CN112642441B - 一种用于催化加氢制备1,2,4-丁三醇的催化剂及其制备方法与应用 - Google Patents
一种用于催化加氢制备1,2,4-丁三醇的催化剂及其制备方法与应用 Download PDFInfo
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- CN112642441B CN112642441B CN202011437640.0A CN202011437640A CN112642441B CN 112642441 B CN112642441 B CN 112642441B CN 202011437640 A CN202011437640 A CN 202011437640A CN 112642441 B CN112642441 B CN 112642441B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000011068 loading method Methods 0.000 claims abstract description 34
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- -1 copper-zinc-aluminum Chemical compound 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 54
- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- 230000009467 reduction Effects 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical compound CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 2
- 239000000006 Nitroglycerin Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960003711 glyceryl trinitrate Drugs 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical group Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- RDLIBIDNLZPAQD-UHFFFAOYSA-N 1,2,4-butanetriol trinitrate Chemical compound [O-][N+](=O)OCCC(O[N+]([O-])=O)CO[N+]([O-])=O RDLIBIDNLZPAQD-UHFFFAOYSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- OAQPVOXRGWEZQS-UHFFFAOYSA-N O.O.O.O.O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] OAQPVOXRGWEZQS-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- PENWRXZLRDTNBI-UHFFFAOYSA-N [3-(hydroxymethyl)oxiran-2-yl]methanol Chemical compound OCC1OC1CO PENWRXZLRDTNBI-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012867 bioactive agent Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 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 1
- 239000011572 manganese Substances 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical group O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002023 wood Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
本发明公开用于催化加氢制备1,2,4‑丁三醇的催化剂,包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;所述活性组分A为铜锌铝混合物;所述活性组分B为Pd、Pt或Ru;所述助剂组分为金属元素C的氧化物,所述金属元素C为Sn、Ga、Ba、Re、Ce、Fe、Co、Ni、Mo、La、Mn、V或Ag;所述催化剂中各组分的负载率如下:所述活性组分A中的Cu、Zn、Al的负载率分别为5‑20%、1.5‑9%、1.0‑6%,活性组分B的负载率为0.5‑5.0%,助剂组分的负载率以金属元素C计为0.05‑0.5%。同时本发明还公开所述催化剂的制备方法及应用。所述催化剂寿命高,活性好。
Description
技术领域
本发明属于化学化工合成技术领域,具体涉及一种催化加氢制备1,2,4-丁三醇催化剂及其制备方法,与所述催化剂在催化苹果酸二甲酯加氢反应中的应用。
背景技术
1,2,4-丁三醇是一种在军工和民用上都具有重要用途的有机合成化学中间体。它是手性多羟基醇,主要用于合成高能材料1,2,4-丁三醇三硝酸酯,后者可用作飞机、火箭、导弹等军事武器的推进剂,较传统的硝化甘油具有冲击敏感性更低、热稳定性更好、挥发性更小和加工安全更高四大优点,是硝化甘油理想、安全的替代品。1,2,4-丁三醇还可用于制备生物活性剂、医药用缓释剂、卷烟添加剂、抗菌剂、彩色显影剂等。在医药上,可以作为药物缓释剂,控制药物释放速率;作为烟草添加剂,可消除硝基化合物对人体毒害,减小焦油成分危害;作为抗菌剂,可有效阻止微生物的生长;在彩色显影剂上可以增加色彩度和粘着力;在高分子材料领域,可以作为高分子材料的交联剂。
1,2,4-丁三醇合成方法有丁烯醇为原料直接水解法,丁烯醇环氧化-氢解两步法,丙烯醇与甲醛和酸酐反应,硼氢化物还原法,生物合成法等。2-丁烯醇-1,4二醇在硫酸作用下直接水解法收率及选择性较差;2-丁烯醇-1,4二醇首先氧化生成2,3-环氧基-1,4-丁二醇,再由Raney-Ni催化氢解,反应条件苛刻,安全性差且收率不高;丙烯醇与甲醛和酸酐反应工艺条件温和、成本低,反应机理复杂,产品提纯困难;生物合成法是一种较为全新的方法,原料价格易得,但是所需酶种类繁多,合成路径较长,酶合成条件要求苛刻。目前报道的以苹果酸二甲酯为原料合成1,2,4-丁三醇的方法较少,专利(CN 111116312 A)报道将苹果酸二甲酯与正丙胺反应得到苹果酸二酰胺,然后再与四氢呋喃混合,在催化剂作用下,发生加氢反应生成1,2,4-丁三醇。
综上所述,如果能够建立一套工艺简单,绿色环保,经济实用的1,2,4-丁三醇合成方法,将具有重要的意义。目前尚未报道采用苹果酸二甲酯为原料直接催化加氢合成1,2,4-丁三醇的方法。固定床连续化工艺技术结构简单,连续运行,操作方便,催化剂机械损耗小,平推流反应,无返混,无需过滤,产品易分离,过程绿色、环保,降低成本。低压连续化固定床工艺技术及配套高选择性加氢催化剂的开发将会是今后发展的热点。
发明内容
针对现有技术的缺陷,本发明一个目的是提供一种用于催化加氢制备1,2,4-丁三醇的催化剂及其制备方法,催化剂活性及寿命高;本发明的另一个目的是提供所述催化剂的应用,即提供一种与所述催化剂相匹配的简单、环保、高效的连续化催化苹果酸二甲酯加氢的方法,反应压力低。
为实现上述目的,本发明采用以下技术方案:
一种用于催化加氢制备1,2,4-丁三醇的催化剂,包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;
所述活性组分A为铜锌铝混合物;
所述活性组分B为Pd、Pt或Ru中的任意一种;
所述助剂组分为金属元素C的氧化物,所述金属元素C为Sn、Ga、Ba、Re、Ce、Fe、Co、Ni、Mo、La、Mn、V或Ag中的任意一种;
所述催化剂中各组分的负载率如下:所述活性组分A中的Cu的负载率为5-20%,活性组分A中的Zn的负载率为 1.5-9%,活性组分A中的Al 的负载率为1.0-6%,活性组分B的负载率为 0.5-5.0%,助剂组分的负载率以金属元素C计为 0.05-0.5%。
优选地,所述活性炭载体地比表面积为800-1200 m2/g、孔容为0.3-0.6cm3/g、粒径为0.5-4mm。
所述活性炭载体的属性及形状不做限制,材质为煤质、果壳、木质、椰壳或树脂活性炭、形状为球形、圆柱形或片形中的任意一种均能实现本发明目的。
所述催化剂的制备方法,其特征在于:包括以下步骤:
(1)载体预处理:将活性炭载体在1-5wt%的稀硝酸溶液中加热煮沸0.2-1h,过滤,洗涤至滤液的pH值为3-7,干燥至恒重;
(2)各组分的负载:
(21)分别将铜、锌、铝的盐溶液混合,搅拌0.5-1h,得到溶液a,将步骤(1)得到的载体浸没于溶液a中,搅拌均匀,静置陈化浸渍,然后用碱液调节浸渍液的pH为8-9.5,静置3-8h,过滤,纯水洗至滤液的pH<7.5,干燥,在氮气气氛下微波加热至450-600℃活化3-5h;
(22)还原处理,得到负载有活性组分A的催化剂前驱体;
(23)将活性组分B的盐溶解在0.5wt%的稀硝酸溶液中,混合均匀得到溶液b;将金属元素C的盐用纯水溶解,得到溶液c;将溶液c加入到溶液b中,混合得到溶液d;向溶液d中加入占所述催化剂质量0.01-1%的络合剂,混合均匀后得到溶液e;将步骤(22)得到产物浸没于溶液e中,混合均匀,静置陈化浸渍,过滤去除上清液,干燥至恒重,在氮气气氛下加热至200-350℃活化2-5h,自然冷却后得到负载有活性组分A、活性组分B和助剂组分的催化剂前驱体;
(3)还原处理,即可。
优选地,步骤(22)所述还原处理具体为:将(21)中所得产物在氮气气氛下以0.5-2℃/min升温速率升温至250-350℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气氛下还原处理2-5h,然后在氮气气氛下冷却至室温。
优选地,步骤(3)所述还原处理具体为:将步骤(2)所得产物在氮气气氛下以0.5-2℃/min升温速率升温至200-300℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理2-5h,然后在氮气气氛下冷却至室温。
优选地,所述铜、锌、铝的盐为硝酸盐、硫酸盐或氯化盐;活性组分B的盐为硝酸盐或氯化盐;金属元素C的盐为水溶性盐,所述水溶性盐为酸盐、氯化盐或钠盐。
优选地,步骤(21)中所述碱液为10-20wt%的碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠或氢氧化钾的水溶液。
优选地,所述络合剂为水杨酸、己二酸、柠檬酸、酒石酸、草酸、甘氨酸、乙二胺四乙酸、乙醇胺、乙二醇、乙酰丙酮或乙二胺。
本发明所述静置陈化浸渍,只要将所述组分负载在活性炭载体上即可;优选地,时间为6-24h、温度为20-40℃。
本发明中所述铜、锌、铝的盐溶液对溶剂无要求,只要能溶解对应的盐即可;优选地,所述盐溶液的溶剂为水。
本发明所述干燥至恒重,只要将附着在国体产物中的溶剂去除使固体产物达恒重即可。优选地,所述干燥的条件为60-150℃,干燥时间为6-48h。
本发明中活性组分A的盐溶液对浓度无要求;负载活性组分B和助剂组分时的固液比也无要求。
所述催化剂在催化苹果酸二甲酯加氢制备1,2,4-丁三醇中的应用。
优选地,所述应用具体为:
(一)将所述催化剂与惰性瓷球逐层交替装填于固定床反应器中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力2-4MPa、氢气流量Q满足20m≤Q≤30m的条件下,将催化剂先以2-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至150-200℃后保温1.5-2.5h,之后降温至80-120℃反应温度后保持恒定;所述m为催化剂的质量,m的单位为g,Q的单位为mL/min;
(三)将原料液苹果酸二甲酯和氢气预热至反应温度后,通入固定床反应器中,进行苹果酸二甲酯催化加氢反应,氢酯摩尔比为(5-25)∶1,反应空速为0.1-0.7g/gcat/hr;
(四)将步骤(三)得到的产物送入气液分离器,分离纯化后得到1,2,4-丁三醇。
本发明的优点:
本发明提供的催化剂先将铜锌铝组分负载在活性炭载体表面,经还原后,再将活性组分B和及助剂组分负载在载体上,得到的催化剂具有良好的结构稳定性,催化剂比表面积较大,孔结构稳定,催化剂寿命高;组分利用率高,活性金属组分分散均匀,在用于催化苹果酸二甲酯加氢制备1,2,4-丁三醇时,表现出较好的低压、低氢酯比加氢活性及产物选择性。
具体实施方式
实施例1
1. 一种用于催化加氢制备1,2,4-丁三醇的催化剂,包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;
所述活性组分A为铜锌铝混合物;
所述活性组分B为Pd;
所述助剂组分为V的氧化物;
所述催化剂中各组分的负载率如下:所述活性组分A中的Cu的负载率为15%,活性组分A中的Zn的负载率为 5%,活性组分A中的Al 的负载率为3%,活性组分B的负载率为0.5%,助剂组分的负载率以金属元素V计为 0.2%;
所述活性炭载体地比表面积为1130 m2/g、孔容为0.46cm3/g、粒径为1.5mm的柱状木质碳。
2. 所述催化剂的制备方法:
(1)载体预处理:将活性炭载体在5wt%的稀硝酸溶液中加热煮沸0.5h,过滤,洗涤至滤液的pH值为3,120℃下干燥14h,恒重;
(2)各组分的负载:
(21)分别将九水硝酸铝、三水硝酸铜、六水硝酸锌的水溶液混合,搅拌0.5h,得到溶液a,将步骤(1)得到的载体浸没于溶液a中,搅拌均匀,在20℃下静置陈化浸渍12h,然后用10wt%的氢氧化钠溶液浸渍液的pH为8,静置6h,过滤,纯水洗至滤液的pH为7,120℃下干燥14h,在氮气气氛下微波加热至500℃活化3h;
(22)还原处理:将(21)中所得产物在氮气气氛下以1℃/min升温速率升温至300℃,氮气吹扫0.5h,然后在摩尔比为1:1的氮气和氢气的混合气氛下还原处理3h,然后在氮气气氛下冷却至室温;
(23)将氯化钯溶解在0.5wt%的稀硝酸溶液中,混合均匀得到溶液b;将偏钒酸钠用纯水溶解,得到溶液c;将溶液c加入到溶液b中,混合得到溶液d;向溶液d中加入占催化剂质量为0.5%的草酸,混合均匀后得到溶液e;将步骤(22)得到产物浸没于溶液e中,混合均匀,20℃静置陈化浸渍12h,过滤去除上清液,120℃干燥12h,在氮气气氛下加热至250℃活化3h,自然冷却后得到负载有活性组分A、活性组分B和助剂组分的催化剂前驱体;
(3)还原处理,将步骤(2)所得产物在氮气气氛下以1℃/min升温速率升温至300℃,氮气吹扫0.2h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理2h,然后在氮气气氛下冷却至室温。
得到的催化剂即为Z1。
实施例2
活性组分B为Pt,制备时,采用的盐为氯化铂;其他同实施例1。得到的催化剂记为Z2。
实施例3
活性组分B为Ru,制备时,采用的盐为三氯化钌;其他同实施例1。得到的催化剂记为Z3。
实施例4
一种用于催化加氢制备1,2,4-丁三醇的催化剂,包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;
所述活性组分A为铜锌铝混合物;
所述活性组分B为Pt;
所述助剂组分为Sn的氧化物;
所述催化剂中各组分的负载率如下:所述活性组分A中的Cu的负载率为5%,活性组分A中的Zn的负载率为1.5%,活性组分A中的Al 的负载率为6%,活性组分B的负载率为5%,助剂组分的负载率以金属元素Sn计为 0.05%;
所述活性炭载体地比表面积为1130 m2/g、孔容为0.46cm3/g、粒径为1.5mm的柱状木质碳。
2. 所述催化剂的制备方法:
(1)载体预处理:将活性炭载体在1wt%的稀硝酸溶液中加热煮沸1h,过滤,洗涤至滤液的pH值为7,120℃下干燥14h,恒重;
(2)各组分的负载:
(21)分别将氯化铝、三水硝酸铜、氯化锌的水溶液混合,搅拌1h,得到溶液a,将步骤(1)得到的载体浸没于溶液a中,搅拌均匀,在20℃下静置陈化浸渍12h,然后用20wt%的氢氧化钠溶液浸渍液的pH为9.5,静置8h,过滤,纯水洗至滤液的pH为7,120℃下干燥14h,在氮气气氛下微波加热至450℃活化5h;
(22)还原处理:将(21)中所得产物在氮气气氛下以0.5℃/min升温速率升温至250℃,氮气吹扫1h,然后在摩尔比为1:1的氮气和氢气的混合气氛下还原处理2h,然后在氮气气氛下冷却至室温;
(23)将氯化铂溶解在0.5wt%的稀硝酸溶液中,混合均匀得到溶液b;将氯化锡用纯水溶解,得到溶液c;将溶液c加入到溶液b中,混合得到溶液d;向溶液d中加入占催化剂质量为1%的水杨酸,混合均匀后得到溶液e;将步骤(22)得到产物浸没于溶液e中,混合均匀,20℃静置陈化浸渍12h,过滤去除上清液,120℃干燥12h,在氮气气氛下加热至200℃活化5h,自然冷却后得到负载有活性组分A、活性组分B和助剂组分的催化剂前驱体;
(3)还原处理,将步骤(2)所得产物在氮气气氛下以0.5℃/min升温速率升温至200℃,氮气吹扫1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理5h,然后在氮气气氛下冷却至室温。
得到的催化剂即为Z4。
实施例5
一种用于催化加氢制备1,2,4-丁三醇的催化剂,包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;
所述活性组分A为铜锌铝混合物;
所述活性组分B为Pd;
所述助剂组分为Ca的氧化物;
所述催化剂中各组分的负载率如下:所述活性组分A中的Cu的负载率为20%,活性组分A中的Zn的负载率为 9%,活性组分A中的Al 的负载率为1.0%,活性组分B的负载率为0.5%,助剂组分的负载率以金属元素Ca计为 0.5%;
所述活性炭载体地比表面积为1130 m2/g、孔容为0.46cm3/g、粒径为1.5mm的柱状木质碳。
2. 所述催化剂的制备方法:
(1)载体预处理:将活性炭载体在2wt%的稀硝酸溶液中加热煮沸0.2h,过滤,洗涤至滤液的pH值为5,120℃下干燥14h,恒重;
(2)各组分的负载:
(21)分别将氯化铝、三水硝酸铜、氯化锌的水溶液混合,搅拌1h,得到溶液a,将步骤(1)得到的载体浸没于溶液a中,搅拌均匀,在20℃下静置陈化浸渍12h,然后用20wt%的碳酸钠溶液浸渍液的pH为9.5,静置3h,过滤,纯水洗至滤液的pH为7,120℃下干燥14h,在氮气气氛下微波加热至600℃活化3h;
(22)还原处理:将(21)中所得产物在氮气气氛下以2℃/min升温速率升温至350℃,氮气吹扫0.2h,然后在摩尔比为1:1的氮气和氢气的混合气氛下还原处理5h,然后在氮气气氛下冷却至室温;
(23)将氯化钯溶解在0.5wt%的稀硝酸溶液中,混合均匀得到溶液b;将氯化钙用纯水溶解,得到溶液c;将溶液c加入到溶液b中,混合得到溶液d;向溶液d中加入负载率为0.05%的乙二醇,混合均匀后得到溶液e;将步骤(22)得到产物浸没于溶液e中,混合均匀,20℃静置陈化浸渍12h,过滤去除上清液,120℃干燥12h,在氮气气氛下加热至350℃活化2h,自然冷却后得到负载有活性组分A、活性组分B和助剂组分的催化剂前驱体;
(3)还原处理,将步骤(2)所得产物在氮气气氛下以2℃/min升温速率升温至200℃,氮气吹扫1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3h,然后在氮气气氛下冷却至室温。
得到的催化剂即为Z5。
实施例6
一种用于催化加氢制备1,2,4-丁三醇的催化剂,包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;
所述活性组分A为铜锌铝混合物;
所述活性组分B为Pd;
所述助剂组分为Mo的氧化物;
所述催化剂中各组分的负载率如下:所述活性组分A中的Cu的负载率为10%,活性组分A中的Zn的负载率为 5%,活性组分A中的Al 的负载率为3%,活性组分B的负载率为1%,助剂组分的负载率以金属元素Mo计为0.2%;
所述活性炭载体地比表面积为1130 m2/g、孔容为0.46cm3/g、粒径为1.5mm的柱状木质碳。
2. 所述催化剂的制备方法:
(1)载体预处理:将活性炭载体在2wt%的稀硝酸溶液中加热煮沸0.5h,过滤,洗涤至滤液的pH值为5,120℃下干燥14h,恒重;
(2)各组分的负载:
(21)分别将氯化铝、三水硝酸铜、氯化锌的水溶液混合,搅拌1h,得到溶液a,将步骤(1)得到的载体浸没于溶液a中,搅拌均匀,在20℃下静置陈化浸渍12h,然后用20wt%的碳酸氢钾溶液浸渍液的pH为9,静置5h,过滤,纯水洗至滤液的pH为7,120℃下干燥14h,在氮气气氛下微波加热至600℃活化3h;
(22)还原处理:将(21)中所得产物在氮气气氛下以2℃/min升温速率升温至350℃,氮气吹扫0.2h,然后在摩尔比为1:1的氮气和氢气的混合气氛下还原处理5h,然后在氮气气氛下冷却至室温;
(23)将氯化钯溶解在0.5wt%的稀硝酸溶液中,混合均匀得到溶液b;将五水硝酸钼用纯水溶解,得到溶液c;将溶液c加入到溶液b中,混合得到溶液d;向溶液d中加入占催化剂质量为0.05%的乙二醇,混合均匀后得到溶液e;将步骤(22)得到产物浸没于溶液e中,混合均匀,20℃静置陈化浸渍12h,过滤去除上清液,120℃干燥12h,在氮气气氛下加热至350℃活化2h,自然冷却后得到负载有活性组分A、活性组分B和助剂组分的催化剂前驱体;
(3)还原处理,将步骤(2)所得产物在氮气气氛下以2℃/min升温速率升温至200℃,氮气吹扫1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3h,然后在氮气气氛下冷却至室温。
得到的催化剂即为Z6。
实施例7
助剂组分为Mn的氧化物,制备时,采用的盐为四水合氯化锰;其他同实施例1。得到的催化剂记为Z7。
实施例8
助剂组分为Ni的氧化物,制备时,采用的盐为硝酸镍;其他同实施例1。得到的催化剂记为Z8。
实施例9
助剂组分为Ag的氧化物,制备时,采用的盐为硝酸银;其他同实施例1。得到的催化剂记为Z9。
实施例10
助剂组分为La的氧化物,制备时,采用的盐为硝酸镧;其他同实施例1。得到的催化剂记为Z10。
应用
本发明提供的催化剂在催化苹果酸二甲酯加氢制备1,2,4-丁三醇中的应用,具体包括以下步骤:
(一)将所述催化剂与惰性瓷球逐层交替装填于固定床反应器中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力2-4MPa、氢气流量Q满足20m≤Q≤30m的条件下,将催化剂先以2-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至150-200℃后保温1.5-2.5h,之后降温至80-120℃的反应温度后保持恒定;所述m为催化剂的质量,m的单位为g,Q的单位为mL/min;
(三)将原料液苹果酸二甲酯和氢气预热至反应温度后,通入固定床反应器中,进行苹果酸二甲酯催化加氢反应,氢酯摩尔比为(5-25)∶1,反应空速为0.1-0.7g/gcat/hr;
(四)将步骤(三)得到的产物送入气液分离器,分离纯化后得到1,2,4-丁三醇。
连续反应2400h,具体反应条件及反应结果见表1,其他反应条件均相同。
表1 反应条件及结果
Claims (10)
1.一种用于催化加氢制备1,2,4-丁三醇的催化剂,其特征在于:包括活性炭载体及负载在所述载体上的活性组分A、活性组分B和助剂组分;
所述活性组分A为铜锌铝混合物;
所述活性组分B为Pd、Pt或Ru中的任意一种;
所述助剂组分为金属元素C的氧化物,所述金属元素C为Sn、Ga、Ba、Re、Ce、Fe、Co、Ni、Mo、La、Mn、V或Ag中的任意一种;
所述催化剂中各组分的负载率如下:所述活性组分A中的Cu的负载率为5-20%,活性组分A中的Zn的负载率为 1.5-9%,活性组分A中的Al 的负载率为1.0-6%,活性组分B的负载率为 0.5-5.0%,助剂组分的负载率以金属元素C计为 0.05-0.5%。
2.根据权利要求1所述用于催化加氢制备1,2,4-丁三醇的催化剂,其特征在于:所述活性炭载体地比表面积为800-1200 m2/g、孔容为0.3-0.6cm3/g、粒径为0.5-4mm。
3.权利要求1所述催化剂的制备方法,其特征在于:包括以下步骤:
(1)载体预处理:将活性炭载体在1-5wt%的稀硝酸溶液中加热煮沸0.2-1h,过滤,洗涤至滤液的pH值为3-7,干燥至恒重;
(2)各组分的负载:
(21)分别将铜、锌、铝的盐溶液混合,搅拌0.5-1h,得到溶液a,将步骤(1)得到的载体浸没于溶液a中,搅拌均匀,静置陈化浸渍,然后用碱液调节浸渍液的pH为8-9.5,静置3-8h,过滤,纯水洗至滤液的pH<7.5,干燥,在氮气气氛下微波加热至450-600℃活化3-5h;
(22)还原处理,得到负载有活性组分A的催化剂前驱体;
(23)将活性组分B的盐溶解在0.5wt%的稀硝酸溶液中,混合均匀得到溶液b;将金属元素C的盐用纯水溶解,得到溶液c;将溶液c加入到溶液b中,混合得到溶液d;向溶液d中加入占所述催化剂质量0.01-1%的络合剂,混合均匀后得到溶液e;将步骤(22)得到产物浸没于溶液e中,混合均匀,静置陈化浸渍,过滤去除上清液,干燥至恒重,在氮气气氛下加热至200-350℃活化2-5h,自然冷却后得到负载有活性组分A、活性组分B和助剂组分的催化剂前驱体;
(3)还原处理,即可。
4.根据权利要求3所述催化剂的制备方法,其特征在于:步骤(22)所述还原处理具体为:将(21)中所得产物在氮气气氛下以0.5-2℃/min升温速率升温至250-350℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气氛下还原处理2-5h,然后在氮气气氛下冷却至室温。
5.根据权利要求4所述催化剂的制备方法,其特征在于:步骤(3)所述还原处理具体为:将步骤(2)所得产物在氮气气氛下以0.5-2℃/min升温速率升温至200-300℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理2-5h,然后在氮气气氛下冷却至室温。
6.根据权利要求5所述催化剂的制备方法,其特征在于:所述铜、锌、铝的盐为硝酸盐、硫酸盐或氯化盐;活性组分B的盐为硝酸盐或氯化盐;金属元素C的盐为水溶性盐,所述水溶性盐为酸盐、氯化盐或钠盐。
7.根据权利要求6所述催化剂的制备方法,其特征在于:步骤(21)中所述碱液为10-20wt%的碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠或氢氧化钾的水溶液。
8.根据权利要求7所述催化剂的制备方法,其特征在于:所述络合剂为水杨酸、己二酸、柠檬酸、酒石酸、草酸、甘氨酸、乙二胺四乙酸、乙醇胺、乙二醇、乙酰丙酮或乙二胺。
9.权利要求1或2所述催化剂在催化苹果酸二甲酯加氢制备1,2,4-丁三醇中的应用。
10.根据权利要求9所述应用,其特征在于:所述应用具体为:
(一)将所述催化剂与惰性瓷球逐层交替装填于固定床反应器中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力2-4MPa、氢气流量Q满足20m≤Q≤30m的条件下,将催化剂先以2-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至150-200℃后保温1.5-2.5h,之后降温至80-120℃反应温度后保持恒定;所述m为催化剂的质量,m的单位为g,Q的单位为mL/min;
(三)将原料液苹果酸二甲酯和氢气预热至反应温度后,通入固定床反应器中,进行苹果酸二甲酯催化加氢反应,氢酯摩尔比为(5-25)∶1,反应空速为0.1-0.7g/gcat/hr;
(四)将步骤(三)得到的产物送入气液分离器,分离纯化后得到1,2,4-丁三醇。
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