KR101002761B1 - Method of producing acrylic acid - Google Patents
Method of producing acrylic acid Download PDFInfo
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- KR101002761B1 KR101002761B1 KR1020070124273A KR20070124273A KR101002761B1 KR 101002761 B1 KR101002761 B1 KR 101002761B1 KR 1020070124273 A KR1020070124273 A KR 1020070124273A KR 20070124273 A KR20070124273 A KR 20070124273A KR 101002761 B1 KR101002761 B1 KR 101002761B1
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- South Korea
- Prior art keywords
- oxide
- reaction
- acrylic acid
- dehydration
- glycerol
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 78
- BSABBBMNWQWLLU-UHFFFAOYSA-N hydroxypropionaldehyde Natural products CC(O)C=O BSABBBMNWQWLLU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- -1 MgSO 4 Chemical class 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
- C07C51/46—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by azeotropic distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 a) 글리세롤 또는 글리세롤 수용액을 탈수반응시켜 제1생성물을 얻는 단계; b) 상기 a) 단계에서 수득된 제1생성물을 산화반응시켜 제2생성물을 얻는 단계; 및 c) 상기 b) 단계에서 수득된 제2생성물을 탈수반응시켜 아크릴산을 얻는 단계를 포함하는 아크릴산의 제조방법에 관한 것이다. The present invention comprises the steps of a) dehydrating glycerol or aqueous solution of glycerol to obtain a first product; b) oxidizing the first product obtained in step a) to obtain a second product; And c) dehydrating the second product obtained in step b) to obtain acrylic acid.
글리세롤, 하이드록시 프로피온알데히드, 하이드록시 프로피온산 Glycerol, Hydroxy Propionaldehyde, Hydroxy Propionic Acid
Description
본 발명은 아크롤레인의 생성 없이 글리세롤 또는 글리세롤 수용액을 탈수반응, 산화반응 및 탈수반응시켜 아크릴산을 제조할 수 있는 아크릴산의 제조방법에 관한 것이다. The present invention relates to a method for producing acrylic acid which can produce acrylic acid by dehydration, oxidation reaction and dehydration reaction of glycerol or aqueous solution of glycerol without production of acrolein.
일반적으로, 아크릴산은 프로필렌의 분자상 산소 함유 가스에 접촉 기상 산화반응시켜 제조되는 방법이 공업적으로 널리 행해지고 있다. 구체적으로, 프로필렌을 분자상 산소 함유 가스에 의해 기상 산화시켜 주로 아크롤레인을 제조하는 전단공정 및 상기 아크롤레인을 포함하는 반응가스를 다시 산화시켜 아크릴산을 제조하는 후단공정으로 이루어지는 2단계 반응에 의해 아크릴산이 제조되고 있다.In general, a method of producing acrylic acid by catalytic gas phase oxidation reaction of a molecular oxygen-containing gas of propylene is widely used industrially. Specifically, acrylic acid is produced by a two-step reaction consisting of a front-end process for producing acrolein mainly by gas phase oxidation of propylene with a molecular oxygen-containing gas and a post-step process for producing acrylic acid by oxidizing the reaction gas containing the acrolein again. It is becoming.
그러나, 프로필렌을 분자상 산소 함유 가스에 의해 산화시키는 전단공정에 있어서, 아크롤레인을 생성하는 주반응 외에 부반응이 일어나 테레프탈산, 말레인산 등과 같은 유기산, 고비점 화합물, 타르상 화합물 등과 같은 부생성물이 생성된다. 이들 부생성물에 의해 반응장치가 오염되고, 심한 경우에는 탄화물 등과 같은 퇴적물이 생성되어, 압력손실이 증가하거나 반응관의 폐색이 일어나 정상적인 조업이 곤란해지거나, 제품 품질의 저하 등과 같은 문제가 발생한다. However, in the shearing step in which propylene is oxidized by a molecular oxygen-containing gas, side reactions occur in addition to the main reaction to generate acrolein, thereby producing by-products such as organic acids such as terephthalic acid and maleic acid, high boiling point compounds, and tar phase compounds. These by-products contaminate the reaction apparatus and, in severe cases, deposits such as carbides are generated, which causes problems such as increased pressure loss or blockage of the reaction tube, making normal operation difficult or degrading product quality. .
이에, 이들 부생성물을 제거하기 위한 정제수단을 마련하려면, 그 설비비용이 커져 제조비용의 상승을 초래하게 된다. 나아가서는, 아크롤레인을 비롯한 반응성이 높은 화합물에 의한 후반응도 발생할 수 있다.Therefore, in order to provide a refining means for removing these by-products, the cost of the equipment becomes large, resulting in an increase in the manufacturing cost. Furthermore, post-reaction with highly reactive compounds, including acrolein, may also occur.
반면, 글리세롤을 이용하여 아크릴산을 제조하는 방법이 공지되어 있다. 구체적으로 글리세롤을 2번 연속으로 탈수 반응시킨 후, 1번의 산화반응을 시켜 아크릴산을 제조하는 방법에 관한 것이다.On the other hand, a method for producing acrylic acid using glycerol is known. Specifically, the present invention relates to a method of producing acrylic acid by performing a dehydration reaction two times in succession, followed by one oxidation reaction.
상기와 같은 방법으로 글리세롤을 이용하여 아크릴산으로 제조하는 경우, 글리세롤이 2번 연속적으로 탈수반응되어 생성된 아크롤레인으로 인해 아크릴산의 정제공정에서 증류탑 하부나 증류탑의 리보일러에 고분자가 생성되어 정상적인 조업이 불가능해지기도 한다. 또한, 아크릴산 반응관의 폐색이 일어나고, 아크릴산의 회수과정에서 아크롤레인을 제거하기 위한 별도의 장치, 예를 들어 탈기탑이 따로 필요한 단점이 있다. In the case of producing acrylic acid using glycerol in the same manner as described above, due to the acrolein produced by the dehydration reaction of glycerol two times in succession, polymers are produced at the bottom of the distillation column or the reboiler of the distillation column due to the acrolein produced. It may be done. In addition, the blockage of the acrylic acid reaction tube occurs, there is a disadvantage that a separate device for removing acrolein, for example, a degassing column is separately required in the recovery process of acrylic acid.
따라서, 본 발명은 상기 문제점을 해결하기 위하여, 아크릴산의 제조과정 중 아크롤레인이 생성되지 않아 추후 아크롤레인을 제거하기 위한 추가공정 장치가 요구되지 않고, 제조비용을 절감하고, 제조설비 규모를 줄일 수 있는 아크릴산의 제조방법을 제공하는 것을 목적으로 한다. Therefore, in order to solve the problem, the present invention does not require acrolein during the manufacturing process of acrylic acid, and thus does not require an additional process device for removing acrolein later, and thus reduces manufacturing cost and reduces the size of manufacturing facilities. An object of the present invention is to provide a manufacturing method.
본 발명은 a) 글리세롤 또는 글리세롤 수용액을 탈수반응시켜 제1생성물을 얻는 단계; b) 상기 a) 단계에서 수득된 제1생성물을 산화반응시켜 제2생성물을 얻는 단계; 및 c) 상기 b) 단계에서 수득된 제2생성물을 탈수반응시켜 아크릴산을 얻는 단계를 포함하는 아크릴산의 제조방법을 제공한다.The present invention comprises the steps of a) dehydrating glycerol or aqueous solution of glycerol to obtain a first product; b) oxidizing the first product obtained in step a) to obtain a second product; And c) dehydrating the second product obtained in step b) to obtain acrylic acid.
본 발명에 따른 아크릴산의 제조방법은 아크릴산의 제조과정 중 아크롤레인이 생성되지 않아 추후 아크롤레인을 제거하기 위한 추가공정 장치가 요구되지 않고, 제조비용을 절감하고, 제조설비 규모를 줄일 수 있다. The method for producing acrylic acid according to the present invention does not produce acrolein during the production of acrylic acid, and thus does not require an additional process device for removing acrolein later, thereby reducing manufacturing costs and reducing the size of manufacturing facilities.
본 발명에 따른 아크릴산의 제조방법은 a) 글리세롤 또는 글리세롤 수용액을 탈수반응시켜 제1생성물을 얻는 단계; b) 상기 a) 단계에서 수득된 제1생성물을 산화반응시켜 제2생성물을 얻는 단계; 및 c) 상기 b) 단계에서 수득된 제2생성물을 탈수반응시켜 아크릴산을 얻는 단계를 포함하는 것을 특징으로 한다. Acrylic acid production method according to the present invention comprises the steps of a) obtaining a first product by dehydrating glycerol or aqueous solution of glycerol; b) oxidizing the first product obtained in step a) to obtain a second product; And c) dehydrating the second product obtained in step b) to obtain acrylic acid.
본 발명에 있어서, 상기 글리세롤 수용액은 물의 함량이 50 중량% 이하인 것이 바람직하고, 물의 함량이 30 중량% 이하이면 더 바람직하다. 물의 함량이 50 중량%를 넘으면 기화하기 위해 사용되는 에너지가 다량 필요하고, 배수처리에도 막대한 비용이 들기 때문에 아크릴산 제조방법을 공업화 하기에 비효율적이다.In the present invention, the aqueous glycerol solution is preferably 50% by weight or less, more preferably 30% by weight or less. If the water content is more than 50% by weight, a large amount of energy used to vaporize is required, and the drainage treatment is expensive, which is inefficient for industrializing the acrylic acid production method.
본 발명에 있어서, 상기 a) 단계의 탈수반응에 의해 하이드록시 프로피온알데히드를 포함하는 제1생성물을 얻고, 상기 b) 단계의 산화반응에 의해 하이드록시 프로피온산을 포함하는 제2생성물을 얻으며, 상기 제2생성물을 탈수반응시켜 아크릴산을 얻을 수 있다. In the present invention, a first product containing hydroxy propionaldehyde is obtained by the dehydration reaction of step a), and a second product containing hydroxy propionic acid is obtained by the oxidation reaction of step b), 2 The product can be dehydrated to obtain acrylic acid.
그러나, 본 발명에 따른 아크릴산의 제조방법은 탈수반응을 연속으로 행하지 않고, 산화반응과 번갈아 행함으로써, 종래와 달리 아크롤레인을 생성시키지 않은 장점이 있다. However, the method for producing acrylic acid according to the present invention has the advantage of not generating acrolein, unlike the prior art, by alternately performing the dehydration reaction with the oxidation reaction.
구체적으로 종래와 같이 탈수반응을 연속적으로 행하는 단계를 포함하는 아크릴산의 제조방법에서는 첫번째 탈수반응에서 HOCH2-CH=CH2OH이 생성되는데, 이는 호변이성(tautomerism)에 의해 CHO-CH2-CH2OH(하이드록시 프로피온알데히드)로 변한다. 상기 첫번째 탈수반응에서 생성된 하이드록시 프로피온알데히드는 탈수반응을 한번 더 거쳐 아크롤레인으로 변하게 되고, 상기 아크롤레인을 산화시키면 아크릴산을 얻게 된다. Specifically, in the method for producing acrylic acid, which includes continuously performing a dehydration reaction as in the related art, HOCH 2 -CH = CH 2 OH is generated in the first dehydration reaction, which is CHO-CH 2 -CH due to tautomerism. 2 OH (hydroxy propionaldehyde). The hydroxy propionaldehyde produced in the first dehydration reaction is converted to acrolein through one more dehydration reaction, and oxidizing the acrolein gives acrylic acid.
그러나, 본 발명에서는 탈수반응을 한번만 해서 하이드록시 프로피온알데히드를 얻은 다음 상기 하이드록시 프로피온알데히드를 산화시켜 하이드록시 프로피 온산(CH2OH-CH2-COOH)을 얻고 이것을 탈수반응시켜 아크릴산을 얻는다. 따라서, 본 발명에서는 아크롤레인을 생성시키지 않아 추후 아크롤레인을 제거하기 위한 추가공정 장치가 요구되지 않고, 제조비용을 절감하고, 제조설비 규모를 줄일 수 있다.However, in the present invention, hydroxy propionaldehyde is obtained by dehydration only once, and then hydroxy propionaldehyde is oxidized to obtain hydroxy propionic acid (CH 2 OH-CH 2 -COOH), which is dehydrated to obtain acrylic acid. Therefore, the present invention does not generate acrolein, so that no further processing apparatus for removing acrolein is required later, and manufacturing cost can be reduced and manufacturing equipment scale can be reduced.
본 발명에 따른 아크릴산의 제조방법에서 상기 a) 단계 또는 상기 c) 단계에 따른 상기 탈수반응은 글리세롤 또는 글리세롤 수용액을 기화시켜 가스상태로 제조하는 반응으로, 촉매에 의해 탈수반응 되는 것이 바람직하다. 상기 촉매로는 카올리나이트(kaolinite), 벤토나이트(bentonite), 몬모릴로나이트(montmorillonite) 및 제올라이트(zeolite)를 포함하는 천연 또는 합성 점토 화합물; 인산이나 황산이 담지된 알루미나로 이루어진 담체; Al2O3, TiO2, ZrO2, SnO2, Cr2O3, MoO3, WO3,V2O5, SiO2-Al2O3, SiO2-TiO2 및 TiO2-WO3 중에서 선택된 1종 이상을 포함하는 무기 산화물 또는 무기 복합 산화물; 및 MgSO4, Al2(SO4)3, K2SO4, AlPO4 및 Zr3(SO4)2 인 금속 황산염, 탄산염, 질산염 및 인산염 중 선택된 1종 이상을 포함하는 고체 산성물질을 포함할 수 있으나, 이에 한정되는 것은 아니다.In the method for preparing acrylic acid according to the present invention, the dehydration reaction according to step a) or c) is a reaction of preparing a gaseous state by vaporizing an aqueous solution of glycerol or glycerol, preferably by dehydration by a catalyst. The catalyst may include natural or synthetic clay compounds including kaolinite, bentonite, montmorillonite and zeolite; A carrier made of alumina on which phosphoric acid or sulfuric acid is supported; Among Al 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , Cr 2 O 3 , MoO 3 , WO 3 , V 2 O 5 , SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 and TiO 2 -WO 3 Inorganic oxides or inorganic composite oxides including at least one selected; And solid acidic materials comprising at least one selected from metal sulfates, carbonates, nitrates and phosphates which are MgSO 4 , Al 2 (SO 4 ) 3 , K 2 SO 4 , AlPO 4 and Zr 3 (SO 4 ) 2 . It may be, but is not limited thereto.
또한, a) 단계 또는 상기 c) 단계의 온도 및 압력은 200 ~ 370℃ 및 0.5 ~ 10기압인 상태에서 탈수반응되는 것이 바람직하나, 이에 한정되는 것은 아니다.In addition, the temperature and pressure of step a) or step c) is preferably dehydrated in a state of 200 to 370 ° C and 0.5 to 10 atmospheres, but is not limited thereto.
상기 a) 단계 및 c) 단계의 탈수반응에서는 글리세롤 또는 글리세롤 수용액 및 제2생성물을 기화하여 가스상태로 하고, 상기 가스를 상기 촉매가 충전되어 있고, 상기 반응 온도 및 압력에 제어되는 반응기에서 유통시키는 것이 바람직하다. 상기 반응기에 유통시킬 때의 가스의 유량은 특별히 제한되는 것은 아니지만, 공간 속도가 100~20000h-1이 바람직하다.In the dehydration of steps a) and c), glycerol or aqueous solution of glycerol and the second product are vaporized to form a gas, and the gas is circulated in a reactor filled with the catalyst and controlled at the reaction temperature and pressure. It is preferable. The flow rate of the gas when flowing through the reactor is not particularly limited, but the space velocity is preferably 100 to 20000 h −1 .
상기 탈수반응에 있어서, 고농도 가스에 의한 폭주 반응을 억제하기 위해 반응물이 기화된 가스에 불활성 가스를 첨가하고, 반응기에 유통되게 하는 것이 바람직하다. 구체적으로, 상기 탈수반응의 반응기에 제공하는 가스 중의 불활성 가스 농도는 50 용량% 이상이 바람직하다. 또한, 상기 불활성 가스는 예를 들어, 질소 가스, 이산화탄소 가스, 희가스, 수증기 등을 이용할 수 있다.In the dehydration reaction, in order to suppress the runaway reaction by the high concentration gas, it is preferable to add an inert gas to the gas vaporized by the reactant and distribute it to the reactor. Specifically, the inert gas concentration in the gas provided to the reactor for dehydration is preferably at least 50% by volume. As the inert gas, for example, nitrogen gas, carbon dioxide gas, rare gas, water vapor, or the like can be used.
본 발명의 아크릴산의 제조방법에 있어서, 상기 b) 단계에 따른 산화반응은 상기 탈수반응으로 생긴 가스상태의 제1생성물을 기상 산화반응을 시키는 것으로, 촉매에 의해 산화반응 되는 것이 바람직하다. 상기 촉매로는 금, 백금, 이리듐, 팔라듐 및 그 산화물 중에서 선택된 1종 이상을 포함하는 촉매; 산화 철, 산화 몰리브덴, 산화 티탄, 산화 바나디움, 산화 텅스텐, 산화 안티몬, 산화 주석 및 산화 구리 중에서 선택된 1종 이상을 포함하는 산화물; 및 상기 산화물을 활성탄, 산화지르코늄, 실리카, 알루미나 및 이들의 복합산화물 또는 탄화규소로 이루어진 담체에 담지시킨 형태를 사용할 수 있으나, 이에 한정되는 것은 아니다.In the production method of acrylic acid of the present invention, the oxidation reaction according to step b) is a gas phase oxidation reaction of the gaseous product resulting from the dehydration reaction, it is preferable that the oxidation reaction by a catalyst. The catalyst includes a catalyst comprising at least one selected from gold, platinum, iridium, palladium and oxides thereof; Oxides containing at least one selected from iron oxide, molybdenum oxide, titanium oxide, vanadium oxide, tungsten oxide, antimony oxide, tin oxide and copper oxide; And a form in which the oxide is supported on a carrier made of activated carbon, zirconium oxide, silica, alumina, and a composite oxide or silicon carbide thereof, but is not limited thereto.
또한, 상기 b) 단계는 100 ~ 250℃ 또는 0.5 ~ 10기압인 상태에서 산화반응 되는 것이 바람직하나, 이에 한정되는 것은 아니다.In addition, the step b) is preferably an oxidation reaction in a state of 100 ~ 250 ℃ or 0.5 ~ 10 atm, but is not limited thereto.
상기 산화반응은 구체적으로, 상기 탈수반응으로 생긴 가스를 상기 촉매가 충전되어 있고, 상기 반응 온도 및 압력에 제어되는 반응기에 유통하게 하는 것이 바람직하다. 상기 반응기에 유통할 때의 가스의 유량은 특별히 제한되지 않지만, 공간 속도가 100~2000 h-1이 되도록 하는 것이 바람직하다. Specifically, the oxidation reaction is preferably such that the gas produced by the dehydration reaction is circulated to the reactor filled with the catalyst and controlled to the reaction temperature and pressure. Although the flow volume of the gas at the time of distributing to the said reactor is not restrict | limited, It is preferable to make space velocity into 100-2000 h <-1> .
상기 산화반응에 있어서, 상기 탈수반응으로 생긴 가스를 상기 산화반응의 반응기에 유통할 때에 탈수반응으로 생긴 가스에 산소 가스를 첨가하고, 산소 농도를 높여 두는 것이 바람직하다. 상기 산소 가스에 의해 산화반응의 반응성이 향상되고, 보다 높은 수율로 아크릴산을 얻을 수 있다. 구체적으로, 상기 산화반응의 반응기에 제공하는 가스 중 산소 농도는 2 용량% 이상으로 하는 것이 바람직하다. 또한, 산소는 너무 비싸고, 연소 범위가 되고 폭발등의 위험을 수반하는 우려가 생기기 때문에 산소 농도의 상한치는 탈수반응으로 생긴 가스 중에 포함되는 미반응의 원료 글리세롤 농도, 반응 온도 등을 고려하고 연소범위를 회피하도록 적절 설정하는 것이 바람직하다. In the oxidation reaction, when the gas generated by the dehydration reaction is passed through the reactor for the oxidation reaction, it is preferable to add oxygen gas to the gas produced by the dehydration reaction and increase the oxygen concentration. By the oxygen gas, the reactivity of the oxidation reaction can be improved, and acrylic acid can be obtained with higher yield. Specifically, the oxygen concentration in the gas provided to the reactor of the oxidation reaction is preferably at least 2% by volume. In addition, the oxygen is too expensive, the combustion range and the risk of explosion, etc., the upper limit of the oxygen concentration in consideration of the unreacted raw material glycerol concentration, reaction temperature, etc. contained in the dehydration gas, combustion range It is desirable to set appropriately so as to avoid the problem.
구체적으로 본 발명의 아크릴산 제조방법을 설명하면 다음과 같다. Specifically, the acrylic acid production method of the present invention will be described.
본 발명의 아크릴산 제조방법에 따라 글리세롤 또는 글리세롤 수용액을 탈수반응을 행한뒤, 탈수반응으로 생긴 가스 상태의 반응물에 상기 기상 산화 반응을 행한 후 다시 탈수반응을 행하여 아크릴산을 얻을 수 있다. According to the acrylic acid production method of the present invention, after carrying out the dehydration reaction of glycerol or aqueous solution of glycerol, the gaseous reaction product produced by the dehydration reaction is subjected to the gas phase oxidation reaction, and then dehydration reaction can be performed to obtain acrylic acid.
예를 들면, 연결한 3개의 반응관을 가진 탠덤(tandem)형 반응기를 이용할 수 있다. 구체적으로 각 3개의 반응관에서 있어서, 탈수반응용 촉매가 채워진 탈수반응기에서 탈수반응이 일어나고; 상기 탈수반응기와 연결되고 산화반응용 촉매가 채워진 산화반응기에서, 상기 탈수반응기에 생성된 생성물이 이송되어 산화반응이 일어나며; 상기 산화반응에 의해 생성된 반응물이 상기 산화반응기와 연결되어 탈수 반응용 촉매가 채워진 탈수반응기에 이송되어 탈수반응이 이루어질 수 있다. For example, a tandem reactor with three connected reaction tubes can be used. Specifically, in each of the three reaction tubes, dehydration reaction occurs in the dehydration reactor filled with the catalyst for dehydration reaction; In an oxidation reactor connected to the dehydration reactor and filled with a catalyst for oxidation reaction, a product generated in the dehydration reactor is transferred to cause an oxidation reaction; The reactant produced by the oxidation reaction may be connected to the oxidation reactor and transferred to a dehydration reactor filled with a catalyst for dehydration reaction to perform a dehydration reaction.
또한, 1개의 반응관을 가진 싱글형 반응기를 사용할 수도 있다. 상기 싱글형 반응관의 반응가스 입출구 측에 탈수반응용 촉매를 충전하고, 반응관의 중앙측에 산화반응용 촉매를 충전하여, 반응관이 입구에서부터 출구까지 차례로 탈수반응, 산화반응 및 탈수반응을 행하는 형태를 사용할 수 있다. 상기 반응기에서 나오는 아크릴산은 기체 상태이므로 흡수탑에서 액체상태의 아크릴산으로 만들고, 물분리탑에서 공비증류제를 사용하여 물분리탑 상부로는 물과 공비증류제를, 물분리탑 하부로는 실질적으로 아크릴산만을 얻을 수 있다. 이후에 통상적인 증류법을 이용해 아크릴산의 순도를 높이거나, 결정화 장치를 이용해 보다 순도 높은 아크릴산을 얻을 수 있다.It is also possible to use a single reactor with one reaction tube. The reaction gas inlet and outlet side of the single type reaction tube is filled with a catalyst for dehydration reaction, and an oxidation reaction catalyst is charged at the center side of the reaction tube, so that the reaction tube sequentially undergoes dehydration, oxidation and dehydration from the inlet to the outlet. The form to perform can be used. Since acrylic acid from the reactor is a gaseous state, it is made of acrylic acid in a liquid state in an absorption tower, and an azeotropic distillation agent is used in the water separation tower, and water and an azeotropic distillation agent is substantially above the water separation tower, and substantially below the water separation tower. Only acrylic acid can be obtained. Thereafter, the purity of acrylic acid may be increased by using a conventional distillation method, or higher purity acrylic acid may be obtained by using a crystallization apparatus.
이하, 본 발명의 실시예를 통해 본 발명에 대해 상세히 설명한다. 그러나, 본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들로 인하여 한정되는 식으로 해석되어서는 안된다. 본 발명의 실시예들은 당업계에서 평균적 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, the present invention will be described in detail through embodiments of the present invention. However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
<실시예 1> ≪ Example 1 >
직경 25mm의 SUS 반응관 3개를 연결시키고, 첫번째 반응관에 감마 알루미나 20g을, 두번째 반응관에는 백금이 5% 담지된 활성탄 20g을, 세번째 반응관에 감마 알루미나 20g을 각각 충전했다. 다음으로, 각 반응관을 전기로를 이용하여 반응관의 온도를 각각 275℃, 200℃ 및 250℃로 맞추었다. 분당 10g의 유량으로 70% 글리 세롤 수용액을 기화시켜, 이것에 공기를 분당 100L 속도로 첫번째 반응관 상단으로 주입하였다. 상기 3개의 반응관에 연속한 후, 아크릴산의 회수공정을 거쳐 아크릴산을 얻었다. 수율은 74.7%이였다.Three SUS reaction tubes having a diameter of 25 mm were connected, and 20 g of gamma alumina was charged into the first reaction tube, 20 g of activated carbon loaded with 5% platinum and 20 g of gamma alumina were charged into the third reaction tube. Next, each reaction tube was adjusted to 275 ° C, 200 ° C and 250 ° C by using an electric furnace. A 70% aqueous solution of glycerol was vaporized at a flow rate of 10 g per minute, and air was injected into the top of the first reaction tube at a rate of 100 L per minute. After continuing to the three reaction tubes, acrylic acid was obtained through a recovery step of acrylic acid. The yield was 74.7%.
<실시예 2><Example 2>
실시예 1과 동일하게 촉매를 충전시키고, 반응관 온도를 맞추었다. 분당 10g의 유량으로 70% 글리세롤 수용액을 기화시키고, 이것에 질소를 분당 80L의 속도로 첫번째 반응관 상단으로 주입하였다. 첫번째 반응관 하단으로 나온 반응기체에 공기를 분당 20L의 속도로 혼합하여 두번째 반응관으로 주입하였다. 상기 3개의 반응관에 연속한 후, 아크릴산의 회수공정을 거쳐 회수하였다. 수율은 82.4%였다.The catalyst was charged and the reaction tube temperature was adjusted in the same manner as in Example 1. A 70% aqueous solution of glycerol was vaporized at a flow rate of 10 g per minute, and nitrogen was injected into the top of the first reaction tube at a rate of 80 L per minute. Air was injected into the reactor to the bottom of the first reaction tube at a rate of 20L per minute and injected into the second reaction tube. After continuing to the three reaction tubes, the product was recovered through an acrylic acid recovery step. Yield 82.4%.
<실시예 3><Example 3>
실시예 2에서 70% 글리세롤 수용액 대신 글리세롤을 사용하는 것을 제외하고는 실시예 2와 동일한 과정으로 아크릴산을 제조하였다. 수율은 78.8%였다.Acrylic acid was prepared in the same manner as in Example 2, except that glycerol was used instead of the aqueous 70% glycerol solution in Example 2. The yield was 78.8%.
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| US9527065B2 (en) | 2013-11-18 | 2016-12-27 | Lg Chem, Ltd. | Catalyst for glycerin dehydration, preparation method thereof, and preparation method of acrolein |
| US10266475B2 (en) | 2016-04-12 | 2019-04-23 | Lg Chem, Ltd. | Method for producing acrylic acid |
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| US9546124B2 (en) | 2013-06-27 | 2017-01-17 | Lg Chem, Ltd. | Method for producing acrylic acid from glycerol |
| KR101634221B1 (en) | 2013-07-08 | 2016-06-28 | 주식회사 엘지화학 | Method for producing acrylic acid from glycerol |
| KR101616528B1 (en) * | 2013-07-16 | 2016-04-28 | 주식회사 엘지화학 | Catalyst for dehydration of glycerin, method of preparing the same, and preparing method of acrolein |
| KR20160011053A (en) | 2014-07-21 | 2016-01-29 | 대아산업주식회사 | Powder tranfer pipe for prevention device blocking of flow path |
| KR101964275B1 (en) * | 2015-09-01 | 2019-04-01 | 주식회사 엘지화학 | Manufacturing method of catalyst for production of acrylic acid and the catalyst therefrom |
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