CN115672304B - Europium-based catalyst, preparation method and application thereof in preparing hydrocyanic acid by methanol ammoxidation - Google Patents
Europium-based catalyst, preparation method and application thereof in preparing hydrocyanic acid by methanol ammoxidation Download PDFInfo
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- CN115672304B CN115672304B CN202211422818.3A CN202211422818A CN115672304B CN 115672304 B CN115672304 B CN 115672304B CN 202211422818 A CN202211422818 A CN 202211422818A CN 115672304 B CN115672304 B CN 115672304B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 66
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- -1 salt compounds Chemical class 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 7
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 6
- 229930182817 methionine Natural products 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- DPYXWFUVSMSNNV-UHFFFAOYSA-L europium(2+);diiodide Chemical compound [I-].[I-].[Eu+2] DPYXWFUVSMSNNV-UHFFFAOYSA-L 0.000 claims description 3
- TWNOVENTEPVGEJ-UHFFFAOYSA-K europium(3+);trifluoromethanesulfonate Chemical compound [Eu+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F TWNOVENTEPVGEJ-UHFFFAOYSA-K 0.000 claims description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 abstract description 8
- 238000011156 evaluation Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000000918 Europium Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ABKDZANKXKCXKG-UHFFFAOYSA-B P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] Chemical compound P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] ABKDZANKXKCXKG-UHFFFAOYSA-B 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
The invention discloses a europium-based catalyst, a preparation method and application thereof in preparing hydrogen cyanide by methanol ammoxidation, wherein the europium-based catalyst is Eu a X b /(C@SiO 2 ) Wherein europium is an active component, X is a co-active component, and is selected from one or more of lanthanum, tungsten, molybdenum, antimony and rhodium, and carbon-based silicon dioxide is used as a carrier; preparing corresponding salt solutions by mixing salt compounds containing active components and auxiliary active components; preparing a carbon-based silicon dioxide carrier by adopting an in-situ synthesis method; and (3) dipping the salt solution on the carrier in a dipping mode, and roasting to obtain the europium-based catalyst. The europium-based catalyst is used for the reaction of preparing hydrogen cyanide by methanol ammoxidation, the yield of hydrogen cyanide is more than 98%, the yield of byproduct formaldehyde is less than 0.02%, and the ammonia conversion rate is more than 99.99%.
Description
Technical Field
The invention relates to the technical field of hydrocyanic acid preparation, in particular to a preparation method of a europium-based catalyst and application of the europium-based catalyst in methanol ammoxidation to prepare hydrocyanic acid.
Background
Hydrocyanic acid is an important chemical raw material, is mainly used for producing adiponitrile, MMA, methionine and other chemical products, and has wide application. However, hydrocyanic acid is a highly toxic chemical and cannot be transported. The requirements related to hydrocyanic acid are thus self-sufficient. At present, the hydrocyanic acid sources in society mainly comprise acrylonitrile byproducts, a methane method and a methanol method. Wherein, with the continuous development of acrylonitrile catalysts, the hydrocyanic acid yield of acrylonitrile byproducts is lower and lower. The methane method requires expensive noble metal catalyst, the reaction temperature exceeds 1000 ℃, and the yield is low, so that the economy is poor. The methanol method is an economic hydrocyanic acid production method, which uses methanol, ammonia gas and air as raw materials to produce hydrocyanic acid under the action of a catalyst, and the process has the advantages of mild production conditions, high hydrocyanic acid yield and relatively high cost.
Patent US4425260 proposes an Fe-Mo catalyst Fe a Mo b O c The patent adds a molybdenum salt solution to an iron salt solution to form a precipitate, and then adds a silica sol, which is expected to be detrimental to the dispersion of molybdenum and iron, with a hydrocyanic acid yield of about 86.4%. In patent US3911089 Mo is disclosed as an ammoxidation catalyst a Bi b Fe c X d Y e Z f O g X is one of Cr, mn, co, ni, zn, cd, sn, W and Pb, Y is one or more of transition elements, the catalyst composition is complex, and the HCN yield is 86%. Patent EP0322796 discloses a catalyst Mo which is commonly used in ammoxidation of one or more organic compounds of methanol, propylene and isobutylene e D f E g F h O y D is mainly selected from Mn, fe, ni, bi, zn, and the HCN yield is only 81%. None of the above patents mention the manner in which the catalyst is shaped and the reactivity of the shaped catalyst of full particle size.
The traditional catalyst for preparing hydrogen from methanol is mostly an iron-molybdenum catalyst, formaldehyde is inevitably generated by the catalyst, and meanwhile, the ammonia conversion rate is lower. The device for producing ten thousand tons of hydrocyanic acid annually has about eight thousand to ten thousand tons of ammonium sulfate byproducts. The byproduct ammonium sulfate needs to be absorbed by a large amount of sulfuric acid, and a large amount of energy is wasted during evaporation and crystallization, so that the economy is not high.
Disclosure of Invention
In order to solve the problems, the invention aims to improve a novel europium-based catalyst, which has the effects of high hydrocyanic acid yield and high ammonia conversion rate, can reduce 80-90% of ammonium sulfate, and has great positive significance on reducing hydrocyanic acid cost.
Another object of the present invention is to provide a method for preparing such europium-based catalyst
It is a further object of the present invention to provide the use of such europium-based catalyst in the ammoxidation of methanol to hydrogen cyanide.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
europium-based catalyst, which is Eu a X b /(C@SiO 2 ) Wherein europium is an active component, X is a co-active component, and carbon-based silicon dioxide is a carrier; wherein a and b are the percentages of the mass of the compound containing the corresponding element and the mass of the carrier, the proportion is the feeding ratio, wherein the value of a is 0.2-10, and the value of b is 0.5-5.
In a specific embodiment, the co-active component X is selected from one or more of lanthanum, tungsten, molybdenum, antimony, rhodium; preferably, when the auxiliary active component X is more than two, the elements are added in equal mass ratio.
In another aspect, the preparation method of the europium-based catalyst comprises the following steps:
(1) Salt compounds containing active components and auxiliary active components are mixed to prepare corresponding salt solutions;
(2) Preparing a carbon-based silicon dioxide carrier by adopting an in-situ synthesis method;
(3) And (3) dipping the salt solution prepared in the step (1) on the carbon-based silicon dioxide carrier prepared in the step (2) in a dipping mode, and roasting to obtain the europium-based catalyst.
In a specific embodiment, the salt compound of the active component is a europium salt selected from at least any one of europium chloride, europium nitrate, europium sulfate, europium iodide, and europium triflate.
In a specific embodiment, the salt compound of the co-active component is selected from any one of a sulfate, a nitrate, a chloride, an ammonium salt, and a phosphate.
In a specific embodiment, step (2) of preparing the carbon-based silica support comprises the steps of:
a) Adding a silicon source in a water bath environment at 20-80 ℃, preferably 30-60 ℃, stirring, and then adding a carbon source and a certain amount of alkali to enable the pH value to be 8.5-9.5;
b) Continuously stirring for 30-90min, transferring to a crystallization kettle with a polytetrafluoroethylene lining, and placing in a 160-200 ℃ oven for reaction for 2-10h;
c) And after the reaction is finished, roasting the mixture in a muffle furnace at 300-600 ℃ for 2-8 hours to obtain the carbon-based silicon dioxide carrier.
In a specific embodiment, the silicon source is selected from any one of ethyl orthosilicate, silica sol and water glass, and the carbon source is selected from any one of methionine, alanine, glucose, methyl formate and urea; the alkali is selected from any one of triethylamine, ammonia water and n-butylamine; preferably, the carbon source accounts for 60-90% of the silicon source by mass, and preferably 70-80%.
In a specific embodiment, the step (3) adopts an excessive impregnation mode to impregnate the salt solution on the carrier, and the catalyst is obtained by drying after impregnation and roasting at 300-600 ℃ for 2-8 h.
In yet another aspect, the europium-based catalyst or the europium-based catalyst prepared by the preparation method is applied to preparing hydrogen cyanide by ammoxidation of methanol.
In a specific embodiment, when the europium-based catalyst is applied to the reaction of preparing hydrogen cyanide by methanol ammoxidation, the yield of hydrocyanic acid is more than 98%, the yield of byproduct formaldehyde is less than 0.02%, and the conversion rate of ammonia gas is more than 99.99%.
Compared with the prior art, the invention has the following beneficial effects:
the invention develops a europium-based catalyst with a novel structure, which can strengthen the adsorption of ammonia gas, thereby greatly improving the utilization rate of the ammonia gas and reducing byproducts such as formaldehyde and the like.
When the europium-based catalyst is applied to the reaction of preparing hydrogen cyanide by methanol ammoxidation, the yield of hydrocyanic acid is more than 98%, the yield of byproduct formaldehyde is less than 0.02%, the conversion rate of ammonia is more than 99.99%, 80-90% of ammonium sulfate byproducts can be reduced, and the corresponding byproduct ammonium sulfate treatment cost is saved.
Detailed Description
So that the technical features and content of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
Preparation method of europium-based catalyst, which can be expressed as Eu a X b /(C@SiO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein europium is an active component, X is a co-active component, and is selected from one or more of lanthanum, tungsten, molybdenum, antimony and rhodium, and carbon-based silicon dioxide is used as a carrier; the preparation of the europium-based catalyst comprises the following steps:
(1) Salt compounds containing active components and auxiliary active components are mixed to prepare corresponding salt solutions;
(2) Preparing a carbon-based silicon dioxide carrier by adopting an in-situ synthesis method;
(3) And (3) dipping the salt solution prepared in the step (1) on the carbon-based silicon dioxide carrier prepared in the step (2) in a dipping mode, and roasting to obtain the europium-based catalyst.
In the present invention, the catalyst expression Eu a X b /(C@SiO 2 ) Wherein a and b are the mass percentages of the corresponding element compounds and the carrier mass, and the ratio is the feeding ratio. For example, a is the percentage of europium salt mass to the carrier mass, and b is the percentage of salt compound of the co-active component to the carrier mass. Wherein a has a value of 0.2-10, e.g. 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, b has a value of 0.5-5, e.g. 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5; preferably, a has a value of 0.5 to 4 and b has a value of 0.8 to 2.5.
In the invention, X is an auxiliary active component, and the component is one or more of lanthanum, tungsten, molybdenum, antimony and rhodium. If the number is plural, the elements are preferably added in equal proportions.
In the present invention, the europium salt used is any one of europium chloride, europium nitrate, europium sulfate, europium iodide and europium triflate. The auxiliary active component is selected from any one of sulfate, nitrate, phosphate, chloride and ammonium salt, such as lanthanum chloride, antimony chloride, tungsten nitrate, molybdenum sulfate and the like.
In the preparation of the carbon-based silica carrier, a silicon source is added in a water bath environment at 20-80 ℃, stirring is carried out, preferably at 30-60 ℃, then the carbon source and a certain amount of alkali are added, wherein the carbon source accounts for 60-90% of the mass of the silicon source, for example, but not limited to 65%, 70%, 75%, 80%, 85%, 90%, preferably 70-85%, and the pH value is 8.5-9.5, preferably 8.8-9.2, and stirring is continued for 30-90min, preferably 50-70min; after stirring, transferring the mixture to a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a baking oven at 160-200 ℃ for reaction for 2-10h, preferably 170-190 ℃ for reaction for 4-8h; after the reaction was completed, the mixture was burned in a muffle furnace at 540℃for 4 hours to obtain a carrier.
In the invention, the silicon source is any one of tetraethoxysilane, silica sol and water glass, and the carbon source is any one of methionine, alanine, glucose, methyl formate and urea. The required alkali is any one of triethylamine, ammonia water and n-butylamine.
In the invention, the europium-based catalyst is obtained by impregnating a salt solution on a carrier in an excessive impregnation mode, drying after the impregnation, and roasting for 2-8h at 300-600 ℃, for example, roasting for 4h at 550 ℃. Among them, volume and excess impregnation are common means for catalyst impregnation preparation. The equivalent volume is to prepare corresponding solution according to the water absorption rate of the carrier; excess impregnation is greater than this value, i.e. excess salt solution.
In the invention, when the prepared europium-based catalyst is applied to the reaction of preparing hydrogen cyanide by methanol ammoxidation, the yield of hydrocyanic acid is more than 98%, the yield of byproduct formaldehyde is less than 0.02%, and the conversion rate of ammonia is more than 99.99%.
Wherein, the reaction condition for the reaction of preparing the cyanic acid by methanol ammoxidation can be referred to the prior art, for example, the catalyst is evaluated by adopting a fixed bed device, the catalyst is filled with 8g, and the space velocity is 3000h -1 The reaction temperature was 360 ℃. Methanol, ammonia gas and air according to the proportion of 1:1.1:98% and 200 ℃ are mixed and preheated, then enter a reactor, and then are sampled and evaluated at the outlet of the reactor.
The invention is further illustrated, but not limited, by the following more specific examples.
The main raw material sources of the examples are as follows:
methanol, available from Shanghai Ala Biochemical technologies Co., ltd;
ammonia gas, purchased from Shanghai liquid air technologies, inc.;
europium nitrate, available from Shanghai Ala Biochemical technologies Co., ltd;
tungsten phosphate, ammonium molybdate, antimony nitrate were purchased from enokak reagent limited.
The methanol conversion rate and the hydroxyacetonitrile selectivity are calculated after analysis by using an Agilent 7820A gas chromatograph, and the test conditions comprise: adopting DB-5 chromatographic column and FID detector, the temperature of vaporization chamber is 260 deg.C, the temperature of detector is 260 deg.C, and carrier gas is high-purity N 2 The flow rate was 30ml/min.
Hydrocyanic acid was titrated by the method of reference HB 7486-87. The residual ammonia is titrated by adopting a hydrochloric acid method, and methyl orange is used as an indicator.
Example 1
80g of ethyl orthosilicate was poured into a beaker and placed in a 50℃water bath for stirring, then 52g of glucose was added and stirred. A certain amount of triethylamine is continuously added, the pH is adjusted to 8.8, and stirring is continuously carried out for 50min. Then the feed liquid is placed in a crystallization kettle, reacted for 4 hours at 170 ℃ in an oven, and baked for 4 hours at 540 ℃ after the completion of the reaction, thus obtaining the carrier.
0.5g of europium nitrate, 0.37g of tungsten phosphate and 15g of water were mixed to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 550 ℃ after drying to obtain the catalyst A.
The catalyst was evaluated using a fixed bed unit, the catalyst was packed in 8g, and the space velocity was 3000h -1 The reaction temperature was 360 ℃. Methanol, ammonia gas and air according to the proportion of 1:1.1:98% and 200 ℃ are mixed and preheated, then enter a reactor, and then are sampled and evaluated at the outlet of the reactor.
Example 2
80g of silica sol was poured into a beaker and placed in a water bath at 70℃with stirring, then 64g of methionine was added and stirred. A certain amount of n-butylamine is continuously added, the pH is regulated to 9.0, and stirring is continued for 70min. Then the feed liquid is placed in a crystallization kettle, reacted for 8 hours at 190 ℃ in an oven, and baked for 2 hours at 600 ℃ after the completion of the reaction, thus obtaining the carrier.
1g of europium sulfate, 0.29g of ammonium molybdate and 15g of water were mixed to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 580 ℃ after drying to obtain the catalyst B.
The evaluation was performed by the evaluation method of example 1.
Example 3
80g of water glass was poured into a beaker and placed in a 60℃water bath for stirring, then 60g of urea was added and stirred. A certain amount of n-butylamine is continuously added, the pH is regulated to 9.2, and stirring is continued for 70min. Then the feed liquid is placed in a crystallization kettle, reacted for 8 hours at 190 ℃ in a baking oven, and baked for 8 hours at 300 ℃ after the completion of the reaction, thus obtaining the carrier.
0.8g of europium sulfate, 0.24g of ammonium molybdate, 0.24g of lanthanum nitrate and 15g of water are taken and mixed to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 550 ℃ after drying to obtain the catalyst C.
The evaluation was performed by the evaluation method of example 1.
Example 4
80g of ethyl orthosilicate are poured into a beaker and placed in a water bath at 30℃for stirring, then 63g of methyl formate are added and stirred. A certain amount of triethylamine is continuously added, the pH is adjusted to 8.8, and stirring is continuously carried out for 45min. Then the feed liquid is placed in a crystallization kettle, reacts for 8 hours at 215 ℃ in a baking oven, and is baked for 4 hours at 540 ℃ after the completion of the reaction, so that the carrier is obtained.
0.02g of europium nitrate, 0.21g of antimony nitrate and 15g of water were mixed to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 550 ℃ after drying to obtain the catalyst D.
The evaluation was performed by the evaluation method of example 1.
Comparative example 1
The commercial iron-molybdenum catalyst for preparing hydrogen cyanide by ammoxidation of methanol was used for evaluation, and the catalyst was designated as E and was evaluated in the manner of evaluation in example 1. The iron-molybdenum catalyst was purchased from the company Botai chemical technology Co., ltd.
Comparative example 2
Pouring 80g of water glass into a beaker, placing the beaker in a water bath at 60 ℃ for stirring, continuously adding a certain amount of n-butylamine without adding a carbon source, adjusting the pH to 9.2, and continuously stirring for 70min. Then the feed liquid is placed in a crystallization kettle, reacted for 8 hours at 190 ℃ in a baking oven, and baked for 8 hours at 300 ℃ after the completion of the reaction, thus obtaining the carrier.
0.8g of europium sulfate, 0.24g of ammonium molybdate, 0.24g of lanthanum nitrate and 15g of water are taken and mixed to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 550 ℃ after drying to obtain the catalyst F.
The evaluation was performed by the evaluation method of example 1.
Comparative example 3
80g of water glass was poured into a beaker and placed in a 60℃water bath for stirring, then 60g of urea was added and stirred. A certain amount of n-butylamine is continuously added, the pH is regulated to 9.2, and stirring is continued for 70min. Then the feed liquid is placed in a crystallization kettle, reacted for 8 hours at 190 ℃ in a baking oven, and baked for 8 hours at 300 ℃ after the completion of the reaction, thus obtaining the carrier.
0.24g of ammonium molybdate, 0.24g of lanthanum nitrate and 15g of water were taken and mixed to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 550 ℃ after drying to obtain the catalyst G.
The evaluation was performed by the evaluation method of example 1.
Comparative example 4
80g of silica sol was poured into a beaker and placed in a water bath at 70℃with stirring, then 64g of methionine was added and stirred. A certain amount of n-butylamine is continuously added, the pH is regulated to 9.0, and stirring is continued for 70min. Then the feed liquid is placed in a crystallization kettle, reacted for 8 hours at 190 ℃ in an oven, and baked for 2 hours at 600 ℃ after the completion of the reaction, thus obtaining the carrier.
1g of europium sulfate was mixed with 15g of water to obtain a salt solution. Then 10g of the support was taken and the salt solution was impregnated onto the support. And (3) baking for 4 hours at 580 ℃ after drying to obtain the catalyst H.
The evaluation was carried out by the evaluation method of example 1, and the evaluation results are shown in the following table.
Catalyst evaluation results table
As shown in the table above, the catalyst ABCD can show good catalytic activity, the ammonia conversion rate is more than 99.99%, and the formaldehyde is less than 0.01%. Catalyst E is a commercially available conventional catalyst having activity lower than the catalysts of the present invention. Catalyst F illustrates that carbon in the support is beneficial to improving adsorption properties and is beneficial to the catalyst. Catalyst G illustrates that europium is beneficial for ammonia conversion and catalyst H illustrates that the co-active component is beneficial for reducing formaldehyde production.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (13)
1. A europium-based catalyst for preparing cyanic acid by methanol ammoxidation is characterized in that the europium-based catalyst is Eu a X b /C@SiO 2 Wherein europium is an active component, X is a co-active component, and carbon-based silicon dioxide is a carrier; wherein a and b are the percentages of the mass of the compound containing the corresponding element and the mass of the carrier, the proportion is the feeding ratio, wherein the value of a is 0.2-10, and the value of b is 0.5-5;
the auxiliary active component X is one or more selected from lanthanum, tungsten, molybdenum, antimony and rhodium.
2. The europium-based catalyst according to claim 1, wherein when the number of the co-active components X is two or more, the respective elements are charged in equal mass ratios.
3. The method for preparing the europium-based catalyst of claim 1 or 2, which comprises the steps of:
(1) Salt compounds containing active components and auxiliary active components are mixed to prepare corresponding salt solutions;
(2) Preparing a carbon-based silicon dioxide carrier by adopting an in-situ synthesis method;
(3) And (3) dipping the salt solution prepared in the step (1) on the carbon-based silicon dioxide carrier prepared in the step (2) in a dipping mode, and roasting to obtain the europium-based catalyst.
4. The method according to claim 3, wherein the salt compound of the active component is a europium salt selected from at least one of europium chloride, europium nitrate, europium sulfate, europium iodide and europium triflate.
5. The method according to claim 3, wherein the salt compound of the co-active ingredient is selected from any one of sulfate, nitrate, chloride, ammonium salt and phosphate.
6. A method of preparing a carbon-based silica support according to claim 3, wherein the step (2) of preparing a carbon-based silica support comprises the steps of:
a) Adding a silicon source in a water bath environment at 20-80 ℃, stirring, and then adding a carbon source and a certain amount of alkali to enable the pH value to be 8.5-9.5;
b) Continuously stirring for 30-90min, transferring to a crystallization kettle with a polytetrafluoroethylene lining, and placing in a 160-200 ℃ oven for reaction for 2-10h;
c) And after the reaction is finished, roasting the mixture in a muffle furnace at 300-600 ℃ for 2-8 hours to obtain the carbon-based silicon dioxide carrier.
7. The method of claim 6, wherein the process is carried out in a water bath at 30-60 ℃.
8. The method according to claim 6, wherein the silicon source is selected from any one of ethyl orthosilicate, silica sol, and water glass, and the carbon source is selected from any one of methionine, alanine, glucose, methyl formate, and urea; the alkali is selected from any one of triethylamine, ammonia water and n-butylamine.
9. The method according to claim 8, wherein the carbon source accounts for 60-90% of the silicon source by mass.
10. The method of claim 9, wherein the carbon source comprises 70-80% by mass of the silicon source.
11. The preparation method according to claim 3, wherein in the step (3), a salt solution is impregnated on the carrier by an excessive impregnation method, and the catalyst is obtained by drying after the impregnation, and roasting at 300-600 ℃ for 2-8 hours.
12. Use of the europium-based catalyst of any one of claims 1-2 or the europium-based catalyst prepared by the preparation method of any one of claims 3-11 in the ammoxidation of methanol to hydrogen cyanide.
13. The use according to claim 12, wherein when the europium-based catalyst is used in the reaction of preparing hydrogen cyanide by ammoxidation of methanol, the yield of hydrogen cyanide is more than 98%, the yield of byproduct formaldehyde is less than 0.02%, and the conversion rate of ammonia gas is more than 99.99%.
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