CN116351367A - Device and method capable of continuously preparing 5-HMF - Google Patents
Device and method capable of continuously preparing 5-HMF Download PDFInfo
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- CN116351367A CN116351367A CN202310371054.8A CN202310371054A CN116351367A CN 116351367 A CN116351367 A CN 116351367A CN 202310371054 A CN202310371054 A CN 202310371054A CN 116351367 A CN116351367 A CN 116351367A
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 202
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000012544 monitoring process Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 80
- 238000001816 cooling Methods 0.000 claims description 72
- 238000004140 cleaning Methods 0.000 claims description 36
- 238000001514 detection method Methods 0.000 claims description 23
- 239000000376 reactant Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 18
- 238000011010 flushing procedure Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000011897 real-time detection Methods 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000005070 sampling Methods 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- 239000000523 sample Substances 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000004676 glycans Chemical class 0.000 claims description 9
- 150000002772 monosaccharides Chemical class 0.000 claims description 9
- 229920001282 polysaccharide Polymers 0.000 claims description 9
- 239000005017 polysaccharide Substances 0.000 claims description 9
- 239000000498 cooling water Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229930091371 Fructose Natural products 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- PJVXUVWGSCCGHT-ZPYZYFCMSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;(3s,4r,5r)-1,3,4,5,6-pentahydroxyhexan-2-one Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO PJVXUVWGSCCGHT-ZPYZYFCMSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920001202 Inulin Polymers 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 3
- 229940029339 inulin Drugs 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000006188 syrup Substances 0.000 claims description 3
- 235000020357 syrup Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- BIWJNBZANLAXMG-YQELWRJZSA-N chloordaan Chemical compound ClC1=C(Cl)[C@@]2(Cl)C3CC(Cl)C(Cl)C3[C@]1(Cl)C2(Cl)Cl BIWJNBZANLAXMG-YQELWRJZSA-N 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 241001415288 Coccidae Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention relates to the technical field of biomass high-value utilization, in particular to a device and a method for continuously preparing 5-HMF. The production condition of the 5-HMF is regulated and controlled through intelligent full-range control and real-time monitoring, and sudden emergency is simply treated in time, so that the loss expansion is avoided, and the comprehensive cost of the 5-HMF is saved. The series-parallel reaction kettles are combined, so that the problem of pipeline blockage possibly caused by 5-HMF byproducts in the actual production process is solved, the equipment loss is reduced, meanwhile, a plurality of reaction kettles work relatively independently, the reaction energy consumption is reduced, the production efficiency is greatly improved, the production condition of any reaction kettle can be regulated and controlled at any time, the reaction process can be flexibly switched according to the characteristics of reaction substrates, the higher 5-HMF yield is ensured, and the stable reaction is ensured. The proportion and the type of the catalyst and the cocatalyst as well as the reaction conditions in the system are regulated, so that the generation of the catalyst and the cocatalyst can be reduced from the source, and the method has great significance for the industrialized mass production of 5-HMF and the opening of the production line of subsequent products.
Description
Technical Field
The invention relates to the technical field of biomass high-value utilization, in particular to a device and a method for continuously preparing 5-HMF.
Background
For nearly 300 years, carbon elements stored in fossil are continuously replaced with CO 2 The form enters the atmosphere, so that not only is a great deal of consumption of non-renewable fossil energy sources in a short period caused, but also the carbon circulation balance in the nature is broken. Therefore, in order to reasonably utilize carbon resources, biomass-derived sugars and derivatives thereof, particularly those that can be used as energy sources, are becoming an important point of attention. The high value added chemical 5-HMF (5-hydroxymethylfurfural) of one of the 12 key biomass-derived key platform molecules is even more representative of it.
The 5-HMF molecular monomer has various functional groups, and can generate fine chemicals with high added value, polymer production monomers, clean fuel, industrial chemical materials and the like through hydrogenation, polymerization, esterification and other modes. However, in the conventional industrial production process of 5-HMF, problems such as high production cost caused by factors such as equipment, manpower and efficiency are often surrounded. First, existing equipment often cannot fully meet the production conditions of 5-HMF, such as the production of 5-HMF on a traditional continuous flow bed often generates black byproducts like coke, which are usually produced by molecular polycondensation between the product and the raw materials under high temperature conditions, and are in soft scale, slag block or even compact and hard block shapes according to the polymerization degree and the different reaction systems, and the byproducts are extremely easy to cause pipeline blockage of continuous production equipment after a large amount of deposition in the equipment. On one hand, the equipment loss rate is higher, the production efficiency is reduced, and on the other hand, the unnecessary maintenance cost is increased; meanwhile, when the intermittent and partially continuous traditional reaction kettles are used for reaction, the temperature rising and reducing process not only ensures that the whole reaction energy is large, the production efficiency is low, and the labor cost is increased; in addition, the product 5-HMF is easy to hydrolyze, and the reaction progress is required to be detected and judged in real time, otherwise, the condition of waste of reaction raw materials or excessive reaction can occur; the factors directly and indirectly increase the comprehensive production cost of the 5-HMF, and the application field and the range of the elbow stopper are enlarged.
Disclosure of Invention
First, the technical problem to be solved
The invention aims to solve the technical problems of large energy loss, low production efficiency and high comprehensive cost in the generation process of 5-HMF.
(II) technical scheme
In order to solve the technical problems, in a first aspect, the invention provides a device capable of continuously preparing 5-HMF, which comprises a reaction system, a material throwing system, a heating system, a cleaning system, a cooling system, a reactant real-time detection system, a material collection system and an integrated processing system; the reaction system comprises one or more groups of reaction kettles, a temperature sensing module and a pressure sensing module are arranged in the reaction kettles, a place is provided for catalytic reaction through the reaction kettles, and the reaction conditions in the reaction kettles are detected in real time through the temperature sensing module and the pressure sensing module; the material throwing system is connected with a feed inlet of the reaction system and is used for providing raw material supply for the reaction system, and the material throwing system comprises a storage tank, a material pump and a signal detection and receiving feedback line; the heating system is connected with the reaction system and comprises a heat source and a heat exchanger module, and is used for providing heat for the catalytic reaction of the reaction system; the cleaning system comprises a flow detection module, a cleaning module arranged in the reaction kettle and a flushing pump externally connected with the reaction kettle; the cooling system is connected with the tail end of the reaction system and is used for cooling and collecting reactants after the reaction; the reactant real-time detection system is arranged at the tail end of the reaction system and is used for monitoring the reaction in real time; the material collecting system is connected with a discharge port of the reaction system and is used for collecting reactants for the reaction system, and the material collecting system is an extraction tank or a liquid separating tank; the integrated processing system is respectively connected with the reaction system, the material storage and delivery system, the heating system, the cleaning system, the cooling system, the reactant real-time detection system and the material collection system, so as to control the material delivery, adjust the temperature and pressure in the reaction process, the flow rate of the feeding flow, the cleaning of the reacted equipment and the emergency stop of production.
Further, a plurality of groups of reaction kettles in the reaction system are arranged in a parallel mode, feed inlets of the reaction kettles are respectively connected with the material throwing system, and discharge outlets of the reaction kettles are respectively connected with the material collecting system.
Further, a plurality of groups of reaction kettles in the reaction system are arranged in a serial connection mode, a plurality of groups of reaction kettles are sequentially connected end to end, wherein a feed inlet of a first group of reaction kettles is connected with the material throwing system, and a discharge outlet of a last group of reaction kettles is connected with the material collecting system.
Further, the reactant real-time detection system comprises a UV (ultraviolet) on-line detector or a machine vision detector and a probe thereof, wherein the probes are respectively arranged on pipelines of outlets of the reaction system and the cooling system and two-phase liquid separation positions of the material collecting system, and the UV on-line detector or the machine vision detector is used for detecting samples transmitted by the sampling probes and feeding back detection data to the integrated processing system.
Further, the cooling system is a cooling tank, a spiral cooling water pipe is arranged in an interlayer in the tank body of the cooling tank, and a back pressure valve is added at the position of a liquid flowing through a pipeline of the cooling tank so as to observe the pressure and the flow rate of the reaction system.
Further, the cooling system is a cooling tank, a spiral cooling water pipe is arranged in an interlayer in the tank body of the cooling tank, a nitrogen gas pressurizing interface is arranged on the tank body of the cooling tank, and the pressure inside and outside the tank is regulated by filling nitrogen gas so that liquid flows.
Further, the device also comprises a preheating system, wherein the preheating system is respectively connected with the cooling system and the heating system and is used for recovering heat energy exchanged by the cooling system and heating raw materials step by step.
In a second aspect, the present invention provides a process for the continuous preparation of 5-HMF comprising the steps of: taking monosaccharide and/or polysaccharide, a solvent, a catalyst and a cocatalyst as raw materials, and uniformly mixing to obtain a homogeneous material; preheating the homogeneous materials, and then respectively feeding the materials into a reaction kettle according to different reaction systems; the reactant real-time detection system detects the reaction progress of the reaction kettle in real time and transmits detection information to the integrated processing system for evaluation; the integrated processing system adjusts the flow rate of the material storage and delivery system according to the detection result, controls the feeding amount of the reaction kettle, and regulates and controls the reaction process; and cooling and recycling a product obtained by the reaction to obtain a 5-HMF solution.
Further, the method further comprises a cleaning step, when the cleaning system detects that the temperature of the reaction kettle is lower than 40 ℃, the pressure is reduced, the flow meter is 0, the temperature exceeds 60 minutes, and no other operation is performed, the cleaning system is started spontaneously, and the interior of the reaction kettle is cleaned and flushed by a scraper.
Further, the solvent in the raw materials comprises an aqueous phase solvent and an organic phase solvent, wherein the organic phase solvent is at least one of 4-methyl-2-pentanone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethyl acetate, 1-butanol, gamma-valerolactone, dimethyl carbonate and dimethyl sulfoxide; the temperature of the preheating system is 50-80 ℃, the operating temperature of the reaction kettle is 90-150 ℃, and the retention time of the materials in the reaction kettle is 0.5-3 h; the mass fraction of the monosaccharide and/or polysaccharide is 10-90%, and the monosaccharide and/or polysaccharide is at least one of glucose, fructose, sucrose, maltose, fructose-glucose syrup, cellulose and inulin; the catalyst is one or more of concentrated sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, orthophosphoric acid, citric acid, maleic acid, formic acid, acetic acid, lactic acid and sulfamic acid; the promoter is at least one of p-toluenesulfonamide, sodium chloride, potassium chloride, calcium chloride, aluminum chloride, magnesium chloride, choline chloride and polyethylene glycol.
(III) beneficial effects
The technical scheme of the invention has the following advantages:
1. the production condition of the 5-HMF is regulated and controlled through intelligent full-range control and real-time monitoring, and sudden emergency is simply treated in time, so that the loss expansion is avoided, and the comprehensive cost of the 5-HMF is saved;
2. the series-parallel reaction kettles are combined, so that the problem of pipeline blockage possibly caused by 5-HMF byproducts in the actual production process is solved, the equipment loss is reduced, meanwhile, a plurality of reaction kettles work relatively independently, the reaction energy consumption is reduced, the production efficiency is greatly improved, the production condition of any reaction kettle can be regulated and controlled at any time, the higher 5-HMF yield is ensured, and the reaction is stable;
3. the proportion and the type of the catalyst and the cocatalyst as well as the reaction conditions in the system are regulated, so that the generation of the catalyst and the cocatalyst can be reduced from the source, and the method has great significance for the industrialized mass production of 5-HMF and the opening of the production line of subsequent products.
Drawings
FIG. 1 is a schematic diagram of an apparatus for continuously producing 5-HMF according to the present invention in some embodiments;
FIG. 2 is a schematic diagram of an apparatus for continuously producing 5-HMF according to one embodiment of the invention.
In the figure: 1. an integrated system processor; 2. an aqueous phase pump; 3. a flushing pump; 4. an organic phase pump; 5. a heat exchanger; 6. a reaction kettle; 7. an automatic sampling detector; 8. a cooling tank; 9. a nitrogen gas charging port; 10. an emergency discharge port; 11. a sewage outlet; 12. a back pressure valve; 13. an extraction tank; 14. a steam heat source inlet; 15. flushing the valve; 16. a liquid separating tank; 17. and a three-way valve.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In a first aspect, the invention provides a device capable of continuously preparing 5-HMF, comprising a reaction system, a material throwing system, a heating system, a cleaning system, a cooling system, a reactant real-time detection system, a material collecting system and an integrated processing system.
The reaction system comprises one or more groups of reaction kettles 6, a temperature sensing module and a pressure sensing module are arranged in the reaction kettles 6, and the temperature sensor and the pressure sensor are respectively connected with the integrated processing system. And a place is provided for the catalytic reaction through the reaction kettle 6, and the reaction conditions in the reaction kettle 6 are detected in real time through the temperature sensing module and the pressure sensing module. The lining of the reaction kettle 6 and the part of the conveying pipeline are all made of polytetrafluoroethylene with high temperature resistance, acid resistance and alkali resistance.
The material throwing system is connected with a feed inlet of the reaction system and is used for providing raw material supply for the reaction system, and the material throwing system comprises a storage tank, a material pump and a signal detection and receiving feedback line; the storage tank is provided with a liquid level recording sensor and is used for daily recording of the material condition of the storage tank; or is provided with a flow regulating device and is connected with the integrated processing system.
The heating system is connected with the reaction system, and comprises a heat source and a heat exchanger 5 module for providing heat for the catalytic reaction of the reaction system.
The cleaning system comprises a flow detection module, a cleaning module arranged in the reaction kettle 6 and a flushing pump 3 externally connected with the reaction kettle 6. The cleaning module is a spiral scraper, the spiral scraper is made of polytetrafluoroethylene, the spiral scraper is placed at the top of the reaction kettle 6, when the temperature is less than 40 ℃, the pressure is greatly reduced, the flow meter is automatically started when the flow meter is 0 to exceed 60 minutes and no other operation is performed, meanwhile, the flushing pump 3 is started, the scraper of the reaction kettle 6 is cleaned and flushed simultaneously, the flushing time is recorded as one cycle, the circulation times can be set as required, the operation is stopped, and the solid by-product humus generated by the reaction is scraped.
The cooling system is connected with the tail end of the reaction system and is used for cooling and collecting reactants after the reaction. The cooling system is a double-layer higher tank body, and a spiral cooling water pipe is arranged in an interlayer inside the cooling tank 8; the top of the tank body of the cooling tank 8 is provided with a safety valve, the middle of the tank body is provided with a continuous discharge port, and the bottom of the tank body is provided with an inverted cone-shaped discharge and cleaning port; the tank body is provided with a back pressure valve 12, a safety valve, a pressure sensor, a temperature sensor and a detector.
The reactant real-time detection system is arranged at the tail end of the reaction system and is used for monitoring the reaction in real time; the signals are instantaneously transmitted to the material throwing system and the reaction system to regulate the flow speed and the flow quantity in time.
The material collecting system is connected with a discharge hole of the reaction system and is used for collecting reactants for the reaction system, and the material collecting system is an extraction tank 13 or a liquid separating tank 16.
The integrated processing system is respectively connected with the reaction system, the material storage and delivery system, the heating system, the cleaning system, the cooling system, the reactant real-time detection system and the material collection system, so as to control the material delivery, adjust the temperature and pressure in the reaction process, the flow rate of the feeding flow, the cleaning of the reacted equipment and the emergency stop of production.
In some embodiments, the reaction kettles 6 in the reaction system are arranged in parallel, the feed inlets of the reaction kettles 6 are respectively connected with the material throwing system, the discharge outlets of the reaction kettles 6 are respectively connected with the material collecting system, and the parallel kettle-type reactors can perform kettle-type reaction relatively independently, so that the conditions of the reaction kettles 6 can be changed simultaneously, and the working quantity of the reaction kettles 6 can be adjusted in real time as required.
In some embodiments, the reaction kettles 6 in the reaction system are arranged in a series connection manner, the reaction kettles 6 are connected end to end in sequence, wherein the feed inlet of the first group of reaction kettles 6 is connected with the material throwing system, the discharge outlet of the last group of reaction kettles 6 is connected with the material collecting system, and the series kettle type reactor can bear the larger pressure generated by the reaction, continuously perform the reaction, and improve the productivity and the production efficiency.
In some embodiments, the reactant real-time detection system includes a UV on-line detector or a machine vision detector and a probe thereof, where the probes are respectively disposed on the pipelines of the outlets of the reaction system and the cooling system and at the two-phase liquid separation position of the material collection system, and the UV on-line detector or the machine vision detector is used to detect the sample transmitted from the sampling probe and feed the detection data back to the integrated processing system, and the integrated processing system can adjust the total amount of the material put into the reaction kettle 6 according to the data, and can monitor the reaction progress and timely adjust the reaction progress when the reaction is abnormal.
In some embodiments, the cooling system is a cooling tank 8, a spiral cooling water pipe is arranged in an interlayer in the tank body of the cooling tank 8, and the back pressure valve 12 is added to the cooling tank 8 at the position where the liquid flows through a pipeline so as to observe the pressure and the flow rate of the reaction system.
In some embodiments, the cooling system is a cooling tank 8, a spiral cooling water pipe is arranged in an interlayer in the tank body of the cooling tank 8, a nitrogen pressurizing interface is arranged on the tank body of the cooling tank 8, and the pressure inside and outside the tank is regulated by charging nitrogen so as to enable liquid to flow.
In some embodiments, the device further comprises a preheating system, wherein the preheating system is respectively connected with the cooling system and the heating system and is used for recovering heat energy exchanged by the cooling system and heating raw materials step by step so as to save the heat energy.
In a second aspect, the present invention provides a process for the continuous preparation of 5-HMF comprising the steps of:
taking monosaccharide and/or polysaccharide, a solvent, a catalyst and a cocatalyst as raw materials, and uniformly mixing to obtain a homogeneous material;
preheating the homogeneous materials, and then respectively feeding the materials into a reaction kettle 6 according to different reaction systems;
the reactant real-time detection system detects the reaction progress of the reaction kettle 6 in real time and transmits detection information to the integrated processing system for evaluation;
the integrated processing system adjusts the flow rate of the material storage and delivery system according to the detection result, controls the feeding amount of the reaction kettle 6, and regulates and controls the reaction process;
and cooling and recycling a product obtained by the reaction to obtain a 5-HMF solution.
In some embodiments, the method further comprises a cleaning step, when the cleaning system detects that the temperature of the reaction kettle 6 is less than 40 ℃, the pressure is reduced, the flow meter is displayed as 0, the temperature exceeds 60 minutes, and no other operation is performed, the cleaning system is started spontaneously, and the interior of the reaction kettle 6 is cleaned and flushed by a scraper.
In some embodiments, the solvent in the feedstock comprises an aqueous phase solvent and an organic phase solvent, the organic phase solvent being at least one of 4-methyl-2-pentanone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethyl acetate, 1-butanol, gamma valerolactone, dimethyl carbonate, dimethyl sulfoxide; the temperature of the preheating system is 50-80 ℃, the operating temperature of the reaction kettle 6 is 90-150 ℃, and the retention time of the materials in the reaction kettle 6 is 0.5-3 h; the mass fraction of the monosaccharide and/or polysaccharide is 10-90%, and the monosaccharide and/or polysaccharide is at least one of glucose, fructose, sucrose, maltose, fructose-glucose syrup, cellulose and inulin; the catalyst is one or more of concentrated sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, orthophosphoric acid, citric acid, maleic acid, formic acid, acetic acid, lactic acid and sulfamic acid; the promoter is at least one of p-toluenesulfonamide, sodium chloride, potassium chloride, calcium chloride, aluminum chloride, magnesium chloride, choline chloride and polyethylene glycol.
Example 1:
as shown in FIG. 1, the preparation method of the 5-HMF in the parallel system provided by the invention comprises the following steps:
300kg of fructose, 500kg of 75% chlordane aqueous solution and 1kg of concentrated sulfuric acid are weighed, and the fructose, the chlordane aqueous solution and the concentrated sulfuric acid are stirred and dissolved and then marked as water phase materials.
The reaction is carried out by the equipment shown in fig. 1, during normal operation, the system is maintained at 100-110 ℃ by heat source steam, the water phase pump 2 pumps water phase raw materials at a rate of 1L/min, the flushing pump 3 is closed, the water phase materials respectively enter from the upper end of the parallel reaction kettle 6 through the heat exchanger 5, and the water phase raw materials are filled into about 2/3 of the volume for reaction. The obtained materials respectively pass through the automatic sampling detectors 7 at the tail ends of the reaction kettles 6 and then enter the cooling tank 8, and meanwhile, the automatic sampling detectors 7 transmit test results to the integrated system processor 1.
The integrated system processor 1 evaluates the reaction progress of the reaction kettle 6 in real time, firstly, signals acquired by the automatic sampling detector 7 are transmitted to the integrated system processor 1, the integrated system processor 1 analyzes the material results after the reaction, and the flow rate and the flow velocity of the pump are regulated according to the detection results, so that the feeding amount of the reaction kettle 6 is controlled, and the reaction progress is regulated.
When the detection result is analyzed by the integrated system processor 1 to obtain a conclusion that the reaction is insufficient, the integrated system processor 1 adjusts a flow regulating device of the object storage and delivery system to reduce the flow rate of a pump, reduce the concentration of materials in the reaction kettle 6 in unit time and prolong the reaction time; when the detection result is analyzed by the integrated system processor 1 to obtain a conclusion of excessive reaction, the integrated system processor 1 adjusts the flow rate of the flow regulating device of the object storage and delivery system, so that the concentration of materials in the reaction kettle 6 in unit time is increased, and the reaction time is shortened.
After the materials obtained by the reaction enter a cooling tank 8, the materials are cooled to 40-50 ℃ in the cooling tank 8. The upper part of the side surface of the cooling tank 8 is provided with a nitrogen charging port 9, the internal and external air pressure is balanced so as to facilitate the circulation of feed liquid, and the pressure of the system is automatically controlled. The lower end of the side surface of the cooling tank 8 is provided with an automatic sampling detector 7, the cooling liquid of the cooling tank 8 is sampled and tested at intervals, and the detection result is transmitted to the integrated system processor 1 for analysis. The cooling tank 8 is also provided with an emergency discharge opening 10, which can be immediately discharged in case of emergency and is closed in normal operation. In addition, the bottom of the cooling tank 8 is also provided with a drain outlet 11, and the drain outlet 11 is mainly used for discharging byproducts deposited at the bottom of the tank during cooling. The cooled reaction mass is led to an automatic extraction tank 13 via a liquid back pressure valve 12 connected to the side of the cooling tank 8.
After the cooled material enters the automatic extraction tank 13, the extraction tank 13 is internally and automatically extracted by an organic solvent, the automatic sampling detector 7 of the extraction tank 13 samples and detects the two-phase solution respectively at intervals, the detection result is transmitted to the integrated system processor 1 for analysis, the extraction progress is judged, and the extraction is regulated and controlled by the integrated control unit to be discharged from the discharge port after the extraction is finished.
The parallel reaction kettles 6 are respectively provided with a steam heat source inlet 14, and the heat source inlets are opened during normal reaction. When a certain reaction kettle 6 connected in parallel cannot be operated or needs to be replaced, the feeding valve of the reaction kettle 6 and the steam heat source inlet 14 can be closed for maintenance or replacement, and other parallel reaction kettles 6 cannot be affected.
In addition, the parallel reactor 6 is easy to clean and maintain. If the series reaction kettle 6 is cleaned, when the flow is 0 and no other operation exists in 60min, the self-cleaning scraper in the reaction kettle 6 is started, meanwhile, the flushing pump 3 is opened, the flushing valve 15 at the bottom of the parallel reaction kettle 6 is respectively opened, the cleaning scraper can be set to clean for 15min, during which the flushing pump 3 continues to run for 45min and is recorded as a cycle, the self-cleaning system is closed after the general cycle is performed for 3 times, and the cleaning time, the flushing time and the cycle times of the scraper can be changed as required.
By detecting and analyzing the material after the reaction, the molar yield of 5-HMF was found to be 50%.
Example 2:
as shown in FIG. 2, the preparation method of the 5-HMF in the serial system provided by the invention comprises the following steps:
300kg of fructose, 200kg of water and 1kg of concentrated sulfuric acid are weighed, stirred and dissolved and marked as a water phase raw material, and 750kg of dimethyl carbonate is marked as an organic phase raw material.
The reaction is carried out by the equipment of FIG. 2, the back pressure valve 12 regulates the pressure to be 1.5Mpa during normal operation, the system is maintained between 130 ℃ and 140 ℃ by heat source steam, the water phase pump 2 and the organic phase pump 4 pump the water phase raw material and the organic phase raw material at the speed of 1L/min and 2.5L/min respectively, and the flushing pump 3 is closed. The water phase material flow is preheated by the heat exchanger 5 and then sequentially enters the series reaction kettle 6 for reaction through the three-way valve 17. The material obtained after the reaction is fed into an automatic sampling detector 7 arranged at the tail end of the reaction, and then fed into a cooling tank 8 for cooling. At the same time the auto-sampling detector 7 transmits the test results to the integrated system processor 1.
After the materials obtained by the reaction enter a cooling tank 8, the materials are cooled to 40-50 ℃ in the cooling tank 8. The upper part of the side surface of the cooling tank 8 is provided with a nitrogen charging port 9 for balancing the internal and external air pressure so as to facilitate the circulation of feed liquid, the system pressure is automatically controlled, and the outlet of the cooling tank 8 is provided with a gas back pressure valve 12. The lower side of the cooling tank 8 is provided with an emergency discharge opening 10 which is closed during normal operation. The bottom of the cooling tank 8 is also provided with a drain outlet 11, and the drain outlet 11 is mainly used for cleaning and discharging sediment at the bottom of the cooling tank 8. The lower end of the side surface of the cooling tank 8 is also provided with an automatic sampling detector 7, samples and tests the cooling liquid of the cooling tank 8 at intervals, and transmits the detection result to the integrated system processor 1 for analysis. In addition, the cooled reaction mass is cooled to a certain temperature and then passed to a liquid separation tank 16. The two-phase solution is sampled and detected by the automatic sampling detector 7 at intervals, and the detection result is transmitted to the integrated system processor 1 for analysis, the condition of the material in the liquid separating tank 16 is judged, and then the integrated processor regulates and controls the material to be discharged from the discharge opening.
The series reaction kettles 6 are respectively provided with steam heat source inlets 14. In normal operation, the heat source inlet is open. If a certain reaction kettle 6 breaks down and needs to be maintained or when the reaction kettles 6 do not need to work together, the reaction kettles 6 can be replaced or subjected to pipeline short-circuiting treatment, and after the short-circuiting treatment, the reaction kettles 6 can be independently cleaned and maintained for later use.
In addition, if the tandem reaction kettle 6 is cleaned after the equipment is normally operated, the flushing pump 3 can be connected by a pipeline, when the flow is 0 and no other operation exists in 60min, the self-cleaning scraper in the reaction kettle 6 is started, meanwhile, the flushing pump 3 is opened, the cleaning scraper can be set to clean for 15min, the cleaning is performed for 30min, 45min is recorded as one cycle, the self-cleaning system is closed after the normal cycle is performed for 3 times, the three-way valve 17 is used for flushing the outlet, and the flushing solvent is discharged. The solvent may also be selected as desired, changing the blade cleaning time, rinsing time and cycle times.
By subjecting the post-reaction mixture to detection analysis, the molar yield of 5-HMF was found to be 70%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (10)
1. The device capable of continuously preparing the 5-HMF is characterized by comprising a reaction system, a material throwing system, a heating system, a cleaning system, a cooling system, a reactant real-time detection system, a material collecting system and an integrated processing system;
the reaction system comprises one or more groups of reaction kettles, a temperature sensing module and a pressure sensing module are arranged in the reaction kettles, a place is provided for catalytic reaction through the reaction kettles, and the reaction conditions in the reaction kettles are detected in real time through the temperature sensing module and the pressure sensing module;
the material throwing system is connected with a feed inlet of the reaction system and is used for providing raw material supply for the reaction system, and the material throwing system comprises a storage tank, a material pump and a signal detection and receiving feedback line;
the heating system is connected with the reaction system and comprises a heat source and a heat exchanger module, and is used for providing heat for the catalytic reaction of the reaction system;
the cleaning system comprises a flow detection module, a cleaning module arranged in the reaction kettle and a flushing pump externally connected with the reaction kettle;
the cooling system is connected with the tail end of the reaction system and is used for cooling and collecting reactants after the reaction;
the reactant real-time detection system is arranged at the tail end of the reaction system and is used for monitoring the reaction in real time;
the material collecting system is connected with a discharge port of the reaction system and is used for collecting reactants for the reaction system, and the material collecting system is an extraction tank or a liquid separating tank;
the integrated processing system is respectively connected with the reaction system, the material storage and delivery system, the heating system, the cleaning system, the cooling system, the reactant real-time detection system and the material collection system, so as to control the material delivery, adjust the temperature and pressure in the reaction process, the flow rate of the feeding flow, the cleaning of the reacted equipment and the emergency stop of production.
2. The device for continuously preparing 5-HMF according to claim 1, wherein a plurality of groups of reaction kettles in the reaction system are arranged in parallel, feed inlets of the reaction kettles are respectively connected with the material throwing system, and discharge outlets of the reaction kettles are respectively connected with the material collecting system.
3. The device for continuously preparing 5-HMF according to claim 1, wherein a plurality of groups of reaction kettles in the reaction system are arranged in a serial manner, the plurality of groups of reaction kettles are sequentially connected end to end, wherein a feed inlet of a first group of reaction kettles is connected with the material throwing system, and a discharge outlet of a last group of reaction kettles is connected with the material collecting system.
4. The apparatus for continuously preparing 5-HMF according to claim 1, wherein the reactant real-time detection system comprises a UV on-line detector or a machine vision detector and a probe thereof, the probe is respectively disposed on the pipelines of the outlets of the reaction system and the cooling system and at the two-phase liquid separation position of the material collection system, and the UV on-line detector or the machine vision detector is used for detecting the sample transmitted from the sampling probe and feeding back the detection data to the integrated processing system.
5. The apparatus for continuously preparing 5-HMF as set forth in claim 1, wherein the cooling system is a cooling tank having a spiral cooling water pipe interposed in a tank body, and the cooling tank is provided with a back pressure valve at a position where the liquid flows through the pipe to observe the pressure and flow rate of the reaction system.
6. The device for continuously preparing 5-HMF according to claim 1, wherein the cooling system is a cooling tank, a spiral cooling water pipe is arranged in an interlayer in the tank body of the cooling tank, a nitrogen gas pressurizing interface is arranged on the tank body of the cooling tank, and the pressure inside and outside the tank is regulated by charging nitrogen gas so as to enable liquid to flow.
7. An apparatus for continuously producing 5-HMF according to any one of claims 1 to 6, further comprising a preheating system connected to the cooling system and the heating system, respectively, for recovering heat energy exchanged by the cooling system and heating the raw material stepwise.
8. A process for the continuous preparation of 5-HMF, comprising the steps of:
taking monosaccharide and/or polysaccharide, a solvent, a catalyst and a cocatalyst as raw materials, and uniformly mixing to obtain a homogeneous material;
preheating the homogeneous materials, and then respectively feeding the materials into a reaction kettle according to different reaction systems;
the reactant real-time detection system detects the reaction progress of the reaction kettle in real time and transmits detection information to the integrated processing system for evaluation;
the integrated processing system adjusts the flow rate of the material storage and delivery system according to the detection result, controls the feeding amount of the reaction kettle, and regulates and controls the reaction process;
and cooling and recycling a product obtained by the reaction to obtain a 5-HMF solution.
9. A method for continuously preparing 5-HMF according to claim 8, further comprising the step of cleaning the inside of the reaction vessel by self-starting the cleaning system when the cleaning system detects that the temperature of the reaction vessel is less than 40 ℃, the pressure is reduced and the flow meter is 0, more than 60min, and no other operation is performed.
10. The method for continuously preparing 5-HMF according to claim 8, wherein the solvent in the raw material comprises an aqueous phase solvent and an organic phase solvent, and the organic phase solvent is at least one of 4-methyl-2-pentanone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethyl acetate, 1-butanol, gamma-valerolactone, dimethyl carbonate and dimethyl sulfoxide; the temperature of the preheating system is 50-80 ℃, the operating temperature of the reaction kettle is 90-150 ℃, and the retention time of the materials in the reaction kettle is 0.5-3 h; the mass fraction of the monosaccharide and/or polysaccharide is 10-90%, and the monosaccharide and/or polysaccharide is at least one of glucose, fructose, sucrose, maltose, fructose-glucose syrup, cellulose and inulin; the catalyst is one or more of concentrated sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, orthophosphoric acid, citric acid, maleic acid, formic acid, acetic acid, lactic acid and sulfamic acid; the promoter is at least one of p-toluenesulfonamide, sodium chloride, potassium chloride, calcium chloride, aluminum chloride, magnesium chloride, choline chloride and polyethylene glycol.
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| WO2024012518A1 (en) * | 2022-07-14 | 2024-01-18 | 中科国生(杭州)科技有限公司 | Production process and device for continuously producing 5-hydroxymethylfurfural |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024012518A1 (en) * | 2022-07-14 | 2024-01-18 | 中科国生(杭州)科技有限公司 | Production process and device for continuously producing 5-hydroxymethylfurfural |
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