CN115178254A - Non-toxic, high-activity and high-stability rare earth group NH 3 -SCR catalyst and preparation technology thereof - Google Patents
Non-toxic, high-activity and high-stability rare earth group NH 3 -SCR catalyst and preparation technology thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 150000002910 rare earth metals Chemical group 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 6
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 96
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003754 zirconium Chemical class 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 7
- 150000000703 Cerium Chemical class 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
- -1 inorganic acid saltA transition metal Chemical class 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract 2
- 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 31
- 238000010438 heat treatment Methods 0.000 claims description 26
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 22
- 229910052684 Cerium Inorganic materials 0.000 claims description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 19
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 1
- 239000005751 Copper oxide Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 2
- 241001275899 Salta Species 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 53
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DLCOPLYGCSRNAY-UHFFFAOYSA-N molybdenum titanium vanadium Chemical compound [Ti][Mo][V] DLCOPLYGCSRNAY-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides a non-toxic, high-activity and high-stability rare earth-based ammonia-selective catalytic reduction (NH 3-SCR) catalyst and a preparation method thereof, belonging to rare earth-based NH 3 -the technical field of SCR catalytic materials. The invention aims to provide the rare earth-based NH which is environment-friendly and has better denitration performance 3 -SCR catalysts and processes for their preparation. The method comprises the following specific steps: reacting zirconium salt solution with inorganic acid or inorganic acid salt solution at a certain temperature, adjusting pH value to a certain value with alkaline solution, and adding a solution containing zirconium and/or inorganic acid saltA transition metal salt solution containing cerium salt, and alkaline solution is used for adjusting the pH value, and the rare earth group NH is obtained after the processes of heat preservation and stirring for a period of time at a certain temperature, suction filtration, drying and roasting 3 -an SCR catalyst. Rare earth group NH obtained by the invention 3 -SCR catalyst at airspeed greater than, equal to, 220000h ‑1 In the temperature range of 290-530 deg.c, the catalyst has NO converting rate over 90%.
Description
Technical Field
The present invention relates to the amino-selective catalytic reduction (NH) of rare earths 3 -SCR) catalytic material, in particular to a cerium-zirconium-based NH 3 -SCR denitration catalyst and preparation thereof.
Background
In recent years, the economy and technology have been rapidly developed, but the environmental pollution problem has come to the end, and the environmental problem has become the focus of attention. The atmospheric pollution is prominent in environmental pollutionNitrogen Oxide (NO) X ) Is one of the main pollutants of atmospheric pollution, and NO X Is also one of the important influencing factors causing acid rain, photochemical smog and greenhouse effect, so for NO X The treatment problem of (2) is a serious test. NH from the past 3 SCR technology is a globally recognized NO removal X Most efficient method, NH 3 The SCR denitration technique is NH 3 As a reducing agent, NOx is reduced to N under the action of a catalyst 2 。
At present, the denitration catalyst mainly comprises four main types, namely a noble metal catalyst, a molecular sieve catalyst, a bifunctional catalyst and a metal oxide catalyst, wherein a vanadium-based catalyst in the metal oxide catalyst has better activity in denitration catalysis, and is widely applied in industry. But poor N at high temperatures due to the narrow temperature window of the vanadium-based catalyst 2 The selectivity, volatility and toxicity of vanadium have not been able to meet the increasingly stringent emission regulations, and therefore, novel highly active, non-toxic, highly stable non-vanadium-based NH was developed 3 SCR catalysts are of great interest. Such as Mn-based catalyst, fe-based catalyst and Ce-based catalyst, in which CeO 2 Because of large storage capacity, excellent oxygen storage capacity and oxidation-reduction property, the catalyst is widely applied to the field of environmental catalysis. But pure CeO 2 NH of (2) 3 The SCR activity is very low, so that other metal and mineral acid solutions are usually introduced to increase the purity of CeO 2 NH of (2) 3 -SCR activity. Yi et al (Yi T, zhang Y, li J, et al 3 P-O 4 on ceria catalyst for selective catalytic reduction of NO by NH 3 [J]Chinese Journal of Catalysis,2016, 37 (2): 300-307.) found to be phosphorylated CeO 2 Catalyst to non-phosphorylated CeO 2 The catalyst has better NH 3 SCR activity, the phosphoric acid being believed to increase its acid strength and thus promote its NH 3 -SCR activity. Han et al (Han Z, li X, wang X, et al. Insight into the improving effect of a support preceding document with a support acid on a selective catalytic reduction performance of CeO 2 /ZrO 2 catalysts[J]Journal of Colloid and Interface Scienee,2022, 608: 2718-2729.) ZrO is treated with sulfuric acid 2 Preparation of CeO from Carrier 2 /ZrO 2 The catalyst has good NH 3 SCR activity, han et al selected several common mineral acids (HCl, HNO) in early work 3 ，H 3 PO 4 ，H 2 SO 4 ) To process ZrO 2 Support, results show use of H 2 SO 4 Treated CeO 2 /ZrO 2 The catalyst has the best NH 3 -SCR activity. In a patent (congratulatory et al, application publication No. CN 103638939A), a catalyst containing cerium sulfate as an active component was disclosed, and it was found that a certain catalytic activity was also exhibited as a soluble sulfate, but the activity was not high. In the patent (Yulin et al, application publication No. CN 110548503A) in order to improve the catalytic activity of the cerium-based catalyst, manganese oxide and vanadium oxide are introduced as active components, and although the low-temperature catalytic activity of the catalyst is improved and the temperature window is widened, the volatility and toxicity of vanadium cannot meet the requirements of increasingly strict emission regulations, so that the application in actual denitration is limited. Although a lot of researches are made on the aspect of rare earth-based denitration catalysts, the existing rare earth-based denitration catalysts either do not completely get rid of the use of vanadium metal, or have low activity and poor stability, and cannot meet the requirements of industrial use, so that the application of the existing rare earth-based denitration catalysts in industrial denitration is less. The invention provides a non-toxic, high-activity and high-stability rare earth-based denitration catalyst and a preparation technology thereof, and the catalyst has a good application prospect.
The invention provides an environment-friendly rare earth-based catalyst with good denitration performance and a preparation method thereof, and the catalyst is prepared by reacting NH 3 In the SCR reaction, when the airspeed is greater than or equal to 220000h -1 Then the NO conversion rate in the temperature range of 290-530 ℃ reaches more than 90 percent, and the specific surface area is not less than 131m 2 G, pore volume of not less than 0.34cm 3 The pore diameter is in the range of 3-20 nm.
Disclosure of Invention
The invention aims to provide an environment-friendly methodType and rare earth base NH with better denitration performance 3 -SCR catalyst and process for its preparation, NH 3 The SCR reaction still has better catalytic activity and heat resistance. The invention has reasonable design and is simple and easy to operate.
The invention relates to a composite comprising a mixture of cerium, zirconium and a transition metal element other than cerium.
The rare earth group NH of the invention 3 -the preparation method of the SCR catalyst comprises the following steps:
(1) Preparing a salt solution containing cerium, zirconium and a transition metal element other than cerium, wherein the cerium oxide concentration is 5.0wt% to 60.0wt%, the zirconium oxide concentration is 5.0wt% to 90.0wt%, the transition metal element oxide concentration other than cerium is 1wt% to 20wt%, and the inorganic acid radical concentration is 0.5wt% to 10.0wt%;
(2) Mixing the salt solution of zirconium prepared in the step (1) and inorganic acid in quantitative deionized water;
(3) Heating the mixed solution obtained in the step (2) to a temperature higher than 40 ℃ under a stirring state, stabilizing for a period of time, and adjusting the pH value of the mixed solution by using an alkaline solution to enable the pH value of the mixed solution to be higher than 5.0;
(4) Adding a cerium salt solution and a transition metal salt solution except cerium into the solution obtained in the step (3), stirring while adding, adjusting the pH to be neutral or alkaline by using an alkali solution after stirring for a period of time, and slowly dropwise adding while stirring;
(5) Keeping the temperature of the solution prepared in the step (4), stirring for a certain time, and filtering to obtain rare earth base NH 3 -SCR catalyst precursor:
(6) And (5) drying and roasting the precursor prepared in the step (5).
The cerium salt solution in the step (1) may be one or a mixture of several soluble cerium salts such as cerium nitrate, cerium oxynitrate, cerium chloride, cerium sulfate and the like, and the zirconium salt solution may be one or a mixture of several soluble zirconium salts such as zirconium nitrate, zirconium oxychloride, zirconium nitrate, zirconium sulfate, zirconium phosphate oxyphosphate and the like, wherein the salt solution contains an oxide with a concentration of 0.1wt% -50wt%.
In the step (2), the mass ratio of the zirconium salt solution (calculated by the weight of the oxide) to the inorganic acid (calculated by the concentration of 100%) is 1: 0.2-1, and the inorganic acid solution is one or a mixture of two of sulfuric acid and phosphoric acid.
In the step (3), the alkaline solution is one or more of ammonia water, hydroxides of alkali metals or alkaline earth metals and anions capable of forming precipitates with zirconium ions, cerium ions and other doped transition metal ions, such as carbonate or bicarbonate; the pH value range adjustment can be carried out in stages, for example, the pH value is firstly adjusted to 2-3, and is adjusted to be more than 5 after the reaction is carried out for a period of time.
The salt solution of cerium and the transition metal element other than cerium in the above step (4) may be added at once, or may be added stepwise or in portions, and the pH is in the range of 7 to 14, preferably 8 to 9.
The temperature range of the heat preservation in the step (5) is 50-100 ℃, and preferably 50-70 ℃.
In the step (6), the roasting temperature is 400-600 ℃, the temperature is programmed to 400-600 ℃, the heating rate is preferably 2 ℃/min, and the roasting time is 0.5-12h, preferably 3-6h.
The invention has the advantages of easily obtained raw materials, simple preparation process, easily controlled experimental conditions and no harm to the environment, and is an environment-friendly rare earth base NH 3 SCR catalyst and has better denitration performance.
The invention provides rare earth group NH 3 The preparation method of the SCR denitration catalyst has scientific and reasonable design and is simple and feasible, and the NH prepared by the method 3 SCR catalyst, with better NH 3 SCR catalytic activity and thermal resistance, in the rare-earth radical NH 3 The SCR catalytic field has better application prospect.
Drawings
FIG. 1 is an XRD pattern of examples 1-5 and comparative example 1.
FIG. 2 is an isothermal adsorption and desorption curve of example 2.
Fig. 3 is a graph of the aperture distribution of example 2.
FIG. 4 shows NH of examples 1 to 5 and comparative example 1 3 -SCR denitration performance evaluation chart.
FIG. 5 shows NH of example 2, comparative example 1 and comparative example 2 3 SCR denitration Performance evaluation graph.
FIG. 6 shows NH of example 2 and comparative example 3 3 SCR denitration Performance evaluation graph.
FIG. 7 shows NH of example 2 and comparative example 4 3 -SCR denitration performance evaluation chart.
FIG. 8 shows NH of example 6 and comparative example 5 3 SCR denitration Performance evaluation graph.
FIG. 9 shows NH of example 2 and comparative example 2 3 -TPD curve.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Firstly, the weight ratio of cerium oxide and zirconium oxide is: 50wt% cerium oxide: 50wt% zirconia was prepared as a solution.
Solution preparation:
preparation of a zirconium oxychloride solution (70.44 g, containing 17.74wt% of zirconium oxide), 35.22g of zirconium oxychloride was dissolved in 35.22g of deionized water, and a zirconium nitrate solution (67.4 g, containing 18.54wt% of cerium oxide) was prepared, and 33.7g of cerium nitrate was dissolved in 33.7g of deionized water.
70.44g of zirconium oxychloride solution and 52.7g of sulfuric acid (8 wt%) are added into 416.6g of deionized water and stirred uniformly, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution with the ammonia water under the condition of 60 ℃ water bath to enable the pH value of the solution to be more than 5, and then continuing to keep the temperature of the water bath for 2 hours under the stirring state.
Adding 67.4g of cerium nitrate into the solution, adjusting the pH value of the solution to 8-9 by using ammonia water, and stirring for 1 hour under the condition of keeping the temperature of a water bath at 60 ℃.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ by adopting a programmed heating mode, heating at a rate of 2 ℃/min, and roasting for 6h to obtain rare earth group NH 3 -an SCR denitration catalyst.
Example 2
Firstly, the weight ratio of cerium oxide and zirconium oxide is: 50wt% cerium oxide: 50wt% zirconia was prepared as a solution.
Solution preparation:
preparation of a zirconium oxychloride solution (70.44 g, containing 17.74wt% of zirconium oxide), 35.22g of zirconium oxychloride was dissolved in 35.22g of deionized water, and a zirconium nitrate solution (67.4 g, containing 18.54wt% of cerium oxide) was prepared, and 33.7g of cerium nitrate was dissolved in 33.7g of deionized water.
70.44g of the zirconium oxychloride solution and 70.2g of sulfuric acid (8 wt%) are added into 416.6g of deionized water and stirred uniformly, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution with the ammonia water under the condition of 60 ℃ water bath to enable the pH value of the solution to be more than 5, and then continuing to keep the temperature of the water bath for 2 hours under the stirring state.
Adding 67.4g of cerium nitrate into the solution, adjusting the pH value of the solution to 8-9 by using ammonia water, and stirring for 1 hour under the condition of keeping the temperature of a water bath at 60 ℃.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ by adopting a programmed heating mode, heating at a rate of 2 ℃/min, and roasting for 6h to obtain rare earth group NH 3 -an SCR denitration catalyst.
Example 3
Firstly, according to the weight ratio of cerium oxide to zirconium oxide: 50wt% cerium oxide: 50wt% zirconia was prepared as a solution.
Solution preparation:
70.44g of a zirconium oxychloride solution (containing 17.74% by weight of zirconia) was prepared, 35.22g of the zirconium oxychloride was dissolved in 35.22g of deionized water, 67.4g of a zirconium nitrate solution (containing 18.54% by weight of ceria) was prepared, and 33.7g of the cerium nitrate was dissolved in 33.7g of deionized water.
70.44g of zirconium oxychloride solution and 78.86g of sulfuric acid (8 wt%) are added into 416.6g of deionized water and stirred uniformly, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution with the ammonia water under the condition of 60 ℃ water bath to enable the pH value of the solution to be more than 5, and then keeping the water bath heat preservation for 2 hours under the stirring state.
Adding 67.4g of cerous nitrate solution into the solution, adjusting the pH value of the solution to 8-9 by using ammonia water, and stirring the solution for 1h at the water bath temperature of 60 ℃ with heat preservation.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ in a temperature programming manner at a heating rate of 2 ℃/min, and roasting for 6h to obtain rare earth base NH 3 -an SCR denitration catalyst.
Example 4
Firstly, the weight ratio of cerium oxide and zirconium oxide is: 50wt% cerium oxide: 50wt% zirconia was prepared as a solution.
Solution preparation:
preparation of a zirconium oxychloride solution (70.44 g, containing 17.74wt% of zirconium oxide), 35.22g of zirconium oxychloride was dissolved in 35.22g of deionized water, and a zirconium nitrate solution (67.4 g, containing 18.54wt% of cerium oxide) was prepared, and 33.7g of cerium nitrate was dissolved in 33.7g of deionized water.
70.44g of zirconium oxychloride solution and 87.51g of sulfuric acid (8 wt%) are added into 416.6g of deionized water and stirred uniformly, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution with the ammonia water under the condition of 60 ℃ water bath to enable the pH value of the solution to be more than 5, and then continuing to keep the temperature of the water bath for 2 hours under the stirring state.
Adding 67.4g of cerous nitrate solution into the solution, adjusting the pH value of the solution to 8-9 by using ammonia water, and stirring the solution for 1h at the water bath temperature of 60 ℃ with heat preservation.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ by adopting a programmed heating mode, heating at a rate of 2 ℃/min, and roasting for 6h to obtain rare earth group NH 3 -an SCR denitration catalyst.
Example 5
Firstly, the weight ratio of cerium oxide and zirconium oxide is: 50wt% cerium oxide: 50wt% zirconia was prepared as a solution.
Solution preparation:
preparation of a zirconium oxychloride solution (70.44 g, containing 17.74wt% of zirconium oxide), and dissolving 35.22g of zirconium oxychloride in 35.22g of deionized water, preparation of a zirconium nitrate solution (67.4 g, containing 18.54wt% of cerium oxide), and dissolving 33.7g of cerium nitrate in 33.7g of deionized water.
70.44g of the zirconium oxychloride solution and 87.51g of sulfuric acid (8 wt%) are added into 416.6g of deionized water and stirred uniformly, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution with the ammonia water under the condition of 60 ℃ water bath to enable the pH value of the solution to be more than 5, and then continuing to keep the temperature of the water bath for 2 hours under the stirring state.
Adding 67.4g of cerous nitrate solution into the solution, adjusting the pH of the solution to 8-9 by using ammonia water, and stirring for 1h at the water bath temperature of 60 ℃.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ by adopting a programmed heating mode, heating at a rate of 2 ℃/min, and roasting for 6h to obtain rare earth group NH 3 -an SCR denitration catalyst.
Example 6
The denitration catalyst obtained in example 2 was charged in a tube furnace, and N was added to the furnace so that the water vapor content was 10vol% 2 Roasting for 6h at 600 ℃ in the atmosphere to obtain the rare earth-based denitration catalyst after hydrothermal aging treatment.
Example 7
Firstly, according to the weight ratio of cerium oxide, zirconium oxide and manganese oxide: 45wt% cerium oxide: 45wt% zirconia: preparing a solution of 10wt% manganese oxide.
Solution preparation:
preparation of a zirconium oxychloride solution (70.44 g, containing 17.74 wt.% of zirconium oxide), and dissolving zirconium oxychloride (35.22 g) in deionized water (35.22 g), preparation of cerium nitrate (67.4 g, containing 18.54 wt.% of cerium oxide), and cerium nitrate (33.7 g) in deionized water (33.7 g), and manganese nitrate solution (11.69 g, containing 21.38 wt.% of manganese oxide), and manganese nitrate (5.845 g) in deionized water (5.845 g).
70.44g of the zirconium oxychloride solution and 115.83g of sulfuric acid (8 wt%) are added into 458.3g of deionized water and stirred uniformly, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution with the ammonia water under the condition of 60 ℃ water bath to enable the pH value of the solution to be more than 5, and then continuing to keep the temperature of the water bath for 2 hours under the stirring state.
67.4g of cerous nitrate solution and 11.69g of manganese nitrate solution are added into the solution, the pH value of the solution is adjusted to 8-9 by ammonia water, and the solution is kept warm and stirred for 1h at the water bath temperature of 60 ℃.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ in a temperature programming manner at a heating rate of 2 ℃/min, and roasting for 6h to obtain rare earth base NH 3 -an SCR denitration catalyst.
Comparative example 1
Firstly, the weight ratio of cerium oxide and zirconium oxide is: 50wt% cerium oxide: 50wt% zirconia was prepared as a solution.
Solution preparation:
70.44g of zirconium oxychloride solution (containing 17.74wt% of zirconium oxide) was prepared, 35.22g of zirconium oxychloride was dissolved in 35.22g of deionized water, 67.4g of cerium nitrate (containing 18.54wt% of cerium oxide) was prepared, and 33.7g of cerium nitrate was dissolved in 33.7g of deionized water.
70.44g of zirconium oxychloride solution and 67.4g of cerous nitrate solution are taken and added into 416.6g of deionized water, and the solution is heated to 60 ℃ in a water bath under the stirring state and is stabilized for 3 hours.
Preparing 6.375wt% ammonia water, adjusting the pH value of the solution to 8-9 with the ammonia water under the condition of 60 ℃ water bath, and then keeping the water bath heat preservation for 2h under the stirring state.
Filtering the solution, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ by adopting a programmed heating mode, heating at a rate of 2 ℃/min, and roasting for 6h to obtain rare earth group NH 3 -an SCR denitration catalyst.
Comparative example 2
4g of the dried sample of comparative example 1 were taken and ground to a powder, which was added to 20ml of sulfuric acid (0.5M) solution and soaked for 3 hours.
Washing the solution with deionized water for several times, filtering, drying in a 100 ℃ oven for 2-4h, transferring to a muffle furnace, heating to 600 ℃ by a programmed heating method at a heating rate of 2 ℃/min, and roasting for 6h to obtain dilute NH 3 -an SCR denitration catalyst.
Comparative example 3
Commercial vanadium molybdenum titanium NH 3 -an SCR denitration catalyst.
Comparative example 4
Commercial vanadium tungsten titanium NH 3 -SCR denitration catalyst
Comparative example 5
The above commercial vanadium tungsten titanium denitration catalyst of comparative example 4 was placed in a tube furnace in N having a water vapor content of 10vol% 2 Roasting for 6 hours at 600 ℃ in the atmosphere to obtain vanadium-tungsten-titanium NH after hydrothermal aging treatment 3 -an SCR denitration catalyst.
NH 3 -SCR denitration catalyst performance testing:
separately subjecting the above samples to NH 3 SCR denitration Activity test with NH reaction gas 3 (500ppm)、NO(500ppm)、10Vol％O 2 、5Vol％CO 2 、5Vol％H 2 O，N 2 As an equilibrium, the reaction temperature is 100-550 ℃, GHSV =220000h -1 。
Specific denitration performance is shown in table 1.
As can be seen from Table 1, in NH 3 The denitration activity temperature window of the example in the SCR denitration performance test result is obviously higher than that of the comparative example, and particularly, the example 2 shows better NH 3 SCR denitration performance, high catalytic activity and wide denitration activity temperature window.
TABLE 1
The specific surface area, pore volume, and pore diameter of the catalysts of examples 1 to 4 and comparative examples 1 to 2 and the sulfur contents of examples 2, 5, and comparative example 1 are as follows in table 2.
In Table 2, the BET method was used to calculate the specific surface area, and the BJH method was used to determine the pore volume and pore diameter.
TABLE 2
| Examples of the invention | Specific surface area (m) 2 /g) | Pore volume (cm) 3 /g) | Aperture (nm) | Sulfur content (%) |
| Example 1 | 78.8076 | 0.0722 | 3.8858 | - |
| Example 2 | 131.7161 | 0.3402 | 11.3669 | 2.0524 |
| Example 3 | 67.0718 | 0.0652 | 3.8884 | - |
| Example 4 | 13.0823 | 0.0548 | 16.7555 | - |
| Example 5 | 16.3471 | 0.0981 | 24.0043 | 2.5365 |
| Comparative example 1 | 75.7095 | 0.0719 | 3.6539 | 2.9293 |
| Comparative example 2 | 67.1769 | 0.0714 | 4.2515 | - |
As can be seen from Table 2, the above examples can obtain a catalyst with a large specific surface area by adjusting the ratio of zirconium salt to sulfuric acid, wherein the fresh specific surface area of example 2 reaches 131m 2 The preparation method can improve the specific surface area of the catalyst by adjusting the acid amount, and further improve the NH of the catalyst 3 -SCR denitration activity.
The above description is only for the purpose of illustrating examples of the present invention and is not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that various modifications, adaptations, and alternatives falling within the spirit and principles of the invention are within the scope and spirit of the invention as set forth in the following claims.
Claims (14)
1. Non-toxic, high-activity and high-stability rare earth-based ammonia-selective catalytic reduction (NH) 3 -SCR) catalyst and process for its preparation, characterized in that: 5.0 to 60.0 weight percent of cerium oxide, 5.0 to 90.0 weight percent of zirconium oxide, 1 to 20 weight percent of transition metal element oxide except cerium, and 0.5 to 10.0 weight percent of inorganic acid radical; the compound has a molecular weight of not less than 131m after being calcined at 600 deg.C/6 hr 2 BET specific surface area/g, pore volume not less than 0.34cm 3 G, the pore diameter is between 3 and 20 nm; the total acid amount of the product is not less than 0.68mmol/g, wherein the central acid amount of weak acid is not less than 0.25mmol/g, and the central acid amount of medium acid is not less than 0.42mmol/g.
2. A rare earth based NH as claimed in claim 1 3 -an SCR catalyst, characterized in that: transition metal oxides other than cerium include, but are not limited to, the following: copper oxide, manganese oxide, molybdenum oxide, iron oxide, and the like.
3. A rare earth based NH as claimed in claim 1 3 -an SCR catalyst characterized in that: the inorganic acid solution is one or a mixture of two of sulfuric acid and phosphoric acid.
4. According to claim 1, the rare earth group NH concerned 3 -the preparation of the SCR catalyst comprises the following steps:
(1) Preparing a salt solution of zirconium, cerium and a transition metal element other than cerium;
(2) Mixing a zirconium salt solution with an inorganic acid solution, heating to a temperature higher than 40 ℃ under a stirring state, stabilizing for a period of time, and adjusting the pH value of the solution by using an alkaline solution to enable the pH value of the solution to be higher than 5;
(3) Adding a salt solution of cerium and a salt solution of a transition metal element other than cerium to the above solution, stirring for a certain period of time, and then treating the mixture with an alkaline solutionAdjusting the pH value of the solution to be neutral or alkaline, keeping the temperature for a period of time under the stirring state, and filtering to obtain rare earth group NH 3 -an SCR catalyst precursor;
(4) And drying and roasting the precursor.
5. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (1), the cerium salt solution may be one or a mixture of several of soluble cerium salts such as cerium nitrate, cerium oxynitrate, cerium chloride, cerium sulfate and the like, and the zirconium salt solution may be one or a mixture of several of soluble zirconium salts such as zirconium nitrate, zirconium oxychloride, zirconium nitrate, zirconium sulfate, zirconium phosphate oxyphosphate and the like, wherein the salt solution contains an oxide with a concentration of 0.1wt% -50wt%.
6. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (2), the mass ratio of the zirconium salt solution (calculated by the weight of the oxide) to the inorganic acid (calculated by the concentration of 100%) is 1: 0.2-1.
7. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (2), the alkaline solution is one or more of ammonia water, hydroxides of alkali metals or alkaline earth metals and anions capable of forming precipitates with zirconium ions, cerium ions and other doped transition metal ions, such as carbonate or bicarbonate.
8. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (2), the pH value range adjustment can be performed in a stepwise manner, for example, the pH value is adjusted to 2-3, and the pH value is adjusted to more than 5 after the reaction is performed for a period of time.
9. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in step (3), the pH valueThe range is 7-14, preferably 8-9.
10. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (3), the salt solution of zirconium, cerium and a transition metal element other than cerium may be added at a time, or may be added stepwise or in portions.
11. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (3), the temperature range of the heat preservation is 50-100 ℃, and preferably 50-70 ℃.
12. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (3), the stirring time is 1-24h, preferably 1-5h.
13. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: in the step (4), the roasting temperature is 400-600 ℃, the temperature is programmed to 400-600 ℃, the heating rate is preferably 2 ℃/min, and the roasting time is 0.5-12h, preferably 3-6h.
14. A rare earth based NH according to claim 4 3 -a process for the preparation of an SCR catalyst, characterized in that: said rare earth based catalyst is in NH 3 In the SCR reaction, when the idle speed is greater than or equal to 220000h -1 Then, the NO conversion rate in the temperature range of 290-530 ℃ reaches more than 90 percent.
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