CN110801848A - Flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and preparation method thereof - Google Patents
Flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and preparation method thereof Download PDFInfo
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- CN110801848A CN110801848A CN201910959462.9A CN201910959462A CN110801848A CN 110801848 A CN110801848 A CN 110801848A CN 201910959462 A CN201910959462 A CN 201910959462A CN 110801848 A CN110801848 A CN 110801848A
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- catalyst
- temperature
- scr denitration
- titanium
- cerium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 169
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 42
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical group [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 41
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 32
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 14
- 231100000572 poisoning Toxicity 0.000 abstract description 13
- 230000000607 poisoning effect Effects 0.000 abstract description 13
- 239000012752 auxiliary agent Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910016978 MnOx Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/40—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention belongs to the fields of environmental protection technology and denitration catalysis, and particularly relates to a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and a preparation method thereof. The carrier of the catalyst is a titanium cerium composite oxide hollow sphere, the active component of the catalyst is vanadium pentoxide, and the catalytic auxiliary agents are ferric oxide, molybdenum trioxide and barium sulfate; the two-step rolling forming process is adopted: first miningLoading a catalytic assistant on the surface of the titanium-cerium composite oxide hollow sphere by an isometric impregnation method, loading a catalyst active component vanadium pentoxide on the surface of a carrier, and forming the catalyst into a flat plate by a roll forming process to obtain the flat plate type SCR denitration catalyst with wide temperature range and sulfur poisoning resistance. The catalyst disclosed by the invention has good catalytic activity and sulfur poisoning resistance in the temperature range of 150-450 ℃, and can solve the problems of low activity and sulfur poisoning of the catalyst in low-temperature flue gas and SO in medium-temperature flue gas2The problem of high oxidation rate is applicable to the denitration of the sulfur-containing flue gas at wide temperature.
Description
Technical Field
The invention belongs to the technical field of environmental protection and denitration catalysis, and particularly relates to a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst. The invention also provides a preparation method of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst.
Background
The Selective Catalytic Reduction (SCR) is the most widely used flue gas denitration technology at present, and has the advantages of high denitration efficiency, good selectivity and the like. The SCR denitration technology is to take ammonia gas and the like as a reducing agent to remove NO in the flue gas under the action of a catalystxSelectively reduced to harmless nitrogen and water.
At present, the most industrially applied SCR flue gas denitration catalyst is V2O5-WO3(MoO3)/TiO2The catalyst has high denitration activity and sulfur resistance, but the active temperature zone is narrow, the catalyst is only suitable for flue gas at the temperature of 300-400 ℃, and when the temperature is lower than the temperature, the denitration activity of the catalyst is obviously reduced, so that the problems of excessive emission of nitrogen oxides and the like caused by reduction of denitration efficiency are easily caused; in addition, SO in flue gas at low temperatures2And SO3The catalyst is easy to react with ammonia and water to generate ammonium sulfate under the action of the catalyst, so that the problems of sulfur poisoning of the catalyst and the like are caused. Chinese patent document CN106732536A discloses CeO2@MnOxLow-temperature SCR denitration catalyst, MnO prepared by precipitation method of catalystxThe nanometer particles are used as the inner core, and CeO is prepared by an in-situ liquid phase deposition method2Is wrapped in MnOxThe CeO with a core-shell structure is prepared by roasting the outer layer of the nano particles2@MnOxThe low-temperature SCR denitration catalyst has excellent SCR catalytic activity within the temperature range of 110-200 ℃; chinese patent application CN103170344A discloses a catalyst for low-temperature SCR denitration, which is composed of titanium dioxide, vanadium pentoxide, molybdenum trioxide and an auxiliary agent, wherein the auxiliary agent is a transition metal acid salt, the denitration efficiency of the catalyst in flue gas at a temperature lower than 200 ℃ can reach more than 95%, and the catalyst has high low-temperature activity. However, the low-temperature catalyst still has low-temperature activity, low-temperature sulfur poisoning and medium-temperature SO2/SO3The conversion rate is high, and the existing catalyst can not cover a low-temperature and medium-temperature region. Therefore, the development of the wide-temperature sulfur-resistant SCR denitration catalyst has important significance.
Disclosure of Invention
The invention aims to solve the problems that the existing SCR denitration catalyst is easy to be poisoned and inactivated by sulfur in water-containing sulfur-containing flue gas and the active temperature zone of the existing SCR denitration catalyst is narrow, and provides a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and a preparation method thereof.
In order to solve the technical problem, an embodiment of the invention provides a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst, which comprises 2-5 wt% of vanadium pentoxide, 1-3 wt% of ferric oxide, 5-12 wt% of molybdenum trioxide, 0.5-2 wt% of barium sulfate, 1-4 wt% of silicon dioxide and 74-90.5 wt% of a titanium-cerium composite oxide hollow sphere, wherein the titanium-cerium composite oxide hollow sphere is a catalyst carrier, the vanadium pentoxide is a catalyst active component, and the ferric oxide, the molybdenum trioxide and the barium sulfate are catalytic aids.
Preferably, the titanium-cerium composite oxide hollow spheres have the diameter of 6-10 microns.
The titanium cerium composite oxide hollow sphere is preferably selected from titanium dioxide and cerium dioxide, wherein the molar ratio of the titanium dioxide to the cerium dioxide is 0.5-1.
Preferably, the thickness of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst is 0.45-0.55 mm.
In order to solve the technical problem, an embodiment of the present invention further provides a preparation method of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst, including the following steps:
step 1: catalyst support preparation comprising:
step 1.1: adding a cerium nitrate solution into a glucose solution under the stirring condition, reacting for 24-48 h under the hydrothermal condition of 150-200 ℃, drying the product for 12-24 h at 60-90 ℃ after filtering, washing and washing with absolute ethyl alcohol, and roasting the obtained precipitate for 2-6 h at 500-600 ℃ in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
step 1.2: dispersing the mixture of cerium oxide and carbon prepared in the step 1.1 in absolute ethyl alcohol, then adding ammonia water, stirring uniformly, slowly dropwise adding tetraethyl titanate, stirring at a constant temperature of 30-50 ℃ for 24-48 h, filtering, washing the obtained precipitate with water and absolute ethyl alcohol, and roasting at a temperature of 500-600 ℃ in air for 12-24 h to obtain a titanium-cerium composite oxide hollow sphere serving as a catalyst carrier;
step 2: catalyst mud preparation, comprising:
step 2.1: respectively preparing ammonium heptamolybdate and ferric nitrate solution;
step 2.2: sequentially adding the ammonium heptamolybdate solution and the ferric nitrate solution into the titanium-cerium composite oxide hollow spheres prepared in the step 1.2, uniformly stirring, adding barium sulfate, uniformly stirring, adding diatomite, glass fiber, stearic acid, polyvinyl alcohol, carboxymethyl cellulose and polyacrylamide, and aging for 24-48 hours under a closed condition to obtain catalyst mud loaded with a catalyst additive;
and step 3: the flat-plate catalyst forming method comprises the following steps:
step 3.1: extruding the catalyst mud material prepared in the step 2.2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and then performing roll coating, pleating, shearing and drying to obtain a flat catalyst blank;
step 3.2: and soaking the prepared catalyst blank in an ammonium metavanadate solution at the temperature of 40-60 ℃ for 15-30 min, and drying and roasting to obtain the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst.
Preferably, in the step 1, the concentration of the cerium nitrate solution is 1-4 mol/L, the concentration of the glucose solution is 2-6 mol/L, and the concentration of ammonia water is 25-28 wt%.
Preferably, in the step 2, the polyacrylamide is anionic and has a molecular weight of 300 to 600 ten thousand.
Preferably, in the step 3, the concentration of the ammonium metavanadate solution is 2-5 mol/L.
Preferably, in the step 3, the drying temperature is 120-160 ℃, and the drying time is 1-5 min; the roasting temperature is 450-550 ℃, and the roasting time is 4-12 h.
Preferably, in the step 3, the thickness of the prepared flat plate type wide-temperature sulfur-resistant SCR denitration catalyst is 0.45-0.55 mm.
According to the technical scheme of the embodiment of the invention, on the basis of a conventional vanadium-titanium system catalyst, a novel titanium-cerium composite oxide hollow sphere is used as a catalyst carrier, and the catalyst is modified and the preparation process is optimized to prepare the flat-plate SCR denitration catalyst with excellent wide-temperature activity and sulfur poisoning resistance; wherein, the active components and the auxiliary agents of the catalyst are loaded on the carrier in two steps: firstly, loading catalytic auxiliaries, namely ferric oxide, molybdenum trioxide and barium sulfate on the surface of a titanium cerium composite oxide hollow sphere by adopting an isometric impregnation method, then loading a catalyst active component, namely vanadium pentoxide, on the surface of a carrier, and forming the catalyst into a flat plate shape by a roll forming process; the beneficial effects of the technical scheme are as follows:
1. the titanium-cerium composite oxide hollow sphere has a special hollow structure and is used as a catalyst carrier, so that the specific surface area of the catalyst is greatly increased, the distribution of active components is facilitated, and the low-temperature denitration activity of the catalyst can be effectively improved;
2. compared with the conventional aggregated titanium dioxide or titanium cerium composite carrier, the titanium cerium composite oxide hollow sphere has a large cavity with the diameter of 6-10 microns, the structure of the hollow sphere is favorable for decomposing ammonium sulfate salt, the generation of ammonium sulfate salt on the surface of the catalyst can be reduced, and the sulfur poisoning resistance of the catalyst is improved;
3. ferric oxide, molybdenum trioxide and barium sulfate which are used as auxiliary agents are firstly loaded on the surface of the titanium cerium composite oxide hollow sphere, and strong electrostatic effect exists between the ferric oxide and the molybdenum trioxide, so that the strong electrostatic effect can be blocked or greatly weakenedTo the action of anions and cations, thereby causing
And
separated, escaped
Under the action of catalyst to react with NO quicklyxThe reaction can catalyze the decomposition of ammonium sulfate salt to further improve the sulfur poisoning resistance of the catalyst, and barium sulfate can provide NH3Strong acid sites required for the SCR reaction, improving the low-temperature and medium-temperature denitration activity of the catalyst, and the addition of barium sulfate can reduce SO2The adsorption on the surface of the catalyst reduces the SO of the catalyst in a wide temperature range2The oxidation rate improves the sulfur poisoning resistance of the catalyst; vanadium pentoxide serving as an active component of the catalyst is loaded later, so that the active component can be uniformly distributed on the surface of the catalyst, the number of exposed active sites is increased, and the wide-temperature denitration activity of the catalyst is improved;
4. by adding various inorganic and organic forming aids, the preparation process is optimized, the thickness of the catalyst is controlled to be 0.45-0.55 mm which is far lower than 0.7mm of the conventional flat-plate catalyst on the basis of keeping the mechanical strength of the catalyst, and the SO of the catalyst can be reduced2The oxidation rate, the sulfur poisoning resistance of the catalyst is improved, the production cost is reduced, and good economic benefits are achieved.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst provided by an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst aiming at the problems that the existing SCR denitration catalyst is easy to be poisoned and inactivated by sulfur in water-containing sulfur-containing flue gas and the active temperature zone is narrow, the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst has a wider denitration active temperature zone, and the sulfur poisoning resistance of the catalyst is improved.
The invention provides a flat plate type wide-temperature sulfur-resistant SCR denitration catalyst, which comprises the following components: the catalyst comprises titanium cerium composite oxide hollow spheres as a catalyst carrier, vanadium pentoxide as a catalyst active component, ferric oxide, molybdenum trioxide and barium sulfate as a catalytic auxiliary agent, and other components such as silicon dioxide as a forming auxiliary agent; the weight percentages of the components are as follows:
2-5% of vanadium pentoxide, 1-3% of ferric oxide, 5-12% of molybdenum trioxide, 0.5-2% of barium sulfate, 74-90.5% of titanium cerium composite oxide hollow spheres and 1-4% of silicon dioxide.
In a preferred embodiment, the diameter of the hollow titanium-cerium composite oxide spheres is controlled to be 6 to 10 μm, and the molar ratio of titanium dioxide to cerium dioxide contained in the hollow titanium-cerium composite oxide spheres is controlled to be 0.5 to 1; the thickness of the catalyst flat plate is controlled to be 0.45-0.55 mm.
The preparation method of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst provided by the invention comprises the following steps as shown in figure 1:
s1, catalyst carrier preparation:
s1.1, adding a cerium nitrate solution into a glucose solution under the stirring condition, reacting for 24-48 h under the hydrothermal condition of 150-200 ℃, drying the product for 12-24 h at 60-90 ℃ after filtering, washing with water and washing with absolute ethyl alcohol, and roasting the obtained precipitate for 2-6 h at 500-600 ℃ in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
s1.2, dispersing the prepared mixture of cerium oxide and carbon in absolute ethyl alcohol, then adding ammonia water, stirring uniformly, slowly dropwise adding tetraethyl titanate, stirring at a constant temperature of 30-50 ℃ for 24-48 hours, filtering, washing the obtained precipitate with water and absolute ethyl alcohol, and roasting at a temperature of 500-600 ℃ in air for 12-24 hours to obtain a titanium-cerium composite oxide hollow sphere;
s2, catalyst mud preparation:
s2.1, respectively preparing ammonium heptamolybdate and ferric nitrate solutions;
s2.2, sequentially adding an ammonium heptamolybdate solution and an iron nitrate solution into the titanium-cerium composite oxide hollow spheres, uniformly stirring, adding barium sulfate, uniformly stirring, adding diatomite, glass fiber, stearic acid, polyvinyl alcohol, carboxymethyl cellulose and polyacrylamide, and aging for 24-48 hours under a closed condition to obtain a catalyst mud;
s3, forming a flat-plate catalyst:
s3.1, extruding the prepared catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and then performing roll coating, pleating, shearing and drying to obtain a flat catalyst blank;
s3.2, soaking the prepared catalyst blank in an ammonium metavanadate solution at the temperature of 40-60 ℃ for 15-30 min, and drying and roasting to obtain the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst.
As a preferred embodiment:
in step S1, the concentration of the cerium nitrate solution is 1-4 mol/L, the concentration of the glucose solution is 2-6 mol/L, and the concentration of the ammonia water is 25-28 wt%.
In step S2, the polyacrylamide is anionic with molecular weight of 300-600 ten thousand.
In the step S3, the concentration of the ammonium metavanadate solution is 2-5 mol/L; the drying temperature is 120-160 ℃, and the drying time is 1-5 min; the roasting temperature is 450-550 ℃, and the roasting time is 4-12 h; the plate thickness of the prepared flat plate type wide-temperature sulfur-resistant SCR denitration catalyst is controlled to be 0.45-0.55 mm and is lower than that of a conventional flat plate type catalyst, SO that the SO of the catalyst is reduced2The oxidation rate.
The flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and the preparation method thereof provided by the invention are further explained by specific examples below.
Example 1
The preparation process of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following steps:
(1) under the condition of stirring, adding 5.84L of 1mol/L cerium nitrate solution into 5L of 2mol/L glucose solution, and reacting for 48h under the hydrothermal condition of 150 ℃; filtering, washing and washing the product with absolute ethyl alcohol, drying at 60 ℃ for 24h, and roasting the precipitate at 500 ℃ for 6h in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
(2) dispersing the mixture in 100L of absolute ethyl alcohol, and then adding 400mL of 25 wt% ammonia water; after stirring uniformly, slowly adding 994g of tetraethyl titanate dropwise, and stirring at the constant temperature of 30 ℃ for 48 hours; filtering, washing and washing the obtained precipitate with absolute ethyl alcohol, and roasting in the air at 500 ℃ for 24 hours to obtain the catalyst carrier titanium cerium composite oxide hollow sphere;
(3) 219.5g of ammonium heptamolybdate and 75.8g of ferric nitrate nonahydrate are respectively dissolved in 800mL of water and 400mL of water to prepare solutions;
(4) sequentially adding an ammonium heptamolybdate solution and an iron nitrate solution into the prepared titanium-cerium composite oxide hollow sphere carrier powder, uniformly stirring, then adding 7.5g of barium sulfate, uniformly stirring, then adding 12g of diatomite, 18g of glass fiber, 5g of stearic acid, 10g of polyvinyl alcohol with the molecular weight of 300 ten thousand, 12g of carboxymethyl cellulose and 2g of polyacrylamide, and finally aging for 24 hours under a closed condition to obtain catalyst mud;
(5) extruding the catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and then carrying out roll coating, pleating, shearing and drying at 120 ℃ for 5min to obtain a flat catalyst matrix;
(6) the prepared flat-plate catalyst is immersed in 2mol/L ammonium metavanadate solution at 40 ℃ for 30min, then dried at 120 ℃ for 5min, and roasted at 450 ℃ for 12h to obtain the flat-plate wide-temperature sulfur-resistant SCR denitration catalyst.
The prepared flat-plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following components in percentage by weight: 2 percent of vanadium pentoxide, 12 percent of molybdenum trioxide, 1 percent of ferric oxide, 0.5 percent of barium sulfate, 2 percent of silicon dioxide and 82.5 percent of titanium cerium composite oxide hollow spheres with the molar ratio of Ti to Ce being 0.5; the diameter of the hollow sphere of the titanium cerium composite oxide is 6 mu m, and the thickness of the catalyst is 0.45 mm.
Example 2
The preparation process of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following steps:
(1) under the condition of stirring, adding 5.84L of 1mol/L cerium nitrate solution into 5L of 2mol/L glucose solution, and reacting for 24 hours under the hydrothermal condition of 200 ℃; filtering, washing and washing the product with absolute ethyl alcohol, drying at 90 ℃ for 12h, and roasting the precipitate at 600 ℃ for 2h in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
(2) dispersing the mixture in 100L of absolute ethyl alcohol, and then adding 376mL of 28wt% ammonia water; after stirring uniformly, slowly adding 994g of tetraethyl titanate dropwise, and stirring at the constant temperature of 50 ℃ for 24 hours; filtering, washing and washing the obtained precipitate with absolute ethyl alcohol, and roasting in the air at 600 ℃ for 12 hours to obtain the titanium-cerium composite oxide hollow sphere carrier;
(3) respectively dissolving 119g of ammonium heptamolybdate and 151.5g of ferric nitrate nonahydrate in 600mL of water and 600mL of water to prepare solutions;
(4) sequentially adding an ammonium heptamolybdate solution and an iron nitrate solution into the prepared titanium-cerium composite oxide hollow sphere carrier powder, uniformly stirring, then adding 30g of barium sulfate, uniformly stirring, then adding 30g of diatomite, 30g of glass fiber, 8g of stearic acid, 6g of polyvinyl alcohol with the molecular weight of 600 ten thousand, 20g of carboxymethyl cellulose and 5g of polyacrylamide, and finally aging for 48 hours under a closed condition to obtain a catalyst mud;
(5) extruding the catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and then carrying out roll coating, pleating, shearing and drying at 160 ℃ for 1min to obtain a flat catalyst matrix;
(6) the prepared flat-plate catalyst is immersed in 3mol/L ammonium metavanadate solution at 60 ℃ for 15min, and then dried at 160 ℃ for 1min and roasted at 550 ℃ for 4h to prepare the flat-plate wide-temperature sulfur-resistant SCR denitration catalyst.
The prepared flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following components in percentage by weight: 3 percent of vanadium pentoxide, 6.5 percent of molybdenum trioxide, 2 percent of ferric oxide, 2 percent of barium sulfate, 4 percent of silicon dioxide and 82.5 percent of titanium cerium composite oxide hollow spheres with the molar ratio of Ti to Ce being 0.5; the diameter of the hollow sphere of the titanium cerium composite oxide is 8 mu m, and the thickness of the catalyst is 0.50 mm.
Example 3
The preparation process of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following steps:
(1) under the condition of stirring, adding 1.21L of 4mol/L cerium nitrate solution into 2L of 5mol/L glucose solution, and reacting for 30 hours under the hydrothermal condition of 180 ℃; filtering, washing and washing the product with absolute ethyl alcohol, drying at 80 ℃ for 15h, and roasting the precipitate at 550 ℃ for 4h in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
(2) dispersing the mixture in 100L of absolute ethyl alcohol, and then adding 350mL of 27 wt% ammonia water; after stirring uniformly, 1641g of tetraethyl titanate is slowly dropped, and stirring is carried out for 32 hours at the constant temperature of 40 ℃; filtering, washing and washing the obtained precipitate with absolute ethyl alcohol, and roasting in the air at 600 ℃ for 12 hours to obtain the titanium-cerium composite oxide hollow sphere carrier;
(3) dissolving 146g of ammonium heptamolybdate and 75g of ferric nitrate nonahydrate in 800mL of water and 400mL of water respectively to prepare solutions;
(4) sequentially adding an ammonium heptamolybdate solution and an iron nitrate solution into the prepared titanium-cerium composite oxide hollow sphere carrier powder, uniformly stirring, then adding 15g of barium sulfate, uniformly stirring, then adding 20g of diatomite, 40g of glass fiber, 16g of stearic acid, 3g of polyvinyl alcohol with the molecular weight of 500 ten thousand, 25g of carboxymethyl cellulose and 2g of polyacrylamide, and finally aging for 48 hours under a closed condition to obtain a catalyst mud;
(5) extruding the catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and then carrying out roll coating, pleating, shearing and drying at 140 ℃ for 3min to obtain a flat catalyst matrix;
(6) the prepared flat-plate catalyst is immersed in 5mol/L ammonium metavanadate solution at 50 ℃ for 20min, and then dried at 130 ℃ for 2min and roasted at 500 ℃ for 6h to obtain the flat-plate wide-temperature sulfur-resistant SCR denitration catalyst.
The prepared flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following components in percentage by weight: 5% of vanadium pentoxide, 8% of molybdenum trioxide, 1% of ferric oxide, 1% of barium sulfate, 4% of silicon dioxide and 81% of titanium-cerium composite oxide hollow spheres with the molar ratio of Ti to Ce being 1; the diameter of the hollow ball of the titanium cerium composite oxide is 10 mu m, and the thickness of the catalyst is 0.55 mm.
Example 4
The preparation process of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following steps:
(1) under the condition of stirring, 2.4L of 2mol/L cerium nitrate solution is added into 3L of 4mol/L glucose solution, and the mixture reacts for 30 hours under the hydrothermal condition of 180 ℃; filtering, washing and washing the product with absolute ethyl alcohol, drying at 80 ℃ for 20h, and roasting the precipitate at 550 ℃ for 6h in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
(2) dispersing the mixture in 100L of absolute ethyl alcohol, and then adding 350mL of 27 wt% ammonia water; after stirring uniformly, 1641g of tetraethyl titanate is slowly dropped, and stirring is carried out for 30h at the constant temperature of 40 ℃; filtering, washing and washing the obtained precipitate with absolute ethyl alcohol, and roasting in the air at 600 ℃ for 12 hours to obtain the titanium-cerium composite oxide hollow sphere carrier;
(3) 164.6g of ammonium heptamolybdate and 151.5g of ferric nitrate nonahydrate are respectively dissolved in 700mL of water and 500mL of water to prepare solutions;
(4) sequentially adding an ammonium heptamolybdate solution and an iron nitrate solution into the prepared titanium-cerium composite oxide hollow sphere carrier powder, uniformly stirring, then adding 30g of barium sulfate, uniformly stirring, then adding 15g of diatomite, 30g of glass fiber, 12g of stearic acid, 4g of polyvinyl alcohol with the molecular weight of 500 ten thousand, 30g of carboxymethyl cellulose and 5g of polyacrylamide, and finally aging for 36 hours under a closed condition to obtain a catalyst mud;
(5) extruding the catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and performing roll coating, pleating, shearing and drying at 150 ℃ for 2min to obtain a flat catalyst matrix;
(6) the prepared flat-plate catalyst is immersed in 3mol/L ammonium metavanadate solution at 50 ℃ for 25min, and then dried at 140 ℃ for 2min and roasted at 500 ℃ for 8h to obtain the flat-plate wide-temperature sulfur-resistant SCR denitration catalyst.
The prepared flat plate type wide-temperature sulfur-resistant SCR denitration catalyst comprises the following components in percentage by weight: 3% of vanadium pentoxide, 9% of molybdenum trioxide, 2% of ferric oxide, 2% of barium sulfate, 3% of silicon dioxide and 81% of titanium-cerium composite oxide hollow spheres with the molar ratio of Ti to Ce being 1; the diameter of the hollow ball of the titanium cerium composite oxide is 7.5 mu m, and the thickness of the catalyst is 0.50 mm.
The active components of a fresh flat plate type medium-temperature SCR denitration catalyst obtained from a certain coal-fired power plant are tested, and the catalyst contains 1.2% of vanadium pentoxide, 5.6% of molybdenum trioxide, 89.1% of titanium dioxide, 1.8% of aluminum oxide and 2.3% of silicon dioxide. The catalyst was used as a comparative catalyst, and the performance of the catalyst was tested together with the catalysts of examples 1 to 4.
The denitration performance of the catalyst in the embodiment is evaluated by adopting simulated flue gas, and under the typical flue gas working condition: NO is 900mg/m3，SO2Is 5000mg/m3，O2Is 5% (v/v), H2O is 10% (v/v), the ammonia-nitrogen ratio is 1:1, N2The space velocity is 3000h for balancing gas-1And testing after the sample is stabilized in the smoke for 48 hours, wherein the test results are as follows:
TABLE 1 denitration efficiency (unit:%) of examples 1 to 4 and comparative catalysts at different temperatures
TABLE 2 SO at different temperatures for examples 1-4 and comparative catalysts2/SO3Conversion rate
As can be seen from the test results shown in the above table, the catalysts of examples 1 to 4 have much higher denitration activity than the conventional catalyst in the temperature range of 150 to 450 ℃ and much higher SO activity than the comparative catalyst2/SO3The conversion is much lower than that of the conventional catalyst. In conclusion, compared with the conventional catalyst, the catalyst provided by the invention has better wide-temperature activity and sulfur poisoning resistance. Therefore, the catalyst can solve the problems of low activity and sulfur poisoning of the catalyst in low-temperature flue gas and SO in medium-temperature flue gas2The problem of high oxidation rate, and is particularly suitable for the denitration of the sulfur-containing flue gas at wide temperature.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the specific embodiments of the present invention, and any modifications and equivalents that do not depart from the spirit and scope of the present invention should be construed as falling within the scope of the present invention.
Claims (10)
1. The flat plate type wide-temperature sulfur-resistant SCR denitration catalyst is characterized by comprising 2-5 wt% of vanadium pentoxide, 1-3 wt% of ferric oxide, 5-12 wt% of molybdenum trioxide, 0.5-2 wt% of barium sulfate, 1-4 wt% of silicon dioxide and 74-90.5 wt% of titanium-cerium composite oxide hollow spheres.
2. The SCR denitration catalyst of claim 1, wherein the titanium-cerium composite oxide hollow spheres have a diameter of 6 to 10 μm.
3. The SCR denitration catalyst of claim 1, wherein a molar ratio of titanium dioxide to cerium dioxide in the hollow titanium-cerium composite oxide spheres is 0.5 to 1.
4. The SCR denitration catalyst of claim 1, having a thickness of 0.45 to 0.55 mm.
5. The preparation method of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst as recited in any one of claims 1 to 4, comprising the steps of:
step 1: catalyst support preparation comprising:
step 1.1: adding a cerium nitrate solution into a glucose solution under the condition of stirring, reacting for 24-48 h under the hydrothermal condition of 150-200 ℃, drying the product for 12-24 h at 60-90 ℃ after filtering, washing and absolute ethyl alcohol washing, and roasting the obtained precipitate for 2-6 h at 500-600 ℃ in a nitrogen atmosphere to obtain a mixture of cerium oxide and carbon;
step 1.2: dispersing the mixture of cerium oxide and carbon prepared in the step 1.1 in absolute ethyl alcohol, then adding ammonia water, stirring uniformly, slowly dropwise adding tetraethyl titanate, stirring at a constant temperature of 30-50 ℃ for 24-48 hours, filtering, washing the obtained precipitate with water and absolute ethyl alcohol, and roasting at a temperature of 500-600 ℃ in air for 12-24 hours to obtain a titanium-cerium composite oxide hollow sphere serving as a catalyst carrier;
step 2: catalyst mud preparation, comprising:
step 2.1: respectively preparing ammonium heptamolybdate and ferric nitrate solution;
step 2.2: sequentially adding the ammonium heptamolybdate solution and the ferric nitrate solution into the titanium-cerium composite oxide hollow spheres prepared in the step 1.2, uniformly stirring, adding barium sulfate, uniformly stirring, adding diatomite, glass fiber, stearic acid, polyvinyl alcohol, carboxymethyl cellulose and polyacrylamide, and aging for 24-48 hours under a closed condition to obtain catalyst mud;
and step 3: the flat-plate catalyst forming method comprises the following steps:
step 3.1: extruding the catalyst mud material prepared in the step 2.2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, and then performing roll coating, pleating, shearing and drying to obtain a flat catalyst blank;
step 3.2: and soaking the prepared catalyst blank in an ammonium metavanadate solution at the temperature of 40-60 ℃ for 15-30 min, and drying and roasting to obtain the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst.
6. The preparation method according to claim 5, wherein in the step 1, the concentration of the cerium nitrate solution is 1-4 mol/L, the concentration of the glucose solution is 2-6 mol/L, and the concentration of the ammonia water is 25-28 wt%.
7. The method according to claim 5, wherein in the step 2, the polyacrylamide is anionic and has a molecular weight of 300 to 600 ten thousand.
8. The method according to claim 5, wherein in the step 3, the concentration of the ammonium metavanadate solution is 2 to 5 mol/L.
9. The preparation method according to claim 5, wherein in the step 3, the drying temperature is 120 to 160 ℃, and the drying time is 1 to 5 min; the roasting temperature is 450-550 ℃, and the roasting time is 4-12 h.
10. The preparation method of claim 5, wherein the thickness of the flat plate type wide-temperature sulfur-resistant SCR denitration catalyst prepared in the step 3 is 0.45-0.55 mm.
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