crystallization membrane component has an inhibition effect on catalytic coking, and reduces the generation of the catalytic coking;
2. the composite crystallization film has the characteristics of high density, carburization prevention and corrosion prevention element permeation, has lower surface energy, and can prevent carbide adhesion generated by condensation coking and free radical coking;
3. the composite crystalline film has high bonding strength with the base material, has similar expansion coefficient with the base material, has lower internal stress generated by the composite crystalline film and the base material in the heat expansion and cold contraction environment, and is free from cracking and falling.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and are not intended to limit the actual scope of the present invention in any way.
The raw materials used in the specific examples of the present invention are all commercially available, and some of them may be self-made by the following preparation methods.
Preparation example 1
Modified nano molybdenum disulfide
100g of emulsifier OP-10 is added into 500ml of absolute ethyl alcohol, and 50g of nanometer MoS with the granularity of 100-500nm is added after the mixture is uniformly mixed 2 Stirring or ball milling the fine powder for 3 hours, filtering, drying and crushing for later use. By selecting nanometer MoS with different particle sizes 2 Can prepare modified nanometer MoS with different granularity 2 。
Preparation example 2
Stabilizer nanometer yttrium oxide
Taking yttrium nitrate as mother liquor, taking urea as precipitant, adding PEG-2000 for dispersing, adjusting pH to 8 by ammonia water, mixing and stirring in water bath, filtering out precipitate, adding a proper amount of n-butanol into a filter cake for fully stirring, distilling to obtain a precursor, and finally calcining in a muffle furnace at 700 ℃ for 5 hours to obtain the nano yttrium oxide powder.
Example 1:
20 parts of aluminum dihydrogen phosphate, 20 parts of zirconium dioxide, 10 parts of silicon dioxide micro powder, 20 parts of silica sol, 6 parts of magnesium oxide, 6 parts of modified molybdenum disulfide, 2 parts of boron carbide, 0.5 part of carbon black, 5 parts of stabilizer, 0.1 part of densification agent, 0.2 part of dispersing agent, 2.5 parts of curing agent, 5 parts of solvent and 3 parts of auxiliary agent. Firstly, putting silica sol and aluminum dihydrogen phosphate into a high-speed dispersing machine, adding a proper amount of deionized water for uniform mixing, then adding powder materials into the dispersing machine one by one, filtering, packaging and sealing after the powder materials are sufficiently uniform, and obtaining the composite crystal film slurry SEC1;
wherein the stabilizer is nano yttrium oxide;
wherein the densification agent is metal aluminum powder;
wherein the curing agent is alumina micropowder;
wherein the solvent is ethyl orthosilicate;
wherein the dispersing agent is organic dispersing agent triethylhexyl phosphate 0.13 weight parts and inorganic dispersing agent sodium tripolyphosphate 0.07 weight parts;
wherein the auxiliary agent consists of a leveling agent and a defoaming agent in a weight ratio of 1:1. The leveling agent is 1.5 parts by weight of acrylate copolymer; the defoamer is 1.5 parts by weight of polydimethylsiloxane.
Example 2:
25 parts of aluminum dihydrogen phosphate, 18 parts of zirconium dioxide, 13 parts of silica micropowder, 15 parts of silica sol, 8 parts of magnesium oxide, 5 parts of modified molybdenum disulfide, 1.5 parts of boron carbide, 0.4 part of carbon black, 4 parts of stabilizer, 0.2 part of densification agent, 0.2 part of dispersing agent, 4 parts of curing agent, 4 parts of solvent and 2 parts of auxiliary agent. Firstly, putting silica sol and aluminum dihydrogen phosphate into a high-speed dispersing machine, adding a proper amount of deionized water for uniform mixing, then adding powder materials into the dispersing machine one by one, filtering, packaging and sealing after the powder materials are sufficiently uniform, and obtaining the composite crystal film slurry SEC2;
wherein the stabilizer is nano yttrium oxide;
wherein the densification agent is metal aluminum powder;
wherein the curing agent is alumina micropowder;
wherein the solvent is ethyl orthosilicate;
wherein the dispersing agent is 0.13 weight part of organic dispersing agent polyvinylpyrrolidone and 0.07 weight part of inorganic dispersing agent sodium hexametaphosphate;
wherein the auxiliary agent consists of a leveling agent and a defoaming agent in a weight ratio of 1:1. The leveling agent is 1 part by weight of acrylate copolymer; the defoamer is 1 part by weight of polydimethylsiloxane.
Example 3:
30 parts of aluminum dihydrogen phosphate, 15 parts of zirconium dioxide, 15 parts of silica micropowder, 10 parts of silica sol, 10 parts of magnesium oxide, 4 parts of modified molybdenum disulfide, 1 part of boron carbide, 0.3 part of carbon black, 3 parts of stabilizer, 0.5 part of densification agent, 0.4 part of dispersing agent, 5 parts of curing agent, 4 parts of solvent and 2 parts of auxiliary agent. Firstly, putting silica sol and aluminum dihydrogen phosphate into a high-speed dispersing machine, adding a proper amount of deionized water for uniform mixing, then adding powder materials into the dispersing machine one by one, filtering, packaging and sealing after the powder materials are sufficiently uniform, and obtaining the composite crystal film slurry SEC3;
wherein the stabilizer is nano yttrium oxide;
wherein the densification agent is metal aluminum powder;
wherein the curing agent is alumina micropowder;
wherein the solvent is ethyl orthosilicate;
wherein the dispersing agent is organic dispersing agent triethylhexyl phosphate 0.27 weight parts and inorganic dispersing agent sodium tripolyphosphate 0.13 weight parts;
wherein the auxiliary agent consists of a leveling agent and a defoaming agent in a weight ratio of 1:1. The leveling agent is 1 part by weight of acrylate copolymer; the defoamer is 1 part by weight of polydimethylsiloxane.
Example 4:
35 parts of aluminum dihydrogen phosphate, 13 parts of zirconium dioxide, 18 parts of silica micropowder, 8 parts of silica sol, 12 parts of magnesium oxide, 3 parts of modified molybdenum disulfide, 0.7 part of boron carbide, 0.2 part of carbon black, 2 parts of stabilizer, 0.3 part of densification agent, 0.5 part of dispersing agent, 6 parts of curing agent, 1 part of solvent and 1 part of auxiliary agent. Firstly, putting silica sol and aluminum dihydrogen phosphate into a high-speed dispersing machine, adding a proper amount of deionized water for uniform mixing, then adding powder materials into the dispersing machine one by one, filtering, packaging and sealing after the powder materials are sufficiently uniform, and obtaining the composite crystal film slurry SEC4;
wherein the stabilizer is nano yttrium oxide;
wherein the densification agent is metal aluminum powder;
wherein the curing agent is alumina micropowder;
wherein the solvent is ethyl orthosilicate;
wherein the dispersing agent is organic dispersing agent triethylhexyl phosphate 0.34 weight parts and inorganic dispersing agent sodium tripolyphosphate 0.16 weight parts;
wherein the auxiliary agent consists of a leveling agent and a defoaming agent in a weight ratio of 1:1. The leveling agent is 0.5 part by weight of acrylate copolymer; the defoamer is 0.5 part by weight of polydimethylsiloxane.
Example 5:
40 parts by weight of aluminum dihydrogen phosphate, 10 parts by weight of zirconium dioxide, 17 parts by weight of silica micropowder, 5 parts by weight of silica sol, 15 parts by weight of magnesium oxide, 2 parts by weight of modified molybdenum disulfide, 0.5 part by weight of boron carbide, 0.1 part by weight of carbon black, 1 part by weight of stabilizer, 0.2 part by weight of densification agent, 0.1 part by weight of dispersing agent, 7.5 parts by weight of curing agent, 1 part by weight of solvent and 1 part by weight of auxiliary agent. Firstly, putting silica sol and aluminum dihydrogen phosphate into a high-speed dispersing machine, adding a proper amount of deionized water for uniform mixing, then adding powder materials into the dispersing machine one by one, filtering, packaging and sealing after the powder materials are sufficiently uniform, and obtaining the composite crystal film slurry SEC5;
wherein the stabilizer is nano yttrium oxide;
wherein the densification agent is metal aluminum powder;
wherein the curing agent is alumina micropowder;
wherein the solvent is ethyl orthosilicate;
wherein the dispersing agent is organic dispersing agent triethylhexyl phosphate 0.66 weight parts and inorganic dispersing agent sodium tripolyphosphate 0.34 weight parts;
wherein the auxiliary agent consists of a leveling agent and a defoaming agent in a weight ratio of 1:1. The leveling agent is 0.5 part by weight of acrylate copolymer; the defoamer is 0.5 part by weight of polydimethylsiloxane.
Comparative example 1:
comparative example 1 in comparison with example 1, the composite crystalline film slurry SEC6 of the present invention was prepared without adding magnesium oxide and aluminum oxide fine powder to the formulation, and other components and preparation process were the same.
Comparative example 2:
comparative example 2 in comparison with example 1, the composite crystalline film slurry SEC7 of the present invention was prepared without adding molybdenum disulfide to the formulation, and other components and preparation process were the same.
Comparative example 3:
comparative example 3 in comparison with example 1, 15 parts by weight of molybdenum disulfide was added to the formulation, and the other components and the preparation process were the same, to prepare the composite crystalline film slurry SEC8 of the present invention.
Comparative example 4:
comparative example 4 in comparison with example 1, the composite crystalline film slurry SEC9 of the present invention was prepared without adding a densification agent to the formulation, and with the same other components and preparation process.
Comparative example 5:
comparative example 5 in comparison with example 1, the formulation was prepared by adding only 0.2 parts by weight of an inorganic dispersant to the dispersant, and other components and preparation processes were the same to prepare a composite crystalline film slurry SEC10 of the present invention.
Comparative example 6:
comparative example 6 in comparison with example 1, the formulation was prepared by adding only 0.2 parts by weight of the organic dispersant to the dispersant, and other components and preparation processes were the same to prepare the composite crystalline film slurry SEC11 of the present invention.
Comparative example 7:
the composite crystal film slurry SEC12 is prepared according to the proportion of a sample SEC7 in Chinese patent CN109401387B, which is a slurry capable of forming a composite crystal film.
Performance test
Preparation of composite crystalline film/coating: spraying by using an air spray gun with the pressure of 0.25MPa, respectively spraying the slurry SEC1-12 prepared in the examples and the comparative examples on a steel substrate with the thickness of 0.1mm, pre-drying for 30min at 50 ℃, drying and solidifying in an oven at 600 ℃ according to a heating curve, and cooling to obtain the composite crystalline film/coating sample. The specific temperature rise system is as follows: the baking time is 28 hours in total, firstly, the temperature is slowly raised at normal temperature, the temperature is raised to 110 ℃ within 8 hours, and the temperature is kept at 110 ℃ for 4 hours. And heating again, heating to 350 ℃ within 4 hours, and preserving heat for 2 hours at 350 ℃. And heating again, heating to 600 ℃ within 6 hours, and keeping the temperature at 600 ℃ for 4 hours to finish, wherein the baking of the crystalline film/coating is finished.
In order to accurately test the performance of the composite crystalline film, the working condition of the heating furnace is simulated to treat a sample: and (3) slowly heating the sample to 1200 ℃ in a laboratory heating furnace, and preserving the temperature for 24 hours, wherein the composite crystal film is completely the same as the composite crystal film under the actual application working condition. After natural cooling, the following test runs were started:
1. anti-coking test:
13 ethylene cracking furnace tubes are selected, the material is 35Cr-45Ni-Nb, SEC1-12 composite crystallization film slurry is prepared on the inner wall of the furnace tubes, and the rest 1 tube is not treated. Ethylene cracking experiments were performed in an ethylene cracking furnace simulation apparatus using 13 furnace tubes, respectively, and the experiment was continued for 168 hours. After the experiment is finished, thickness measurement and appearance comparison are carried out on the coking condition of the inner walls of 13 furnace tubes;
2. adhesion detection
The SEC1-12 sample is subjected to adhesion detection, and the coating pull-off strength standard is measured according to an ASTM D4541-17 portable viscosity tester;
3. porosity detection
The method comprises the steps of detecting the porosity of a SEC1-12 sample, and testing the aperture distribution and the thermal shock performance of the solid material according to GB/T21650.1-2008 by using a mercury porosimetry and a gas adsorption method;
4. high temperature resistance and thermal shock resistance test at 1200 DEG C
The SEC1-12 composite crystalline film slurry is prepared on the surface of the same metal substrate, is respectively heated to 1200 ℃ under the air atmosphere, is subjected to heat preservation for 10 minutes, is cooled by water, is circulated for 20 times, and is subjected to package Kuang Kailie, peeling, falling off and color change compared with the appearance damage condition of the composite crystalline film.
The results of the above test are shown in Table 1.
Conclusion:
1. in the comparison of SEC1, SEC2, SEC3, SEC4 and SEC5 examples, when the components are in the preferred weight parts, the difference of the properties of the materials is small, and the properties of the composite crystalline film are not affected.
2. Example 1 was compared with comparative examples 1-7, common furnace tubes:
(1) Comparative example 1 was not sufficiently dense due to the non-generation of spinel structure, resulting in slight coking;
(2) In the comparative example 2, molybdenum disulfide with a layered structure is not added, materials permeate through the composite crystallization membrane and undergo catalytic coking reaction, so that coking is obvious;
(3) The comparative example 3 shows that molybdenum disulfide plays a role of isolating materials, can prevent element infiltration and has basically normal coking condition;
(4) Comparative example 4 also produced significant coking due to the presence of micro-pores;
(5) The comparative examples 5 and 6 have good coking prevention effect, but the non-uniform coking is caused by the non-uniform components of the composite crystalline film;
(6) Comparative example 7 does not apply to the ethylene cracking furnace conditions because the formulation design does not take into account the prevention of carbide coking at high temperatures;
(7) The comparison of the common furnace tubes shows that the common furnace tubes have the most serious coking, and the application effect is similar to that of the actual ethylene cracking furnace tubes.
3. Example 1 is compared with comparative example 1: the magnesia and the alumina can be used as curing agents and reinforcing agents, play a role of a ceramic framework in the material, and generate magnesia-alumina spinel, so that the strength and the thermal shock property of the composite crystalline film are improved simultaneously. When magnesium oxide and aluminum oxide are not added, the material has various properties which are reduced at 1200 ℃.
4. Example 1 was compared with comparative example 2, comparative example 3: when molybdenum disulfide is not added, the adhesive force and the high-temperature performance of the material are not affected. However, the molybdenum disulfide with a layered structure lacks barrier pores, the porosity of the material becomes large, and at the moment, some elements possibly permeate the composite crystalline film to oxidize and corrode the substrate. When excessive molybdenum disulfide is added, the adhesion force of the material is greatly reduced due to the lubricity of the molybdenum disulfide, and meanwhile, the expansion coefficient of the material is not matched with that of a metal base material, so that the thermal shock performance is poor.
5. Example 1 vs. comparative example 4: when the densification agent is not added, the porosity is improved because tiny pores of the material are not plugged, and harmful elements can permeate through the composite crystalline film to oxidize and corrode the substrate. Although the adhesive force, the high temperature resistance and the thermal shock resistance are not affected, the service life of the composite crystal film can be reduced under the working condition of an ethylene cracking furnace, and the anti-coking effect is poor.
6. Example 1 was compared with comparative example 5 and comparative example 6: the type of the dispersing agent is important for preparing the slurry by powder, the smaller the particle size is, the higher the surface energy is, the more adaptive dispersing agent with higher adsorption strength is needed, and the agglomeration and flocculation of particles are effectively reduced by the compound use of the organic dispersing agent and the inorganic dispersing agent. Experimental comparison shows that each component in the slurry cannot be uniformly distributed by using one dispersant alone, and the material is subjected to foaming and flaking due to stress concentration at high temperature, so that each performance cannot achieve the design effect.
7. Compared with comparative example 7, the component design of the embodiment improves the high temperature resistance of the composite crystallization film and the thermal shock resistance, the use temperature of the new scheme can reach 1200 ℃, and the use temperature of the SEC12 scheme is below 850 ℃.
It should be understood that these examples are for the purpose of illustrating the invention only and are not intended to limit the scope of the invention. Furthermore, it is to be understood that various changes, modifications and/or variations may be made by those skilled in the art after reading the technical content of the present invention, and that all such equivalents are intended to fall within the scope of protection defined in the claims appended hereto.
Claims (10)
1. The composite crystallization film slurry for the inner wall of the furnace tube of the ethylene cracking furnace is characterized by being prepared by mixing the following components: 20-40 parts of aluminum dihydrogen phosphate, 10-20 parts of zirconium dioxide, 10-20 parts of silicon dioxide micro powder, 5-20 parts of silica sol, 5-15 parts of magnesium oxide, 2-6 parts of modified molybdenum disulfide, 0.5-2 parts of boron carbide, 0.1-0.5 part of carbon black, 1-5 parts of stabilizer, 0.1-0.5 part of densification agent, 0.1-0.5 part of dispersing agent, 1-5 parts of curing agent, 1-5 parts of solvent and 1-3 parts of auxiliary agent.
2. The composite crystalline film slurry of claim 1, wherein the modified nano molybdenum disulfide is prepared by: adding modifier into absolute ethanol, mixing uniformly, adding nanometer MoS 2 Stirring or ball milling the fine powder for 2-4h, filtering, drying, and pulverizing to obtain modifier and nanometer MoS 2 The mass ratio of the fine powder is 2:1, the mass/volume ratio of the modifier to the absolute ethyl alcohol is 1:4-6, and the modifier is one or a combination of a silane coupling agent and an emulsifier OP-10.
3. The composite crystalline film slurry of claim 1, wherein the stabilizer is nano yttrium oxide prepared by the steps of: taking yttrium nitrate as mother liquor, taking urea as precipitant, adding PEG-2000 for dispersing, adjusting pH to 8 by ammonia water, mixing and stirring in water bath, filtering out precipitate, adding a proper amount of n-butanol into a filter cake for fully stirring, distilling to obtain a precursor, and finally calcining in a muffle furnace at 700 ℃ for 5 hours to obtain the nano yttrium oxide powder.
4. The composite crystalline film slurry as defined in claim 1, wherein the aluminum dihydrogen phosphate is a white powder in which Al (H 2 PO 4 ) 3 The content is more than 98 percent, fe 2 O 3 Less than 0.01%.
5. The composite crystalline film slurry of claim 1, wherein the silica mass fraction in the silica sol is greater than 30%, na 2 O is less than 0.5%, and the diameter of the silicon dioxide particles is 3-50nm.
6. The composite crystalline film slurry according to claim 1, wherein the MgO content in the magnesium oxide is more than 98% and the particle size is 0.3 to 1 μm.
7. The composite crystalline film slurry according to claim 1, wherein the densification agent is a metal aluminum powder, the Al content is 99% or more, and the particle size is 0.5 to 10 μm.
8. The composite crystalline film slurry as claimed in claim 1, wherein the curing agent is alumina micropowder, wherein Al is contained in the alumina micropowder 2 O 3 The content is more than 99%, and the granularity is 0.3-1 μm.
9. The composite crystalline film slurry of claim 1, wherein the solvent is ethyl orthosilicate; the dispersing agent is a mixture of an inorganic dispersing agent and an organic dispersing agent, wherein the inorganic dispersing agent is sodium tripolyphosphate or sodium hexametaphosphate, the organic dispersing agent is triethylhexyl phosphoric acid or polyvinylpyrrolidone, and the weight ratio of the inorganic dispersing agent to the organic dispersing agent is 1:2.
10. the composite crystalline film slurry according to claim 1, wherein the auxiliary agent is composed of a leveling agent and an antifoaming agent, the leveling agent is at least one of a fluorine modified acrylate copolymer and an acrylate copolymer, the antifoaming agent is polydimethylsiloxane, and the ratio of the leveling agent to the antifoaming agent is 1:1 by weight.
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