CN117654498A - Catalyst for pretreatment of carbon tetraalkylation raw material, preparation method and pretreatment method - Google Patents
Catalyst for pretreatment of carbon tetraalkylation raw material, preparation method and pretreatment method Download PDFInfo
- Publication number
- CN117654498A CN117654498A CN202210949936.3A CN202210949936A CN117654498A CN 117654498 A CN117654498 A CN 117654498A CN 202210949936 A CN202210949936 A CN 202210949936A CN 117654498 A CN117654498 A CN 117654498A
- Authority
- CN
- China
- Prior art keywords
- carbon
- catalyst
- raw material
- tetraalkylating
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002994 raw material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000002203 pretreatment Methods 0.000 title abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 24
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 238000005262 decarbonization Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 46
- 238000005804 alkylation reaction Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 25
- 230000029936 alkylation Effects 0.000 abstract description 23
- 150000001993 dienes Chemical class 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 51
- 238000005984 hydrogenation reaction Methods 0.000 description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 18
- 238000006317 isomerization reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 150000004763 sulfides Chemical class 0.000 description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 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 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZQNAPEGQCXAPLV-UHFFFAOYSA-N methoxymethane;2-methylpropan-2-ol Chemical compound COC.CC(C)(C)O ZQNAPEGQCXAPLV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- -1 alkaline matters Chemical compound 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- Y02P20/10—Process efficiency
Abstract
The invention discloses a catalyst for pretreatment of a carbon tetraalkylating raw material, a preparation method and a pretreatment method, and belongs to the technical field of carbon four light hydrocarbon processing. The technical proposal is as follows: the method comprises the steps that carbon tetraalkylation raw materials firstly enter an extraction tower for extraction, the water-washed carbon tetraalkylation raw materials extracted from the tower top enter a catalytic rectifying tower, the catalytic rectifying tower is divided into a rectifying section, a reaction section and a stripping section from top to bottom, and the catalyst is placed in the reaction section; feeding the carbon tetraalkylation raw material into a reaction section, reacting butadiene with hydrogen, and continuously removing generated 2-butene in the reaction process; and (3) extracting the pretreated carbon tetraalkylation raw material from the bottom of the catalytic rectifying tower. The pretreatment method of the invention carries out corresponding pretreatment such as desulfurization, denitrification, deoxidization, diene removal and the like before the carbon tetraalkylation raw material enters the alkylation device, meets the requirements of the alkylation feeding material on raw material impurities, improves the quality of the alkylation oil, and reduces the material loss of the alkylation process.
Description
Technical Field
The invention relates to the technical field of carbon four light hydrocarbon processing, in particular to a catalyst for pretreatment of a carbon four-alkylation raw material, a preparation method and a pretreatment method.
Background
Alkylation is one of the important processing technologies of refineries, and is a process of generating alkylate (isooctane) by reacting isobutane with carbon tetraolefin under the action of a catalyst. The alkylated oil contains no olefin and aromatic hydrocarbon, has high research octane number and motor octane number, and is an ideal gasoline blending component. Along with the improvement of environmental protection requirements, the gasoline standard is correspondingly exported, and the standard has more strict requirements on indexes such as olefin content, aromatic hydrocarbon content, benzene content, sulfur content and the like. The alkylate oil stands out in the oil upgrading process, and has wide development space.
In the alkylation process, liquid acid (sulfuric acid, hydrofluoric acid and ionic liquid) or solid acid is used as a catalyst, the composition of the used raw materials is different, the impurity content is different, and the quality, the yield and the acid consumption of the device of the alkylate are greatly influenced. Due to the difference of crude oil sources and processing technologies, sulfide such as butadiene, mercaptan, thioether, disulfide and the like, and impurities such as nitride, chloride, oxygen-containing compounds, heavy metals and the like are also toxic substances in alkylation reaction in the carbon four raw materials, so that the influence is great. In the alkylation process of butadiene in the C4, acid-soluble oil (Aso) with high molecular weight, viscosity and high viscosity and heavy alkylate with low octane number and high dry point are generated by reaction, so that the quality and yield of the alkylate are reduced, and the acid consumption and the production cost are greatly increased. Sulfide, nitride, chloride, oxygen-containing compounds, heavy metals and other impurities, and for the liquid acid catalyst, the acid consumption is obviously increased; the solid acid catalyst causes deactivation of the catalyst, and the service life is seriously affected. With the increase of the blending amount of residual oil in the catalytic device of the oil refinery and the appearance of a novel oil refining process, the content of impurities such as butadiene, sulfide and the like in the carbon four is in an ascending trend, so that corresponding removal measures are very necessary to be added, and the impurities in the carbon four raw materials are controlled so as to ensure the operation of an alkylation device.
The process for removing butadiene from carbon number four generally adopts a selective hydrogenation method, and in the hydrogenation process, besides converting butadiene into mono-olefin, 1-butene can be isomerized into 2-butene, so that the octane number of the alkylate is improved. The active metal for selective hydrogenation is usually a noble metal catalyst based on palladium, but the noble metal catalyst has higher requirements on impurities in raw materials, and the activity of the hydrogenation catalyst is reduced or even deactivated due to the existence of the impurities. At present, the oil refining device has double-stripping technology to remove sulfides such as hydrogen sulfide, mercaptan and the like, but a small amount of residues still exist due to the technology, and new impurities such as caustic soda and the like are introduced while removing the impurities. There have been reports on how to solve the problem of the influence of impurities on alkylation catalysts.
Patent CN 105601460B provides a method for refining an alkylation feedstock, wherein an alkylation feedstock containing impurities is subjected to a water washing tower, a dehydration tower, a desulfurizing tower, a dechlorination tower, a denitrification tower, a dealkylation tower, a preheater and a selective hydrogenation reactor to obtain a refined alkylation feedstock. The method can effectively remove various impurities such as sulfide, nitride, chloride, oxygen-containing compounds and the like in the alkylation raw material, obviously reduce the impurity content in the alkylation raw material, avoid poisoning of a solid acid catalyst in a subsequent alkylation reaction, and improve the catalytic activity and the service cycle of the alkylation solid acid, and has the defect of overlarge investment.
Patent CN 1621396A provides a process for the selective hydrodeoxygenation of small amounts of diolefins in the carbon tetra-alkylated feedstock, by contacting in a fluid bed, a carbon tetra-alkylated feedstock containing small amounts of diolefins with a magnetic noble metal catalyst consisting of a spherical support and one or more noble metal active components selected from palladium, platinum, ruthenium and rhodium, wherein the spherical support consists of alumina and magnetic particles, and wherein the magnetic particles consist of SiO 2 The coating layer and the inner core of the iron-containing substance can be separated and recovered from the reaction product very easily under the action of a magnetic field. The disadvantage is that the raw materials only consider the carbon four after the ether and the low sulfur material, and the method has no universality.
Patent CN 107118072A discloses a method for producing isomeric C8 alkane by four carbon fractions, the technological route is that the four carbon fractions of a refinery firstly enter a depropanizer and then enter a weighter, the four carbon fractions are divided into light components and heavy components, 2-butene is separated from the heavy components, butadiene in the light components is converted into 1-butene and 2-butene through hydrogenation, and then 2-butene and isobutene are converted into 1-butene through isomerization; separating n-butane from heavy component, isomerizing to isobutane, and reacting 1-butene with isobutane to produce isomerised C8 alkane. The carbon four components are utilized to the maximum extent, and most of impurities can be removed, but the energy consumption is higher.
Patent CN 206624800U discloses a device for refining alkylated raw gas by isooctane, which is characterized in that an operation unit for refining alkylated raw gas by isooctane is additionally arranged by utilizing the difference of boiling points and solubilities of different components of the raw gas, isooctane is used as an absorbent, and organic sulfur and organic chlorine in the etherified carbon four raw gas are removed, so that the problem of deactivation of a 1, 3-butadiene catalytic hydrogenation catalyst is well solved. The disadvantages are that the removal of impurities with isooctane as an absorbent causes isooctane loss and the recompression of carbon four gasification adds additional energy consumption.
In summary, the process disclosed in the prior art mainly relates to an adsorbent or raw material extraction process, and part of the process solves the problems of complex flow, high investment and energy consumption and the like although impurities in raw materials affect an alkylation catalyst. Therefore, there is a need to develop a new pretreatment process that accommodates feedstocks of various origins, increasing the flexibility and industrial applicability of alkylation units.
Disclosure of Invention
The invention aims to solve the technical problems of complex impurities, long purification process flow, high investment and easy loss or inactivation of an alkylation catalyst of a carbon tetraalkylation raw material in the prior art, provides a pretreatment method capable of removing impurities from raw materials with different sources, and simultaneously provides a novel selective hydrogenation catalyst which can be better adapted to the impurities. The method can be suitable for the pretreatment of corresponding desulfurization, denitrification, deoxidization, deolefination and the like of the carbon four fractions in the light hydrocarbon generated by the oil refining, ethylene cracking and other processes before entering an alkylation device, meets the requirements of alkylation feeding on raw material impurities, improves the quality of the alkylate, and reduces the material loss of the alkylation process.
The technical scheme of the invention is as follows:
in one aspect, the invention provides a catalyst for pretreating a carbon tetraalkylating raw material, which is characterized in that the catalyst is formed by loading a main active component Pd and a co-active component La or Ce on a mixed-phase alumina carrier taking a delta phase as a main phase.
Preferably, in the alumina carrier, delta phase alumina accounts for 80-95 wt% and the balance is gamma phase alumina.
Preferably, the catalyst has a main active component Pd content of 0.05 to 0.5wt%, preferably 0.1 to 0.3wt%; the content of the auxiliary active component La or Ce is 0.05-3.0 wt%, preferably 0.1-2.0 wt%.
Preferably, the specific surface area of the alumina carrier is 30 to 300 square meters per gram, preferably 50 to 200 square meters per gram; the specific pore volume is 0.2-0.8 ml/g, and the pore radius is 5.0-15 nm (nitrogen adsorption method).
Preferably, the catalyst is in a circular ring structure, a plurality of ribs are radially arranged in the catalyst, and the ribs are in a shape of a Chinese character' miThe catalyst is in a cylinder of a multi-rib wheel in a ten shape; the particle size of the catalyst is 6-30mm so as to meet the process requirements of being uniformly mixed with random packing or used as independent separation capacity packing; the catalyst particles as filler have higher specific surface area of fluid of 200-500 m 2 /m 3 。
In a second aspect, the invention provides a preparation method of the catalyst for pretreating the carbon tetraalkylating raw material, which is characterized in that carbonate, nitrate or chloride of a main active component and a co-active component is prepared into a metal salt solution, and an organic acid (formic acid, acetic acid, oxalic acid or the like) and nitric acid or hydrochloric acid are added to make the solution acidic so as to prevent the metal salt solution from being hydrolyzed to generate precipitation in an alkaline environment. Immersing the alumina carrier in water solution at normal temperature-60 deg.C, drying at 100-300 deg.C, and calcining at 300-600 deg.C for 3-6 hr. In the molding, the binder and the pore-expanding agent are known substances, and the addition amount is based on the weight of the alumina carrier, preferably, the addition amount of the pore-expanding agent is 2-4wt% and the addition amount of the binder is 1-3wt%.
In a third aspect, the present invention also provides a method for pretreating a carbon tetraalkylating raw material by using the catalyst, wherein the carbon tetraalkylating raw material from an upstream device or a tank area firstly enters the lower part of an extraction tower to be extracted, and then is in countercurrent contact with desalted water entering the upper part of the extraction tower, so as to extract and remove water-soluble impurities such as metal ions, alkali nitrides, oxygen-containing compounds (methanol, ether, etc.) and the like. The desalted water is a continuous phase, the carbon tetraalkylation raw material is a disperse phase, the materials extracted from the bottom of the extraction tower are sent to a sewage treatment device, and the extracted carbon tetraalkylation raw material is deposited, separated and dehydrated by a coalescer and then enters a catalytic rectifying tower. The inner part of the extraction tower is a sieve plate or a filler, and the extraction theoretical stage number is more than 2. The washed carbon tetraalkylation raw material enters a catalytic rectifying tower which is divided into a rectifying section, a reaction section and a stripping section from top to bottom, wherein the reaction section is provided with a catalyst for removing butadiene through hydrogenation and isomerising 1-butene into 2-butene. The method is characterized in that a carbon tetraalkylating raw material enters from the upper part of a reaction section, hydrogen enters from the bottom of the reaction section, contacts with the carbon tetraalkylating raw material from bottom to top in the reaction section, and butadiene in the carbon tetraalkylating raw material reacts with the hydrogen to generate butene, 1-butene is isomerized into 2-butene under the hydrogen condition, and the generated 2-butene is continuously removed in the reaction process. The top of the catalytic rectifying tower is provided with a cut-off fire torch pipe network of carbon four containing hydrogen, carbon three, oxygen-containing compounds (dimethyl ether, methanol, water and the like), light sulfides (hydrogen sulfide, carbonyl sulfide, light mercaptan and the like) and a small amount of isobutane and the like, and the bottom of the catalytic rectifying tower is provided with a carbon four-alkylation raw material which does not contain butadiene and other impurities and meets the requirements of an alkylation device.
Preferably, the carbon tetraalkylating feedstock is treated in a decarbonizing five column prior to entering the extraction column. When the carbon tetraalkylation raw material contains impurities such as carbon five components and heavy sulfides, the carbon tetraalkylation raw material is treated in a decarbonization five tower, the impurities such as the components and the heavy sulfides with the boiling points higher than that of the carbon five are removed, and then the carbon tetraalkylation raw material enters an extraction tower for treatment.
Preferably, the operating conditions of the decarbonization five towers are as follows: the pressure is 0.3-1.0 MPa, the tower top temperature is 40-90 ℃, and the reflux ratio is 0.2-3.0; the operating conditions of the extraction column were: the pressure is 0.3-0.6 MPa, the temperature is normal temperature-60 ℃, and the oil-water volume ratio is 3-20:1; the operating conditions of the catalytic rectifying column are as follows: the pressure is 1.0-1.8 MPa, the tower top temperature is 40-60 ℃, and the reflux ratio is 20-50; the operating conditions of the reaction section of the catalytic rectifying tower are as follows: pressure of 0.4-2.0 MPa, temperature of 40-90 ℃ and volume space velocity of carbon four liquid phases of 5-30 h -1 The molar ratio of hydrogen to butadiene is 1.0-5.0, the molar ratio of hydrogen to butadiene is too low, the butadiene removal is incomplete, and the side reaction of olefin hydrogenation to alkane occurs when the molar ratio of hydrogen to butadiene is too high.
Preferably, the catalytic rectifying tower is provided with a plurality of reaction sections, the catalyst is scattered in the reaction sections, the catalyst is independently piled up or uniformly mixed with scattered packing, a liquid distributor is arranged above each reaction section, the carbon tetraalkylating raw material enters the reaction section from the liquid distributor, a hydrogen feeding distribution pipe is arranged below the reaction section, and hydrogen enters the reaction section from the hydrogen feeding distribution pipe; a separation tray is arranged between two adjacent reaction sections. In addition, the number of tower plates of the catalytic rectifying tower is 60 theoretical plates, the rectifying section is 15-30 theoretical plates, the reaction section is 5-10 theoretical plates, and the stripping section is 25-30 theoretical plates.
In the catalytic rectifying tower, the upward flowing gas phase material hydrogen passes through the reaction section, the downward flowing liquid phase material carbon tetraalkylation raw material enters the reaction section after being distributed and undergoes hydrogenation and isomerization reaction under the action of a catalyst to generate butene, and most of 1-butene is isomerized into 2-butene. The reacted materials are separated in a reaction section, and the high-boiling-point 2-butene is continuously removed from the reaction section, so that the chemical reaction balance between the 1-butene and the 2-butene is broken, the conversion rate and the isomerization rate of the reaction are improved, and the 1-butene is deeply converted. The gas-liquid two-phase material is subjected to heat and mass transfer in the reaction section, and the reaction heat and the isomerism heat can be used for vaporizing part of the material, so that the heat is effectively utilized, and the economy of the catalytic rectifying tower is improved. The reaction structure is simple, the catalyst is convenient to assemble and disassemble, and the reactant is in direct contact with the catalyst, so that the reaction is more facilitated.
The reaction section is arranged below the feed inlet, and light sulfide (such as methyl mercaptan, hydrogen sulfide, carbonyl sulfide and the like) and oxygen-containing compound (alcohol, ether and the like) impurities flow in the top direction of the column at the feed inlet, so that the contact between the light sulfide and a hydrogenation catalyst in the reaction section below is reduced, and the possibility of influencing the activity and the service life of the hydrogenation catalyst is reduced.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, most of sulfide, nitride, chloride, oxygen-containing compound, heavy metal and other impurities and diene in the carbon tetraalkylating raw material can be removed through treatments such as removal of carbon penta-components, extraction, selective hydrogenation and the like, so that the quality of the alkylate is improved, and the consumption of liquid acid catalyst of an alkylation device is reduced. For the alkylation of the solid acid, the total amount of impurities entering the adsorption unit can be effectively reduced, and the operation period of the adsorbent and the service life of the solid acid catalyst are prolonged.
2. The selective hydrogenation catalyst has better adaptability to a small amount of oxygen-containing compounds and light sulfides (mercaptan and the like), and can keep higher hydrogenation activity at a lower temperature. The reasons for this may be: (1) The co-active component lanthanum or cerium is transition metal but has alkaline earth metal property in certain aspects, and the existence of lanthanum oxide/cerium oxide reduces the acidity of the catalyst surface and reduces the adsorption of sulfide; (2) The auxiliary active component lanthanum or cerium can reduce the granularity of palladium crystals, increase the dispersity of the palladium crystals, be favorable for loading palladium on a carrier, avoid sintering and agglomeration in the roasting process, and improve the activity of the catalyst; (3) The auxiliary active component is an electron donor, the electron density of palladium is regulated and controlled, and the adsorption of sulfide is weakened; (4) The catalyst carrier is regulated to make the most probable pore diameter in proper range so as to reduce the entry of oxygen-containing compounds, sulfides, etc. such as alcohol, ether, etc. into the catalyst pore canal.
3. The invention carries out selective hydrogenation reaction in the catalytic rectifying tower to remove butadiene, which not only can utilize the separation capability of the reaction section to fractionate impurities harmful to hydrogenation catalyst, but also can break the chemical balance between 1-butene and 2-butene and improve the isomerization rate of 1-butene. The heat generated by the hydrogenation reaction heat and the isomerization of the 1-butene can be used for separating components, so that the steam consumption of the rectification reaction is reduced. The liquid materials in the catalytic rectifying tower are utilized to wash, so that the carbon deposition on the surface of the catalyst is reduced, and the service life of the selective hydrogenation catalyst is prolonged.
4. The catalyst adopts a multi-rib wheel structure, has better gas and liquid dispersing effect, increases the specific surface area of the catalyst, increases the contact area of materials on the surface of the catalyst, has good separation capability, ensures the distribution of liquid materials on the surface of the catalyst, improves the hydrogenation effect, and simplifies the filling mode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic structural view of the present invention.
FIG. 2 is a schematic structural view of the reaction section of the catalytic rectifying tower of the present invention.
FIG. 3 is a schematic structural view of the catalyst of the present invention.
In the figure, a five-column for 1-decarburization, a 2-extraction column, a 3-coalescer, a 4-catalytic rectifying column, a 41-rectifying section, a 42-reaction section, a 421-liquid distributor, a 422-separation tray, a 423-hydrogen feeding distribution pipe, a 43-stripping section and a 6-rib.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation process of the hydrogenation catalyst in the embodiment comprises the following steps: 100g of pseudo-boehmite and 4g of pore-forming agent are weighed and mixed uniformly, 2g of solution containing binder is added, and after kneading, the mixture is extruded in a die to form the eight-bar wheel shape (like the shape of the Chinese character 'mi' shown in figure 3). The granularity of the catalyst is phi 8 multiplied by 8mm, and the catalyst is put into a muffle furnace and baked for 4 hours at the temperature of 1000 ℃ to obtain the alumina carrier. The palladium chloride, the lanthanum nitrate and the hydrochloric acid are respectively added into water to prepare a metal solution, the alumina carrier is weighed according to weight, the alumina carrier is immersed into the metal solution at normal temperature, and is dried at 200 ℃, and then is baked for 3 hours at 500 ℃ to obtain the hydrogenation catalyst of the embodiment.
XRD detection shows that delta phase alumina accounts for 95wt% and the rest is gamma phase alumina. The specific surface area of the carrier is 180 square meter/g, the specific pore volume is 0.6ml/g, the pore radius is 9nm (nitrogen adsorption method), the content of Pd metal loaded is 0.2wt%, and the content of La metal is 1.5wt%.
According to the process flow shown in fig. 1-2, catalytic carbon four is used as a raw material, the composition of the raw material is shown in table 1-1, the composition of impurity sulfide in the raw material is shown in table 1-2, and the composition of impurity oxygen-containing compound is shown in table 1-3.
The raw material flow I enters a decarbonization five-tower, the operation pressure of the decarbonization five-tower is 0.5MPa, the tower top temperature is 54 ℃, and the reflux ratio is 0.5. The top of the column is obtained a carbon four stream II from which the carbon five is removed, wherein the content of heavy sulfides such as dimethyl disulfide and the like is less than 5ppm, and the content of the carbon five is less than 0.1 percent. The four carbon material flows II enter the bottom of an extraction tower, the pressure of the extraction tower is 0.4MPa, the temperature is 40 ℃, and the oil-water volume ratio is 20:1, and the content of alkali nitride and metal ions in the extracted carbon four material flow is less than 1ppm after countercurrent extraction with water.
The carbon four material flow V with most of metal ions and alkali nitrides removed is extracted from the top of the extraction tower and enters a catalytic rectifying tower, the operating pressure of the catalytic rectifying tower is 1.0MPa, the temperature of the top of the catalytic rectifying tower is 54 ℃, and the reflux ratio is 50. Hydrogen enters the tower from the lower part of the reaction section, contacts with the carbon four materials in the reaction section from bottom to top, and the catalytic rectifying tower is provided with a reaction section. Under the action of a hydrogenation catalyst, hydrogen and butadiene are subjected to hydrogenation reaction to generate butene, 1-butene component is isomerized into 2-butene under the condition of hydrogen, and the 2-butene generated by the reaction can rapidly leave the reaction section downwards through the rectification separation function, so that the isomerization balance of double bonds of butene in the reaction section is broken, and the 1-butene in the reaction section can be subjected to deep reaction. The material flow VII containing light components such as carbon three, water, hydrogen, a small amount of methyl mercaptan and the like is extracted from the top of the tower, and the high-quality carbon tetraalkylation material flow VIII which does not contain impurities such as butadiene, sulfide, oxygen-containing compounds and the like after being purified is obtained from the bottom of the tower. The compositions of the raw materials and impurities in each stream are shown in tables 1-4 and tables 1-5.
The filling amount of the selective hydrogenation catalyst in the reaction section is 200ml, and the space velocity of the hydrogenation liquid phase is 10h -1 The hydrogen-diene ratio was 2.5mol/mol, the temperature was 70℃and the pressure was 1.0MPa. The diolefin in the raw material is removed, the diolefin content in the reacted material is less than 100ppm, and the isomerization rate of 1-butene is more than or equal to 85 percent.
TABLE 1-1 raw material composition
TABLE 1-2 sulfide composition in raw materials
Tables 1 to 3 composition of oxygenate in raw materials
| Composition of the composition | Methanol | MTBE | Dimethyl ether | Tert-butanol | Water and its preparation method |
| wt，％ | - | - | - | - | 0.01 |
Tables 1 to 4 raw material composition in each stream
Tables 1-5 impurity composition in each stream
Stream VIII represents the pretreated end product, and as can be seen from tables 1-4 and 1-5, the process of this embodiment can remove impurities such as carbon five, most of sulfides, alkalides, oxygenates, heavy metals, and diolefins from the carbon tetraalkylating feedstock, and the pretreated carbon tetraalkylating feedstock of this embodiment meets the impurity requirements for feeding into the alkylation unit.
Example 2
The hydrogenation catalyst of this example was prepared by weighing 100g of pseudo-boehmite and 3g of a pore-forming agent, mixing them uniformly, adding 3g of a binder-containing solution, kneading them, and extruding them in a die to give the eight-bar wheel shape of the present invention (in the shape of "rice" as shown in FIG. 3). The granularity of the catalyst is phi 6 multiplied by 6mm, and the catalyst is put into a muffle furnace and baked for 4 hours at 900 ℃ to obtain the alumina carrier. Adding palladium chloride, cerium nitrate and a small amount of nitric acid into water respectively to prepare a metal solution, weighing an alumina carrier, soaking in the metal solution at normal temperature, drying at 200 ℃, and roasting at 400 ℃ for 3 hours to obtain the hydrogenation catalyst of the embodiment.
XRD detection shows that delta phase alumina accounts for 85wt% of the alumina carrier, and the rest is gamma phase alumina. The specific surface area of the carrier is 180 square meter/g, the specific pore volume is 0.4ml/g, the pore radius is 8nm (nitrogen adsorption method), the content of supported Pd metal is 0.2wt% and the content of Ce metal is 1.2wt%.
According to the process flow shown in fig. 1-2, carbon four after the catalytic ether is used as a raw material flow II, the raw material composition is shown in table 2-1, the impurity sulfide in the raw material is shown in table 2-2, and the impurity oxygen-containing compound is shown in table 2-3.
The heavy sulfides in the material flow II are less, the material flow II does not enter into the decarburization five towers, and directly enters into the bottom of the extraction tower, the pressure of the extraction tower is 0.4MPa, the temperature is 40 ℃, and the oil-water volume ratio is 3: and 1, after countercurrent extraction with water, the methanol content in the four-carbon material is less than 50ppm. The stream V with most of metal ions and alkaline matters removed is extracted from the top of the extraction tower and enters a catalytic rectifying tower, the operating pressure of the catalytic rectifying tower is 1.8MPa, the temperature of the top of the catalytic rectifying tower is 66 ℃, and the reflux ratio is 50. Hydrogen enters the tower from the lower part of the reaction section and contacts with the carbon four materials in the reaction section from bottom to top. Under the action of a hydrogenation catalyst, hydrogen and butadiene are subjected to hydrogenation reaction to generate butene, 1-butene component is isomerized into 2-butene under the condition of hydrogen, a material flow VII containing light components such as carbon three, dimethyl ether, methanol, water, hydrogen, a small amount of methyl mercaptan and the like is produced at the top of the tower, and a purified high-quality carbon tetra-alkylated material flow VIII is obtained at the bottom of the tower. Wherein the butadiene content is less than 100ppm, the sulfide content is less than or equal to 15ppm, the methyl alcohol is not contained, the dimethyl ether is less than 40ppm, and the water is less than 50ppm. The compositions of the raw materials and impurities in each stream are shown in tables 2-4 and tables 2-5.
The filling amount of the selective hydrogenation catalyst in the reaction sections is 200ml, and the selective hydrogenation catalyst is mixed with random metal stainless steel theta mesh ring filler with similar granularity to form two reaction sections, and the sections are separated by regular filler. The space velocity of the hydrogenation liquid phase is 15h -1 The hydrogen-diene ratio is 4.0mol/mol, the temperature is 92-100 ℃, and the pressure is 1.80MPa. The diolefin in the raw material is removed, the diolefin content in the reacted material is less than 100ppm, and the isomerization rate of 1-butene is more than or equal to 90 percent.
TABLE 2-1 composition of raw materials
TABLE 2-2 sulfide composition in raw materials
Tables 2-3 composition of oxygenate in feedstock
| Composition of the composition | Methanol | MTBE | Dimethyl ether | Tert-butanol | Water and its preparation method |
| wt，％ | 0.0103 | 0.0077 | 0.1603 | 0.0013 | 0.047 |
Tables 2-4 composition of the streams
Tables 2-5 impurity composition of each stream
Stream VIII represents the final product after pretreatment, and as can be seen from tables 2-4 and 2-5, the method of this embodiment can remove most of sulfide, alkaline matters, oxygen-containing compounds, heavy metals and other impurities and diolefins in the carbon tetraalkylating raw material, and the carbon tetraalkylating raw material pretreated by this embodiment meets the impurity requirement of the alkylation unit.
Comparative example 1
In contrast to example 6 of publication No. CN108865243B, a palladium-molybdenum based selective strengthening catalyst was used, nickel pseudo-boehmite was used as a carrier, and the carrier was prepared by mixing and kneading with nitric acid, phosphoric acid, lithium citrate, calcium nitrate and water, extrusion molding, drying at 110℃and firing at 1040℃for 4 hours. Preparing palladium chloride, molybdenum oxide and potassium carbonate into an active component impregnating solution, regulating the pH value of the solution, impregnating the prepared impregnating solution onto a carrier, removing residual liquid after 30 minutes, washing with distilled water, aging, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the catalyst. The active metal content of the catalyst is 0.32 percent of palladium, 1 percent of nickel, 1.42 percent of molybdenum oxide, 1.45 percent of lithium oxide and 5.1 percent of phosphorus oxide.
Taking the optimal data provided in this patent, example 6, the test material was mixed carbon four, butadiene content 0.17%, fixed bed pilot plant, and reduced at 100 ℃ for 6 hours under hydrogen atmosphere. The reaction inlet temperature is 50 ℃, the reaction pressure is 1.3MPa, and the liquid space velocity is 9.5h -1 The molar ratio of hydrogen to butadiene was 3.5. As a result, the removal rate of butadiene after hydrogenation was 98.7%, and the isomerization rate of 1-butene was 70%. The impurity content of the butadiene and other impurities before and after the hydrogenation reaction is unchanged because of no purification process.
As can be seen from comparative example 1 and examples 1-2, the pretreatment method of the invention has the characteristics of high removal rate of sulfide, nitride, oxide, diene and other impurities, simple flow and high isomerization rate of 1-butene. The butadiene hydrogenation catalyst has high activity, the diene is efficiently removed by selective hydrogenation of the raw material C4, and simultaneously, the isomerization balance of the 1-butene is broken by utilizing catalytic distillation, so that the isomerization rate of the 1-butene is greatly improved. The structure of the catalyst ensures that the hydrogenation catalyst maintains the separation effect while hydrogenating, and the liquid in the tower scours the surface of the catalyst, thereby being beneficial to prolonging the service life of the catalyst and simplifying the filling structure of the reaction section. The pretreatment method of the invention can also be used in a process flow of non-alkylation purification.
Comparative example 2
The catalyst B of the patent with publication number CN1238239A is used as a contrast, the palladium selective hydrogenation catalyst is prepared according to the preparation steps, the palladium content is 0.2%, the auxiliary active component is gold, the content is 0.02%, and the catalyst granularity is phi 2.2X3-5 mm. The catalytic C-IV (the composition of raw material 1 is shown in table 1-1) and the etherified C-IV (the composition of raw material 2 is shown in table 2-1) are respectively taken as raw materials, and the reaction pressure is 1.5MPa, the temperature is 50 ℃ and the space velocity is 10h -1 The molar ratio of hydrogen to butadiene was 2.5 and the results are shown in Table 3, which were obtained by reacting with the catalyst prepared in example 2 of the present invention under the same process conditions.
TABLE 3 results of the operation of the catalysts of comparative example 2 and example 2
As is clear from Table 3, the residual butadiene content of the feedstock 1 after hydrogenation of the comparative example 2 was 0.002%, the residual butadiene content of the feedstock 2 was 0.0017%, the butadiene removal rates were 99.1% and 99.3%, and the 1-butene isomerization rates were 59.7 and 56.2%, respectively. The catalyst of example 2 of the present invention had undetected butadiene residual amounts, 100% butadiene removal, and 1-butene isomerization rates of 68.5 and 67.7%, respectively, under the same process conditions. Therefore, the catalyst of the invention has better activity under the same raw material condition.
Comparative example 3
The catalyst B of the patent with publication number CN1238239A is used as a contrast, the palladium selective hydrogenation catalyst is prepared according to the preparation steps, the palladium content is 0.2%, the auxiliary active component is gold, the content is 0.02%, and the catalyst granularity is phi 2.2X3-5 mm. Loading into catalytic rectifying tower, loading catalyst into the tower, and having tower height of 3m and tower diameter of 25mm. The raw materials are shown in Table 2-1, the materials are fed into a tower, the feeding rate is 400ml/h, and the reflux ratio is 50; the rectification was carried out under the same process conditions as the catalyst prepared in example 2 of the present invention, and the results are shown in tables 4-1 and 4-2.
TABLE 4-1 comparison of the compositions of the raw materials after the catalyst of comparative example 3 and example 2 was operated
TABLE 4-2 comparison of impurity compositions after run of comparative example 3 and example 2 catalyst
As can be seen from tables 4-1 and 4-2, the catalyst of example 2 of the present invention has better rectification separation effect and separation efficiency for light and heavy components of the four-carbon hydrocarbon when the four-carbon rectification is carried out in the catalytic rectification column compared with the hydrogenation catalyst of comparative example 3.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The catalyst for pretreating the carbon tetraalkylating raw material is characterized in that the catalyst is prepared by loading a main active component Pd and an auxiliary active component La or Ce on a mixed-phase alumina carrier taking delta phase as a main phase.
2. The catalyst for pretreatment of a carbon tetraalkylating feedstock according to claim 1, wherein delta phase alumina is 80 to 95wt% and the balance is gamma phase alumina in the alumina carrier.
3. The catalyst for pretreatment of a carbon tetraalkylating feedstock according to claim 1, wherein the main active component Pd content of the catalyst is 0.05 to 0.5wt%, preferably 0.1 to 0.3wt%; the content of the auxiliary active component La or Ce is 0.05-3.0 wt%, preferably 0.1-2.0 wt%.
4. The catalyst for pretreatment of a carbon tetraalkylating raw material according to claim 1, wherein the specific surface area of the alumina carrier is 30 to 300 square meters/g, preferably 50 to 200 square meters/g; the specific pore volume is 0.2-0.8 ml/g, and the pore radius is 5.0-15 nm.
5. The catalyst for pretreating a carbon tetraalkylating feedstock according to claim 1, wherein the catalyst has a circular ring-shaped structure, and a plurality of ribs are radially provided inside the catalyst.
6. The method for preparing a catalyst for pretreatment of a carbon tetraalkylating raw material according to any one of claims 1 to 5, wherein carbonates, nitrates or chlorates of the main active component and the auxiliary active component are prepared into an aqueous solution, and an organic acid, nitric acid or hydrochloric acid is added to make the aqueous solution acidic; immersing the alumina carrier in aqueous solution at normal temperature-60 ℃, then drying at 100-300 ℃, and roasting at 300-600 ℃ for 3-6 hours to obtain the alumina carrier.
7. A method for pretreating a carbon tetraalkylating raw material by using the catalyst according to any one of claims 1 to 5, wherein the carbon tetraalkylating raw material is extracted by first entering an extraction tower, the water-washed carbon tetraalkylating raw material is extracted from the top of the tower and enters a catalytic rectifying tower, the catalytic rectifying tower is divided into a rectifying section, a reaction section and a stripping section from top to bottom, and the catalyst according to any one of claims 1 to 6 is placed in the reaction section; feeding the carbon tetraalkylation raw material into a reaction section, reacting butadiene with hydrogen, and continuously removing generated 2-butene in the reaction process; and (3) extracting the pretreated carbon tetraalkylation raw material from the bottom of the catalytic rectifying tower.
8. The process of claim 7 wherein the carbon tetraalkylating feedstock is treated in a decarbonizing five column prior to entering the extraction column.
9. The method of claim 8, wherein the operating conditions of the decarbonization five column are: the pressure is 0.3-1.0 MPa, the tower top temperature is 40-90 ℃, and the reflux ratio is 0.2-3.0; the operating conditions of the extraction column were: the pressure is 0.3-0.6 MPa, the temperature is normal temperature-60 ℃, and the oil-water volume ratio is 3-20:1; the operating conditions of the catalytic rectifying column are as follows: the pressure is 1.0-1.8 MPa, the tower top temperature is 40-60 ℃, and the reflux ratio is 20-50; the operating conditions of the reaction section of the catalytic rectifying tower are as follows: pressure of 0.4-2.0 MPa, temperature of 40-90 ℃ and volume space velocity of carbon four liquid phases of 5-30h -1 The molar ratio of the hydrogen to the butadiene is 1.0-5.0.
10. The method of claim 7, wherein the catalytic rectification column is provided with a plurality of reaction sections, a liquid distributor is arranged above each reaction section, and the carbon tetraalkylating raw material enters the reaction section from the liquid distributor; a separation tray is arranged between two adjacent reaction sections.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210949936.3A CN117654498A (en) | 2022-08-09 | 2022-08-09 | Catalyst for pretreatment of carbon tetraalkylation raw material, preparation method and pretreatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210949936.3A CN117654498A (en) | 2022-08-09 | 2022-08-09 | Catalyst for pretreatment of carbon tetraalkylation raw material, preparation method and pretreatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117654498A true CN117654498A (en) | 2024-03-08 |
Family
ID=90069984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210949936.3A Pending CN117654498A (en) | 2022-08-09 | 2022-08-09 | Catalyst for pretreatment of carbon tetraalkylation raw material, preparation method and pretreatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117654498A (en) |
-
2022
- 2022-08-09 CN CN202210949936.3A patent/CN117654498A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101270301B (en) | Light gasoline etherification technique and catalytically cracked gasoline modification method containing the technique | |
| CN103121897B (en) | By the method for the mixture preparing aromatic hydrocarbon containing hydrocarbon with condensed rings | |
| CN102212394B (en) | Fluid catalytic cracking (FCC) gasoline modification method comprising light gasoline etherification process | |
| CN105152840B (en) | Process for refining C-4 hydrocarbon fluid | |
| CN101914387B (en) | Catalysis upgrading method for cracking ethylene by-product carbon-9 | |
| CN101787307A (en) | Gasoline hydrodesulfurization method | |
| CN103382147B (en) | A kind of method improving mixed c 4 utility value | |
| CN112007646A (en) | Carbon-tetrahydrocarbon full-hydrogenation catalyst, preparation method thereof and carbon-tetrahydrocarbon hydrogenation method | |
| CN1216968C (en) | Method for separating and refining etherification material from catalytic cracking gasoline | |
| CN107557064B (en) | Coal tar combined bed hydrogenation method and system for coal tar combined bed hydrogenation | |
| CN111574645B (en) | Hydrogenation method for high-sulfur petroleum resin | |
| CN101322945B (en) | Method for preparing sulphur-containing condensate oil modifying catalyst and use | |
| CN112143519B (en) | Solid acid alkylation of isoparaffin with olefin | |
| CN103540359B (en) | A kind of inferior heavy oil catalytic conversion process improving low-carbon alkene and yield of gasoline | |
| CN103160317B (en) | Production method of propylene and gasoline with high-octane rating | |
| CN102041093B (en) | Catalytic conversion method for improving cetane number and yield of diesel | |
| CN102041082B (en) | Process of hydrogenation of heavy oil feedstock | |
| CN101376831B (en) | Hydrogenation method for hydrocarbon oil containing acid | |
| CN117654498A (en) | Catalyst for pretreatment of carbon tetraalkylation raw material, preparation method and pretreatment method | |
| CN1990832A (en) | Quality modified method for hydrocarbon oil | |
| CN1211458C (en) | Process for preparing isooctane and liquefied petroleum gas for vehicle by oligomerizing and hydrogenating mixed C4 | |
| CN111073687B (en) | Preparation method of clean gasoline | |
| CN103540356A (en) | Low-grade heavy oil catalytic conversion process for increasing yield of low-carbon olefins and diesel oil | |
| CN105541539A (en) | Method for deolefination non-hydrofining of xylene fraction in reformate | |
| CN112125993A (en) | Method for liquid-phase hydrofining of polyvinyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |