CN111185205B - Supported catalyst and application thereof in preparation of hydroxyalkyl acrylate - Google Patents
Supported catalyst and application thereof in preparation of hydroxyalkyl acrylate Download PDFInfo
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- CN111185205B CN111185205B CN202010116498.3A CN202010116498A CN111185205B CN 111185205 B CN111185205 B CN 111185205B CN 202010116498 A CN202010116498 A CN 202010116498A CN 111185205 B CN111185205 B CN 111185205B
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- catalyst
- iron
- copper
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- zinc
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- -1 hydroxyalkyl acrylate Chemical compound 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000004820 halides Chemical class 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 229940048053 acrylate Drugs 0.000 description 18
- 238000005886 esterification reaction Methods 0.000 description 10
- 230000032050 esterification Effects 0.000 description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001263 acyl chlorides Chemical class 0.000 description 6
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a supported catalyst and application thereof in preparing hydroxyalkyl acrylate, wherein the catalyst is obtained by loading any one simple substance, oxide, sulfate and halide of metal magnesium, calcium, iron, copper, zinc or aluminum on a carrier, and the weight ratio of the simple substance, oxide, sulfate and halide of metal magnesium, calcium, iron, copper, zinc and aluminum is 1:1 to 3:1 to 10: 1-5, the weight dosage of the carrier is 1-5 times of the total weight dosage of simple substances, oxides, sulfates and halides of magnesium, calcium, iron, copper, zinc and aluminum. The catalyst used in the invention has the advantages of cheap and easily available components, low manufacturing cost, simple operation process, mild conditions, convenient post-treatment, high activity of the catalyst, long service life and repeated use after regeneration. The catalyst is used for preparing the hydroxyalkyl acrylate, has simple process and safe production process, does not need a polymerization inhibitor, and can be continuously carried out, the conversion rate of raw materials is more than 96 percent, and the purity of products is more than 99 percent.
Description
Technical Field
The invention relates to a catalyst, in particular to a supported catalyst and application of the supported catalyst in preparation of hydroxyalkyl acrylate.
Background
The hydroxyalkyl acrylate is an important chemical raw material, is a colorless and transparent liquid and has two functional groups of carbon-carbon double bond and hydroxyl. The product has active property and wide application range, and is mainly used for fiber processing, paint, light-cured resin, adhesive, paper processing, rubber industry and the like. The material has a certain representativeness in terms of the characteristics of the preparation process and the material. The hydroxyalkyl acrylate as the special acrylate has seven synthetic process routes: 1) The ring-opening reaction method is to introduce alkylene oxide into acrylic acid and react under the action of catalyst and inhibitor to produce hydroxyalkyl acrylate and small amount of side product directly. The ring-opening reaction method is reasonable from the economical point of view, and is a general method for preparing hydroxyalkyl acrylate at present. The method has the characteristics of quick reaction, low reaction temperature, less side reaction, particularly less polymerization reaction, high reaction yield up to about 95 percent, simple post-treatment, easy distillation to obtain high-purity products and suitability for large-scale production. The method has the disadvantages of strict requirements on production equipment and operation conditions and high technical level requirements. 2) The one-step method is that acrylic acid, chlorohydrin and sodium hydroxide solid are heated to react, and the reaction end point is determined by analyzing the content of sodium chloride by a silver nitrate method. When the reaction reaches a certain conversion rate, the reaction is stopped. After cooling, sodium chloride produced by the reaction and unreacted sodium acrylate were filtered off under reduced pressure using a Buchner funnel. Adding a certain amount of diethylene glycol and hydroquinone into the obtained reaction mother liquor, carrying out reduced pressure distillation to separate out excessive chlorohydrin, and collecting hydroxyalkyl acrylate fractions. The one-step process is fast but the conversion increases very slowly by the end and the polymer increases with time. The chlorohydrin is in excess to ensure completion of the reaction, but the reaction solution is too viscous, which makes the reaction and separation difficult. The temperature has large influence on the reaction, the temperature is increased, the reaction rate is accelerated, but under the condition of pressurization and temperature rise, the polymerization is easy to occur, and the industrialization is difficult. 3) The direct esterification method is a reversible reaction of bimolecular, and is carried out under the catalysis of acid, and commonly used catalysts are sulfuric acid, hydrochloric acid, sulfonic acid, tin salt, organic titanate, cation exchange resin and the like. In view of corrosion of equipment in industry, benzenesulfonic acid, p-toluenesulfonic acid or cation exchange resins are generally used as catalysts. The direct esterification method is slow in reaction at low temperature, and the reaction temperature is often increased to increase the reaction rate; however, the esterification yield is low in the esterification process, and the selectivity problem of the monoester and the diester exists. In the prior art, concentrated hydrochloric acid is used as a catalyst, benzene is used as a water-carrying agent to synthesize hydroxyethyl acrylate, and a reaction mixed solution is subjected to neutralization, filtration and reduced pressure distillation to obtain a product, wherein the yield is 64%. The 001X 7 strong acid type cation exchange resin is used as a catalyst for synthesizing hydroxyethyl acrylate in high-class Changyan in China, the conversion rate reaches over 90 percent, the yield reaches 78.2 percent, and the purity reaches 98.1 percent. 4) The ester exchange method is that dihydric alcohol and methyl acrylate are subjected to ester exchange reaction, the ester exchange is generally carried out by methyl (ethyl) acrylate and the dihydric alcohol, and commonly used catalysts are strong bases such as sodium alkoxide, magnesium alkoxide, sodium hydroxide, calcium hydroxide, tetramethylammonium hydroxide and hexadecyltrimethylammonium hydroxide and strong acids such as concentrated sulfuric acid and sulfonic acid. In 1984, a czech researcher adopts tetramethylammonium hydroxide as a catalyst to obtain high-purity hydroxyethyl methacrylate only containing 0.1-0.3 percent of ethylene glycol dimethacrylate. Cheap methyl methacrylate reacts with ethylene glycol at home, hydroquinone is used as a polymerization inhibitor under the catalysis of hexadecyl trimethyl ammonium hydroxide to synthesize the hydroxyethyl methacrylate, and the yield is 92.3 percent. 5) The acyl chloride esterification method is characterized in that dihydric alcohol reacts with acryloyl chloride, and the acyl chloride and alcohol are subjected to esterification reaction in the presence of an acid remover (such as sodium ethoxide, sodium carbonate, pyridine, triethylamine, picoline and other alkaline substances) to generate ester. This is an irreversible reaction, the esterification of the acid chloride proceeds very easily and the acylation ability is stronger than that of the corresponding acid anhydride. The esterification of acyl chloride in the acyl chloride esterification method has the following advantages: (1) the byproduct generated in the acyl chloride reaction is hydrogen chloride gas which is easy to remove; (2) the acyl chloride has strong reactivity, high reaction rate and lower reaction temperature; (3) HCl generated in the esterification reaction can be removed with an acid remover to generate insoluble ammonium salt, so that the reaction is complete and the yield is high. However, the cost of acid chlorides is much higher than that of the corresponding carboxylic acids, and thus, the industrial application thereof is very limited. 6) Under the catalysis of alkaline resin and the protection of nitrogen, dihydric alcohol carbonate reacts with acrylic acid to prepare hydroxyalkyl acrylate. The advantage of the reaction of the glycol carbonate with acrylic acid is that the carbon dioxide formed in the reaction is easily removed. The disadvantages are long reaction time, high reaction temperature, easy generation of side reaction and low yield. 7) The chlorohydrin process is the reaction of a carboxylic acid salt with an active halide (or benzylic halide) to form an ester. Acrylic acid is first converted to sodium acrylate which is then reacted with chlorohydrin to form the hydroxyalkyl acrylate. The chlorohydrin method has the advantages of rapid reaction, mild conditions and safe production process. However, since the inorganic salt is precipitated during the reaction, the operation and the post-treatment are troublesome.
In the research of hydroxyalkyl acrylate catalysts, the catalysts used at home and abroad at present can be roughly classified into chromium-based, iron-based, copper-based, cobalt-based organic amines and the like, the chromium-based catalysts have high activity and high selectivity, but the catalysts are difficult to prepare, need to be matched with special auxiliaries and polymerization inhibitors, chromium is heavy metal, and chromium in refined residual liquid is difficult to recover and treat, so that the pollution to the environment is large. Iron series, copper series, cobalt series and organic amine catalysts are environment-friendly catalysts and belong to clean production technology. However, cobalt-based catalysts are limited by the source of raw materials and are difficult to scale up; the iron-based and copper-based catalysts have short service life and high production cost, and are required to be further researched.
The carbon-silicon material is considered to be a good carrier, has good hydrothermal stability, large specific surface area and rich pore structure, and is easy to load metal by a simple method. Modification of carbon materials can significantly change the valence electron cloud of the carbon materials, increase defect sites, increase the adsorption capacity of reactants, and the like, which may be beneficial to the progress of catalytic reactions or change product distribution, and the like. Therefore, the method for preparing the metal carbon-based heterogeneous catalyst with high activity, high stability and long service life by using the acrylic acid and the alkylene oxide as raw materials to carry out condensation reaction and using the carbon-silicon material as a simple carrier to be compounded with the metal simple substance and the compound thereof is a good development direction in the field of catalysis.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel supported catalyst, which can prepare hydroxyalkyl acrylate products with high conversion rate and high purity by using acrylic acids and alkylene oxide as raw materials at low cost.
In order to solve the technical problem, the invention discloses a supported catalyst which is obtained by loading any one simple substance, oxide, sulfate and halide of metal magnesium, calcium, iron, copper, zinc or aluminum on a carrier,
the weight ratio of the simple substances, oxides, sulfates and halides of the metal magnesium, calcium, iron, copper, zinc and aluminum is 1:1 to 3:1 to 10:1 to 5 of the total weight of the mixture,
the weight consumption of the carrier is 1-5 times of the total weight consumption of simple substances, oxides, sulfates and halides of magnesium, calcium, iron, copper, zinc and aluminum.
Furthermore, the oxides of the metals of magnesium, calcium, iron, copper, zinc and aluminum are MgO, caO, feO and Cu 2 O、CuO、ZnO、Al 2 O 3 Any one of them.
Further, the sulfate of the metal magnesium, calcium, iron, copper, zinc and aluminum is MgSO 4 、CaSO 4 、FeSO 4 、Cu 2 SO 4 、CuSO 4 、ZnSO 4 、Al 2 (SO 4 ) 3 Any one of them.
Further, the halide of the metal magnesium, calcium, iron, copper, zinc and aluminum is MgCl 2 、MgBr 2 、CaCl 2 、CaBr 2 、FeCl 2 、CuCl、CuCl 2 、CuBr、CuBr 2 、ZnCl 2 、AlCl 3 Any one of them.
Further, the carrier is one or a mixture of more than two of active carbon, carbon fiber or diatomite.
Further, the catalyst is prepared by the following method:
putting any simple substance of magnesium, calcium, iron, copper, zinc or aluminum, oxide, sulfate, halide and carrier into a reactor according to a certain proportion, fully mixing, drying for 3 hours at 110 ℃, grinding into powder by a grinder, replacing for 3 times by high-purity nitrogen, and vacuumizing for 3 hours under a vacuum pump of-60 to-80 kPa to obtain the catalyst.
The invention also discloses an application of the supported catalyst in preparation of hydroxyalkyl acrylate, wherein the hydroxyalkyl acrylate is prepared by taking acrylic acid and alkylene oxide as reaction raw materials and performing ring-opening reaction.
Further, separately mixing acrylic acid and toluene in a weight ratio of 1:1, adding the mixture into a preheater, preheating and gasifying the mixture, and then introducing the mixture into a tubular reactor;
in a further mixer, alkylene oxide and nitrogen are mixed in a weight ratio of 1:1 mixing and then introducing into a tubular reactor;
the tubular reactor is filled with the supported catalyst,
at the temperature of 120-200 ℃ and 1-10 kg/cm 2 Reacting under absolute pressure, after the reaction is finished, distilling the materials into a condensation separation tower for separation to obtain hydroxyalkyl acrylate;
the molar ratio of the acrylic acid to the alkylene oxide is 1:1 to 1.6.
After the reaction product is metered, the reaction product is analyzed and detected by gas chromatography. The gas chromatography detection conditions comprise that a chromatographic column is an elastic quartz capillary column with the diameter of 30m multiplied by 0.32mm multiplied by 0.5 mu m, SE 254 (high inertia crosslinking), the column temperature is 160 ℃, the detector temperature is 250 ℃, the vaporization temperature is 270 ℃, and the sample injection amount is 0.4L.
Further, the acrylic is methacrylic acid or acrylic acid.
Further, the alkylene oxide is ethylene oxide or propylene oxide.
When different acrylic acids and alkylene oxides are used, the hydroxyalkyl acrylate obtained by the invention can be four types of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
The invention has the following beneficial effects:
1) The catalyst used in the invention has the advantages of cheap and easily available components, low manufacturing cost, simple operation process, mild conditions, convenient post-treatment, high activity of the catalyst, long service life and repeated use after regeneration.
2) The catalyst is used for preparing the hydroxyalkyl acrylate, the process is simple, the production process is safe, a polymerization inhibitor is not needed in the reaction due to the adoption of the combination of specific metal simple substances, oxides, sulfates and halides, the production process can be continuously carried out, the conversion rate of raw materials reaches more than 96%, and the purity of products reaches more than 99%.
Detailed Description
The present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples, and any modification or variation of the present invention is within the scope of the present invention.
Example 1 preparation of catalyst 1
Mixing Mg 1kg, mgO 1kg, mgSO 4 5kg、MgCl 2 1kg of activated carbon (8 kg) was thoroughly mixed in a reactor, dried at 110 ℃ for 3 hours, ground into powder with a grinder, replaced with high-purity nitrogen gas for 3 times, evacuated with a vacuum pump of-60 kPa for 3 hours, and then directly charged into a tubular reactor.
Example 2 preparation of catalyst 2
Adding Zn 1kg, mgO 3kg and CuSO 4 5kg、MgCl 2 1kg and 15kg of active carbon are fully mixed in a reactor, dried for 3 hours at 110 ℃, ground into powder by a grinder, replaced by high-purity nitrogen for 3 times, vacuumized for 3 hours under a vacuum pump of 60 kPa, and directly filled into a tubular reactor.
Example 3 preparation of catalyst 3
1kg of Zn, 1kg of FeO and CuSO 4 10kg、MgCl 2 1kg and 26kg of carbon fiber are fully mixed in a reactor, dried for 3 hours at 110 ℃, ground into powder by a grinder, replaced by high-purity nitrogen for 3 times, vacuumized for 3 hours under a vacuum pump of 60 kPa, and directly filled into a tubular reactor.
Example 4 preparation of catalyst 4
Mixing Al 1kg, cuO 3kg and FeSO 4 1kg、AlCl 3 5kg, 10kg of activated carbon, 10kg of carbon fiber and 10kg of diatomite are fully mixed in a reactor, dried for 3 hours at 110 ℃, ground into powder by a grinder, replaced by high-purity nitrogen for 3 times, vacuumized for 3 hours under a vacuum pump of-60 kPa, and then directly filled into a tubular reactor.
Example 5 preparation of catalyst 5
1kg of Zn, 1kg of CuO and CuSO 4 10kg、AlCl 3 1kg, 15kg of activated carbon and 15kg of diatomite are fully mixed in a reactor, then dried for 3 hours at 110 ℃, ground into powder by a grinder, replaced by high-purity nitrogen for 3 times, vacuumized for 3 hours under a vacuum pump of-60 kPa, and then directly filled into a tubular reactor.
EXAMPLE 6 preparation of hydroxyethyl acrylate
Adding 72 kg/h of acrylic acid and 72 kg/h of toluene into a preheater for preheating and gasifying, and then introducingA tubular reactor already charged with catalyst 1; at the same time, 45 kg/h of ethylene oxide and 45 kg/h of nitrogen were mixed in a further mixer and introduced into the tubular reactor which had been charged with catalyst 1. At 120 ℃ under a reaction pressure of 1kg/cm 2 The reaction is carried out under absolute pressure, the materials are distilled into a condensation separation tower for separation, and 112 kg/h of hydroxyethyl acrylate is obtained, the conversion rate is 96.6 percent, and the purity is 99.2 percent.
EXAMPLE 7 preparation of hydroxypropyl acrylate
Adding 72 kg/h of acrylic acid and 72 kg/h of toluene into a preheater, preheating and gasifying the acrylic acid and the toluene, and introducing the acrylic acid and the toluene into a tubular reactor filled with a catalyst 1; simultaneously, 92 kg/h of propylene oxide and 92 kg/h of nitrogen were mixed in a further mixer and then fed into the tubular reactor containing catalyst 1. At 200 ℃, the reaction pressure is 1kg/cm 2 The reaction is carried out under absolute pressure, and the materials are distilled into a condensation separation tower for separation to obtain 126 kg/h of hydroxypropyl acrylate, the conversion rate is 96.2 percent, and the purity is 99.1 percent.
EXAMPLE 8 preparation of hydroxyethyl methacrylate
Adding 86 kg/h of acrylic acid and 86 kg/h of toluene into a preheater, preheating and gasifying the acrylic acid and the toluene, and introducing the acrylic acid and the toluene into a tubular reactor filled with a catalyst 2; at the same time, 50 kg/h of ethylene oxide and 50 kg/h of nitrogen were mixed in a further mixer and then introduced into the tubular reactor which had been charged with catalyst 2. At 150 ℃, the reaction pressure is 1kg/cm 2 The reaction is carried out under absolute pressure, the materials are distilled into a condensation separation tower for separation, 125 kg/h of hydroxyethyl acrylate is obtained, the conversion rate is 98.0 percent, and the purity is 99.8 percent.
EXAMPLE 9 preparation of hydroxypropyl methacrylate
Adding 86 kg/h of methacrylic acid and 86 kg/h of methylbenzene into a preheater, preheating, gasifying and introducing into a tubular reactor filled with a catalyst 3; while 75 kg/h of propylene oxide and 75 kg/h of nitrogen were mixed in a further mixer and then introduced into the tubular reactor which had been charged with catalyst 3. At 120 ℃ under a reaction pressure of 1kg/cm 2 The reaction is carried out under absolute pressure, the materials are distilled into a condensation separation tower for separation, and 141 kg/h hydroxypropyl methacrylate is obtained, the conversion rate is 98.1 percent, and the purity is 99.2 percent.
EXAMPLE 10 preparation of hydroxyethyl methacrylate
Adding 86 kg/h of methacrylic acid and 86 kg/h of methylbenzene into a preheater, preheating, gasifying and introducing into a tubular reactor filled with a catalyst 4; at the same time, 53 kg/h of ethylene oxide and 53 kg/h of nitrogen were mixed in a further mixer and then introduced into the tubular reactor which had been filled with catalyst 4. At 150 ℃, the reaction pressure is 10kg/cm 2 The reaction is carried out under absolute pressure, the materials are distilled into a condensation separation tower for separation, 125 kg/h of hydroxyethyl methacrylate is obtained, the conversion rate is 97 percent, and the purity is 99 percent.
EXAMPLE 11 preparation of hydroxypropyl methacrylate
Adding 86 kg/h of methacrylic acid and 86 kg/h of methylbenzene into a preheater, preheating, gasifying and introducing into a tubular reactor filled with a catalyst 5; at the same time, 53 kg/h propylene oxide and 53 kg/h nitrogen were mixed in a further mixer and then introduced into the reactor which had been filled with catalyst 5. At 160 ℃ and a reaction pressure of 5kg/cm 2 The reaction is carried out under absolute pressure, the materials are distilled into a condensation separation tower for separation, and 137 kg/h of hydroxypropyl methacrylate is obtained, the conversion rate is 98.2 percent, and the purity is 99.9 percent.
Claims (7)
1. The application of a supported catalyst in preparing hydroxyalkyl acrylate is characterized in that the hydroxyalkyl acrylate is prepared by taking acrylic acid and alkylene oxide as reaction raw materials through a ring opening reaction, and specifically comprises the following components:
respectively mixing acrylic acid and toluene in a weight ratio of 1:1, adding the mixture into a preheater, preheating and gasifying the mixture, and then introducing the mixture into a tubular reactor;
in a further mixer, alkylene oxide and nitrogen are mixed in a weight ratio of 1:1 mixing and then introducing into a tubular reactor;
the tubular reactor is loaded with the supported catalyst,
at the temperature of 120-200 ℃ and the concentration of 1-10 kg/cm 2 Reacting under absolute pressure, distilling the materials into a condensation separation tower for separation to obtain hydroxyalkyl acrylate;
the acrylic acid is methacrylic acid or acrylic acid,
the molar ratio of the acrylic acid to the alkylene oxide is 1:1 to 1.6 of the total weight of the mixture,
the supported catalyst is obtained by loading any one simple substance, oxide, sulfate and halide of metal magnesium, calcium, iron, copper, zinc or aluminum on a carrier,
the weight ratio of the simple substances, oxides, sulfates and halides of the metal magnesium, calcium, iron, copper, zinc and aluminum is 1:1 to 3:1 to 10:1 to 5 percent of the total weight of the mixture,
the weight consumption of the carrier is 1-5 times of the total weight consumption of simple substances, oxides, sulfates and halides of magnesium, calcium, iron, copper, zinc and aluminum.
2. Use according to claim 1, characterized in that: the oxides of the metal magnesium, calcium, iron, copper, zinc and aluminum are MgO, caO, feO and Cu 2 O、CuO、ZnO、Al 2 O 3 Any one of them.
3. The method for preparing hydroxyalkyl acrylate with the supported catalyst as claimed in claim 1, wherein: the sulfate of the metal magnesium, calcium, iron, copper, zinc and aluminum is MgSO 4 、CaSO 4 、FeSO 4 、Cu 2 SO 4 、CuSO 4 、ZnSO 4 、Al 2 (SO 4 ) 3 Any one of them.
4. Use according to claim 1, characterized in that: the halide of the metal magnesium, calcium, iron, copper, zinc and aluminum is MgCl 2 、MgBr 2 、CaCl 2 、CaBr 2 、FeCl 2 、CuCl、CuCl 2 、CuBr、CuBr 2 、ZnCl 2 、AlCl 3 Any one of them.
5. Use according to claim 1, characterized in that: the carrier is one or a mixture of more than two of active carbon, carbon fiber or diatomite.
6. Use according to claim 1, characterized in that: the catalyst is prepared by the following method:
putting any simple substance of magnesium, calcium, iron, copper, zinc or aluminum, oxide, sulfate, halide and carrier into a reactor according to a certain proportion, fully mixing, drying for 3 hours at 110 ℃, grinding into powder by a grinder, replacing for 3 times by high-purity nitrogen, and vacuumizing for 3 hours under a vacuum pump of-60 to-80 kPa to obtain the catalyst.
7. Use according to claim 1, characterized in that: the alkylene oxide is ethylene oxide or propylene oxide.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1137071A (en) * | 1966-04-28 | 1968-12-18 | Japan Gas Chemical Co | Process for preparing hydroxyalkyl acrylate or hydroxyalkyl methacrylate |
| CN1192943A (en) * | 1997-03-12 | 1998-09-16 | 厦门大学 | Supported solid-acid catalyst for producing butyl acetic ether |
| JP2000297062A (en) * | 1999-04-14 | 2000-10-24 | Dainippon Ink & Chem Inc | Production of hydroxyalkyl (meth)acrylate |
| CN1355161A (en) * | 2000-11-24 | 2002-06-26 | 中国石化集团齐鲁石油化工公司 | Process for preparing polyol di(methy) acrylate |
| CN104640835A (en) * | 2012-09-24 | 2015-05-20 | 株式会社日本触媒 | Hydroxyalkyl acrylate and method for producing same |
| CN110026212A (en) * | 2019-05-23 | 2019-07-19 | 临海市利民化工有限公司 | A kind of catalyst for cracking and the method using the catalyst preparation sitafloxacin intermediate |
-
2020
- 2020-02-25 CN CN202010116498.3A patent/CN111185205B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1137071A (en) * | 1966-04-28 | 1968-12-18 | Japan Gas Chemical Co | Process for preparing hydroxyalkyl acrylate or hydroxyalkyl methacrylate |
| CN1192943A (en) * | 1997-03-12 | 1998-09-16 | 厦门大学 | Supported solid-acid catalyst for producing butyl acetic ether |
| JP2000297062A (en) * | 1999-04-14 | 2000-10-24 | Dainippon Ink & Chem Inc | Production of hydroxyalkyl (meth)acrylate |
| CN1355161A (en) * | 2000-11-24 | 2002-06-26 | 中国石化集团齐鲁石油化工公司 | Process for preparing polyol di(methy) acrylate |
| CN104640835A (en) * | 2012-09-24 | 2015-05-20 | 株式会社日本触媒 | Hydroxyalkyl acrylate and method for producing same |
| CN110026212A (en) * | 2019-05-23 | 2019-07-19 | 临海市利民化工有限公司 | A kind of catalyst for cracking and the method using the catalyst preparation sitafloxacin intermediate |
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Denomination of invention: A supported catalyst and its application in the preparation of hydroxyalkyl acrylate Granted publication date: 20230117 Pledgee: Agricultural Bank of China Limited Dongzhi County Branch Pledgor: Chizhou Fangda Technology Co.,Ltd.|Chen Fang Registration number: Y2024980002081 |