CN101133012A - Process for removing methacrylic acid from liquid phase comprising acrylic acid as a main constituent and target product, and methacrylic acid as a secondary component - Google Patents
Process for removing methacrylic acid from liquid phase comprising acrylic acid as a main constituent and target product, and methacrylic acid as a secondary component Download PDFInfo
- Publication number
- CN101133012A CN101133012A CNA2006800068559A CN200680006855A CN101133012A CN 101133012 A CN101133012 A CN 101133012A CN A2006800068559 A CNA2006800068559 A CN A2006800068559A CN 200680006855 A CN200680006855 A CN 200680006855A CN 101133012 A CN101133012 A CN 101133012A
- Authority
- CN
- China
- Prior art keywords
- vinylformic acid
- liquid phase
- acid
- weight
- methacrylic acid
- Prior art date
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- Granted
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 179
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000007791 liquid phase Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 86
- 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 37
- 230000008569 process Effects 0.000 title claims description 8
- 239000000470 constituent Substances 0.000 title 1
- 238000002425 crystallisation Methods 0.000 claims abstract description 39
- 239000012452 mother liquor Substances 0.000 claims abstract description 39
- 230000008025 crystallization Effects 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 37
- 238000007254 oxidation reaction Methods 0.000 claims description 37
- 230000036961 partial effect Effects 0.000 claims description 35
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 24
- 230000005494 condensation Effects 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 15
- 239000001294 propane Substances 0.000 claims description 15
- 239000002075 main ingredient Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 39
- 239000007789 gas Substances 0.000 description 38
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 20
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 235000019260 propionic acid Nutrition 0.000 description 10
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical class CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RNYZJZKPGHQTJR-UHFFFAOYSA-N protoanemonin Chemical compound C=C1OC(=O)C=C1 RNYZJZKPGHQTJR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYKASZBHFXBROF-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2-(2,5-dioxopyrrol-1-yl)acetate Chemical compound O=C1CCC(=O)N1OC(=O)CN1C(=O)C=CC1=O TYKASZBHFXBROF-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- SGDYNMJTXCTTAF-UHFFFAOYSA-N 3,6-dihydro-2h-thiazine Chemical compound C1NSCC=C1 SGDYNMJTXCTTAF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical group CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a method for eliminating methacrylic acid from a liquid phase (P) containing acrylic acid as a main component and target product and methacrylic acid as a secondary component. According to said method, the methacrylic acid is eliminated using crystallization, the acrylic acid accumulating in the formed crystallized product and the methacrylic acid accumulating in the remaining mother liquor.
Description
The present invention relates to a kind of from comprising vinylformic acid as the method for removing methacrylic acid main ingredient and target product and the liquid phase of methacrylic acid as secondary component.
Vinylformic acid is to find directly or for example be used to obtain be suitable for its alkyl ester form to make the polymkeric substance of tackiness agent or a kind of important monomer of super water absorbent polymer (for example referring to WO 02/055469 and WO 03/078378).
Worldwide, the heterogeneously catalyzed partial oxidation method that vinylformic acid is only gone up on technical scale substantially by (two-stage usually) propylene prepares (for example referring to EP-A 990636, US-A 5,198,578, EP-A 10 15 410, EP-A 14 84 303, EP-A 14 84 308, EP-A 14 84 309 and US-A 2004/0242826).Used initial propylene is more highly purified propylene (referring to DE-A 101 31 297).Obtain this pure crude propylene, inconvenient and expensive relatively.It derive from thick paraffinic hydrocarbons usually and generally include different purification phase with the propylene that will form with highly pure isolated in form (referring to DE-A 35 21 458).These purification phase generally include from the alkene except that propylene and neutralize from the secondary component except that propylene, comprise in the secondary component that is included in the thick paraffinic hydrocarbons and separating.
Relevant herein is that propylene is separated from its association propane.Because the physical similarity of two kinds of compounds, thisly remove that especially capital and energy consumption are big.Because the crude propylene that therefore obtains of main amount is used for polymerization (for example preparing polypropylene) subsequently in a large number, (high purity described here is absolutely necessary) and experience high added value, aforementioned removing usually regardless of relevant cost and inconvenience, forms the present state-of-art of industry together with refinery's cracking and steam cracking furnace.Compare with polyacrylic demand, these flow to partial oxygen and change into acrylic acid crude propylene partly for than minor, and are the still acceptable secondary required materials flow of cost of material.
No matter preparing acrylic acid feature by catalyzing part oxidation in this purer propylene gas phase is the purity of available raw material, vinylformic acid is not direct, and especially because parallel side reaction, obtain as the component of the product gas mixture that must therefrom remove it subsequently.
This product gas mixture also comprises not the reactant that transforms fully usually, if the suitable intermediate that does not transform fully and in order to improve heat passage and to guarantee explosion-proof behavior and the extra inert dilution gas of using.
In this file, inert dilution gas is interpreted as showing as inertia under the correlated response condition and every kind of inert reaction gaseous fraction is seen separately, maintenance is preferably greater than 97 moles of % greater than 95 moles of %, or 98 moles of % or the 99 moles of % reactive gas species of chemical transformation not.
Basically the common trait of all relevant therewith known separation method be if suitable after above-mentioned product gas mixture directly and/or is indirectly cooled off, and the vinylformic acid that is included in the product gas mixture is transferred to condensation (especially liquid) phase removing substantially in the step.
This can be for example by absorbing to the solvent that is fit to (water for example, high boiling organic solvent, the aqueous solution) undertaken (about this theme in and/or by part or whole basically condensation (for example fractional condensation), see the document that begins to quote, and document EP-A 13 88 533, EP-A 13 88 532, DE-A 102 35 847, EP-A 79 28 67, WO 98/01415, EP-A 10 15 411, EP-A 10 15 410, WO 99/50219, WO 00/53560, WO 02/09839, DE-A 102 35 847, WO 03/041833, DE-A 102 23 058, DE-A 102 43 625, DE-A 103 36 386, EP-A 85 41 29, US-A 4,317,926, DE-A 198 37 520, DE-A 196 06 877, DE-A 190 50 1325, DE-A 102 47 240, DE-A 197 40 253, EP-A 69 57 36, EP-A 98 22 87, EP-A 10 41 062, EP-A 11 71 46, DE-A 43 08 087, DE-A 43 35 172, DE-A 44 36 243, DE-A 19 924 532, DE-A 103 32 758 and DE-A 19 924 533).Acrylic acid remove also can be as described in EP-A 98 22 87, EP-A 98 22 89, DE-A 103 36 386, DE-A 101 15 277, DE-A 196 06 877, DE-A 197 40 252, DE-A 196 27 847, EP-A 92 04 08, EP-A 10 68 174, EP-A 10 66 239, EP-A 10 66 240, WO 00/53560, WO 00/53561, DE-A 100 53 086 and the EP-A 98 22 88 and carry out.The favourable mode of removing also is described among document WO 2004/063138, WO 2004/035514, DE-A 102 43 625 and the DE-A 102 35 847.
Other are removed vinylformic acid with the known method of prior art from the liquid phase (condensation) that comprises the vinylformic acid target product and obtain separate on described basis and carry out, depend on other by products that except that vinylformic acid, comprise, especially the partial oxidation condition that depends on the special-purpose catalyst that is used for partial oxidation and other selections, the multiple combination by extraction, desorb, rectifying, component distillation and/or crystallization method reaches acrylic acid required purity.When being used for preparing super water absorbent polymer (polyacrylic acid or its an alkali metal salt),, extra high purity requirement is arranged for vinylformic acid because this polymkeric substance is particularly useful for being suitable for the health field of medical science standard.Therefore, most vinylformic acid preparation methods' target is this very economical feasible method that is suitable for the glacial acrylic acid of super-absorbent.
Described conventional vinylformic acid preparation method's characteristic feature is that it comprises mainly due to the high purity of used crude propylene at the most analytically can not detect or analytically inapparent amount formation methacrylic acid by product.Therefore, even following prior art document major part comprises the secondary component analysis of blow by blow, but these documents even none are mentioned methacrylic acid as the possible secondary component of vinylformic acid: WO 98/01414, WO 01/92197, EP-A 648 732, EP-A 1305097, EP-A 14 84 308, EP-A 14 84 309, US-A 2004/0242826, DE-A 103 36 386, WO 02/055469, WO 03/078378, WO 01/77056, WO 03/041833, DE-A 196 06 877, EP-A 792 867, EP-A 920 408, EP-A 10 15 411, EP-A 10 15 410, DE-A 198 38 845, WO 03/041833, WO 02/090310, DE-A 101 22 787, WO 03/041832, EP-A 10 68 174, EP-A 10 66 239, EP-A 11 63 201, EP-A 11 59 249, EP-A 11 89 861, EP-A 12 52 129, WO 01/77056, DE-A 102 35 847, DE-A 102 43 625 and WO 2004/035514.Same statement is applicable to the document that is called specific present state-of-art in above-mentioned document.
On the other hand, the still not mentioned methacrylic acid of formation of will following as secondary component then in acrylic acid preparation of prior art will desirably not followed vinylformic acid especially.This will be especially because owing to be different from the positive induction effect of acrylic acid methyl, the radical polymerization tendency of methacrylic acid is compared the situation of obvious reduction with acrylic acid same tendency.
In other words, when using even only comprise the polymkeric substance of the super suction of vinylformic acid preparation radical polymerization of methacrylic acid with trace, must expect methacrylic acid insufficient polymerization and being retained in as ethylenically unsaturated compounds in the polymkeric substance of formation under the concrete polymerizing condition of selecting, this is problematic in health field is used.The existence of methacrylic acid is impact polymer quality (for example molecular weight distribution, degree of crosslinking etc.) unfriendly also.
Become acrylic acid propylene source at the more economical feasible heterogeneously catalyzed partial oxidation that is used for of searching, also planned to originate in thick propane and in the step of reaction of preceding propylene partial oxidation, make its conversion by homogeneous phase and/or heterogeneous catalytic oxidation dehydrogenation and/or heterogeneous catalysis dehydrogenation, part becomes propylene, and the partial oxidation that uses the latter to be used to be correlated with, from unconverted propane, do not remove it (for example referring to WO 03/076370 with expensive and inconvenient mode, WO 01/96271, EP-A 117 146, WO 03/011804, US-A 3,161,670, DE-A 33 13 573, the prior art of reference in WO 01/96270 and these documents).According to DE-A 102 46 119 and DE-A 102 45 585, it is such that program should be: the separating step that is fit to guarantees that the initial action gaseous mixture that is used for the propylene partial oxidation that obtains comprises the C of minimum degree
4Hydrocarbon is as the impurity of undesired weakening catalyst performance.The shortcoming of this program is that above-mentioned lock out operation is costliness and inconvenient, and is what forbid economically under for some situation that only crude propylene is considered as the vinylformic acid raw material, or only realizes limited separation when they use more economically.
Simultaneously, significantly comprise saturated or unsaturated C
4The thick propane of hydrocarbon can obtain on market especially cheaply, no matter they in the method for the ultrapure thick propane of preparation as saving costliness and inconvenient C in very little available secondary stream or the production process fully at them
3/ C
4Hydrocarbon separates.
Under the discrete situation, this favourable cost of material is the overcompensation downstream reduction for preparing catalyst performance in the vinylformic acid by the partial oxidation heterogeneous catalysis economically then, or the too early requirement that changes for catalyzer.
Can be to depend on for the residue shortcoming of the acrylic acid program of described attracting preparation in addition by corresponding C
4The propylene heterogeneously catalyzed partial oxidation that the hydrocarbon content is upset is with preparation vinylformic acid used catalyzer, and it is attended by because the C that carries out side by side with main propylene partial oxidation
4Hydrocarbon (as iso-butylene and Trimethylmethane) partial oxidation and form the methacrylic acid secondary component has described shortcoming (referring to DE-A 102 19 686, DE-A 33 13 573 and EP-A 297 445).When vinylformic acid comprises C by partial direct oxidation
4Hydrocarbon is as the propane of impurity and when obtaining, and same shortcoming can be depending on used catalyzer and reaction conditions and produces, and for example as EP-A 608 838, DE-A 198 35 247, and document DE-A 102 45 585 and DE-A 102 46 119 are described in detail.Be used for other possible had C of heterogeneous preparation by the acrylate moiety oxidation
4The C of hydrocarbon or their oxidized derivatives
3Precursor is propenal (referring to EP-A 700 893 and EP-A 700 714).
Therefore, the purpose of this invention is to provide a kind of from comprising vinylformic acid as the very effective method of removing methacrylic acid main ingredient and target product and the liquid phase of methacrylic acid as secondary component.
Therefore, found from comprising vinylformic acid as the method for removing methacrylic acid main ingredient and target product and the liquid phase P of methacrylic acid as secondary component, it comprises by crystallization removes, vinylformic acid accumulates in the crystal of formation, and methacrylic acid is stayed in the remaining mother liquor.
Said procedure is effective when not mixing methacrylic acid in the crystal basically in vinylformic acid crystalline forming process only.The loss factor A that this is normally relevant with crystallization
MASSituation for 〉=15.Loss factor A is interpreted as staying impurity and the ratio of staying the impurity in the crystal in the mother liquor usually and (is expressed as the weight % based on mother liquor total amount or crystal total amount under every kind of situation; For example mother liquor and crystal can and can be measured by subsequent analysis A by centrifugal or be separated from each other substantially fully by centrifugal and/or washing; For this reason, the degree that mother liquor is removed for its total amount greater than 90 weight %, be preferably greater than 95 weight %, or 97 or 98 weight %, or 99 weight % are normally enough).
At acetate (A
ES) and propionic acid (A
PS) under the situation as vinylformic acid impurity, loss factor is generally≤10 value.In other words, they also mix in the vinylformic acid crystal and only can for example extract from these crystal by the washing that is fit to difficultly.In other words, common need to use poor efficiency and capital-intensive multistage crystallization method are removed in these two kinds of impurity crystallizations from vinylformic acid, as recommended among the EP-A 616 998 for example dynamically and the multistage array configuration of stationary crystallization, except that multi-stage process, require at least one dynamic and at least one stationary crystallization device.Be preferably in (especially referring to WO 03/078378 and WO 01/77056) under the crystalline special boundary condition, form the vinylformic acid crystalline form, therefrom can with comparalive ease acetate and propionic acid be removed by washing with the fused pure acrylic acid subsequently.
AMAS is big more, and to remove methacrylic acid just attractive more in crystallization from vinylformic acid.
Because detailed research, be surprisingly found out that from comprise vinylformic acid as main ingredient and target product and methacrylic acid as the liquid phase of secondary component crystallization remove in the methacrylic acid, even do not have the centrifuge mother liquor/crystalline follow and remove usually with reaching 30 (in a word: 30) and bigger (under the situation that washing tower is removed, this is corresponding at least 〉=100 A
MAS, under favourable situation 〉=1000) loss factor A
MASYet,, from comprising methacrylic acid as main ingredient and target product, vinylformic acid is removed under acrylic acid reverse situation as crystallization in the liquid phase of secondary component, vinylformic acid loss factor A
ASBe generally≤15.These discoveries are unexpected.(fusing point=14 ℃) and pure methacrylic acid because pure acrylic acid (fusing point=15 ℃) have substantially the same fusing point (under 1 bar pressure) (for example referring to R mpps Chemie-Lexikon), so they are especially unexpected.On the contrary, the more remarkable basically difference of their boiling behavior under standard pressure (vinylformic acid boiling point=141 ℃, methacrylic acid boiling point=161 ℃) and advise that for example methacrylic acid is removed in rectifying.The above-mentioned physics fact illustrates also in acrylic acid crystallization and purification of carrying out usually in the prior art that described vinylformic acid is purified (for example referring to EP-A 616 998) in advance by other thermal separation methods, and vinylformic acid is further purified, and does not have methacrylic acid fully.In this file, there is not methacrylic acid nail base vinylformic acid no longer to detect by vapor-phase chromatography.
Along with above-mentioned experimental result, program of the present invention has been opened and has been prepared in the method for the glacial acrylic acid that is applicable to super-absorbent, removes the possibility of the methacrylic acid impurity that hinders this purposes in single separating step in single crystallisation stage with satisfactory way.
Phrase " comprises vinylformic acid as main ingredient and target product and the methacrylic acid liquid phase P (or gaseous mixture or product gas mixture) as secondary component " and only is intended to the liquid phase P (or gaseous mixture or product gas mixture) that the mol ratio V that refers to at least 3: 2 vinylformic acid and methacrylic acid comprises vinylformic acid and methacrylic acid in presents.Certainly, the V in the inventive method also can be at least 2: 1, or at least 3: 1, or at least 4: 1, or at least 5: 1, or at least 6: 1, or at least 7: 1, or at least 8: 1, or at least 9: 1, or at least 10: 1.When V is at least 15: 1, or at least 20: 1, or at least 25: 1, or at least 30: 1, or at least 35: 1, or at least 40: 1, or at least 45: 1, or at least 50: 1, or at least 60: 1, or at least 70: 1, or at least 80: 1, or at least 90: 1, or at least 100: 1 o'clock, the inventive method also is fit to.
Under the situation of many related application, V will be at least 200: 1, or at least 300: 1, or at least 400: 1, or at least 500: 1, or at least 600: 1, or at least 700: 1, or at least 800: 1, or at least 900: 1, or at least 1000: 1.
Yet, when V is at least 2000: 1, or at least 3000: 1, or at least 4000: 1, or at least 5000: 1, or at least 6000: 1, or at least 7000: 1, or at least 8000: 1, or at least 9000: 1, or at least 10000: 1 o'clock, the inventive method also is important.Certainly the V in the inventive method also can be at least 20000: 1, or at least 30000: 1, or at least 40000: 1, or at least 50000: 1, or at least 60000: 1, or at least 70000: 1, or at least 80000: 1, or at least 90000: 1, or at least 100000: 1.
In other words, when liquid phase P (or gaseous mixture or product gas mixture) comprises the acrylic acid content based on it, only during 10 ppm by weight methacrylic acids, the inventive method especially prepares under acrylic acid situation still significant in technical scale.
In other words, V can for example be 3 in the inventive method: 2-100000: 1, or 2: 1-70000: 1, or 3: 1-50000: 1, or 4: 1-30000: 1, or 5: 1-10000: 1, or 6: 1-8000: 1, or 7: 1-6000: 1, or 8: 1-5000: 1, or 9: 1-2000: 1, or 10: 1-1000: 1, or 20: 1-800: 1, or 30: 1-600: 1, or 40: 1-400: 1, or 50: 1-300: 1, or 60: 1-200: 1, or 70: 1-100: 1.
When liquid phase P comprises at least 10 weight % vinylformic acid, or at least 20 weight % vinylformic acid, or at least 30 weight % vinylformic acid, or at least 40 weight % vinylformic acid, or at least 50 weight % vinylformic acid, or at least 60 weight % (or at least 65 weight %) vinylformic acid, or at least 70 weight % vinylformic acid, or at least 80 weight % vinylformic acid, or at least 90 weight % vinylformic acid, or at least 93 weight % vinylformic acid, or at least 94 weight % vinylformic acid, or at least 95 weight % vinylformic acid, or at least 96 weight % vinylformic acid, or at least 97 weight % vinylformic acid, or at least 98 weight % vinylformic acid, or at least 99 weight % vinylformic acid, or at least 99.5 weight % vinylformic acid, or at least 99.7 weight % vinylformic acid, or at least 99.9 weight % vinylformic acid, or at least 99.95 weight % vinylformic acid, or even during more vinylformic acid, above-mentioned commentary is especially relevant.
Common mode with the inventive method, based on the acrylic acid amount that is included in the above-mentioned liquid phase P, their methacrylic acid content can be 0.001-15 weight %, or 0.01-15 weight %, or 0.02-10 weight %, or 0.03-7 weight %, or 0.04-5 weight %, or 0.05-3 weight %, or 0.07-2 weight %, or 0.09-1.5 weight %, or 0.1 or 0.15 to 1 or to 0.5 weight %.
Under individual cases, whether the vinylformic acid crystal isolates the total composition that depends on liquid phase P in the process of cooling of the liquid phase P with this composition.According to the instruction of WO 03/078378, this can in addition for comprising 0.5-90 weight %, or 7-50 weight %, or 10-25 weight %, or 10-85 weight %, or 15-80 weight %, or the situation of the liquid phase P of 25-75 weight % water.
EP-A 002 612 for example discloses by adding salt and has eliminated water-acrylic acid eutectic obtaining aqueous acrylic acid solution, and therefore acrylic acid crystallization can even take place (this assist measure also can be used in the inventive method) under low relatively acrylic acid content.
In a similar manner, WO 99/06348 has recommended to add polar organic matter matter (this assist measure also can be used in the inventive method) remove crystalline polypropylene acid from water P before.
DE-A 198 38 845 has instructed when liquid phase P and has comprised＞60 to＜99.9 weight % vinylformic acid, 0.1-40 during the secondary component that weight % high boiling organic solvent and＞0 to 35 weight % obtain in catalyzing propone acid preparation in gas phase, usually vinylformic acid is separated from comprise the liquid phase P that vinylformic acid and boiling point under standard conditions be higher than acrylic acid organic solvent in process of cooling.The liquid phase P that constitutes the DE-A 198 388 45 of presents integral part also is useful for the inventive method, and condition is that they have methacrylic acid impurity of the presently claimed invention.
According to the above, can think that vinylformic acid is comprising 〉=65 weight % vinylformic acid and crystallize out in the process of cooling of pending liquid phase P according to the present invention regularly at least.
Therefore, when liquid phase P comprises 65-99.5 weight %, or 70-99.5 weight %, or 80-99.5 weight %, or 85-99 weight %, or 90-98 weight %, or during 93-97 weight % vinylformic acid, the inventive method especially can advantageously be applied to the liquid phase P of methacrylic acid pollution.This especially works as based on the vinylformic acid that is comprised, the methacrylic acid content is 0.01-15 weight % simultaneously, or 0.02-10 weight %, or 0.03-7 weight %, or 0.04-5 weight %, or 0.05-3 weight %, or 0.07-2 weight %, or 0.09-1.5 weight %, or 0.1 or 0.15 to 1 or to the situation of 0.5 weight %.
In addition, the present invention is pending comprise vinylformic acid can be in a manner known way as main ingredient and methacrylic acid as the liquid phase P of secondary component, for example in mode as described in having described as prior art by the acrylic acid C that pollutes
3Obtain (coming from this) (propane, propylene and/or propenal in the product gas mixture of the heterogeneously catalyzed partial oxidation of precursor; Possible C
3Precursor also comprises propionic acid, propyl alcohol and/or propionic aldehyde; In this case, partial oxidation is the heterogeneous catalytic oxidation dehydrogenation).The residue composition of these product gas mixtures will be essentially as known in the acid of propylene oxide from the known gas phase preparation.In addition, crystallization method of the present invention can carry out and be incorporated in an identical manner whole removing in (ice) acrylic acid in an identical manner from product mixtures, especially instruct as following prior art document, all these for the integral part of presents (based on the acrylic acid amount that wherein comprises, the common methacrylic acid content of this product gas mixture for example is 0.01 to 15 weight %, or to 10 weight %, or to 5 weight %, often be 0.02-4 weight %, under many situations 0.03-3 weight %, be generally 0.04-2 weight %, but also be 0.05-1 weight %, or 0.07-0.75 weight %, or 0.1-0.5 weight %, or 0.2-0.4 weight %): WO 02/055469, WO 03/078378, WO 01/77056, WO 03/041833, DE-A 196 06 877, DE-A 103 36 386, WO 98/01414, WO 01/77056, EP-A 14 84 308, EP-A 14 84 309, US-A 2004/0242826, DE-A 102 43 625, DE-A 196 06 877, EP-A 792 867, EP-A 10 15 410, EP-A 920 408, EP-A 11 89 861, EP-A 10 15 411, EP-A 10 68 174, WO 2004/035514, EP-A 10 66 293, EP-A 11 63 201, EP-A 1,159 249, WO 02/090310, DE-A 101 22 787, WO 03/041832, DE-A 102 35 847, EP-A 12 52 129, EP-A 616 998, EP-A 13 88 533, EP-A 11 25 912 and EP-A 11 16 709.
When the separation method that uses at least a not unique (indistinct) from acrylic acid at least a C
3Obtain comprising in the heterogeneously catalysed partial gas phase oxidation d product gas mixture of precursor vinylformic acid as main ingredient and target product and methacrylic acid as secondary component, and during pending liquid phase P, the inventive method is especially significant according to the present invention.This is especially when removing the situation for the moment that remaining mother liquor to small part in the residual methacrylic acid is recycled to not unique at least separation method at subsequent crystallisation.
The foundation structure that not unique separation method of this crystalline and crystalline uniqueness (distinct) separation method are used in combination is for example by DE-A 196 06 877, EP-A 792 867, and EP-A 14 84 308, EP-A 14 84 309, EP-A 11 16 709, especially EP-A 10 15 410 instructions.
Not unique separation method be defined as a kind of when using this separation method that form and phase composite that comprise the target product that gathers significantly depend on the separation method of the composition of mixture to be separated, and crystallization treatment of the present invention is unique separation method, forms the degree that independent basically (independent fully ideally) formed in liquid phase P to the vinylformic acid crystalline that forms.
Under the situation of this uniqueness and the combination of not unique separation method, more meaningful with regard to the inventive method, in this program operate continuously, because mother liquor comprises the methacrylic acid of the form of gathering, mother liquor recirculation methacrylic acid as a result accumulates in the pending liquid phase P of the present invention.In other words, in the product gas mixture of gaseous oxidation in addition the smaller methacrylic acid content problem that can therefore become serious.The methacrylic acid content that increases also can be included in the liquid phase P, for example the further crystallization of mother liquor that obtains when the inventive method to be improving yield, or when the secondary stream that contains methacrylic acid that obtains in not unique separation method is handled with the raising yield according to the present invention.
This means at loss factor A
MASUnder＜15 the situation, this program will be extremely invalid.The required efficient of technical scale surprisingly according to the present invention only by found＞15 A
MASAnd reach.
Usually, from acrylic acid at least a C
3Obtain the employed at least a not unique separation method of the pending liquid phase P of the present invention in the product gas mixture of the heterogeneously catalysed partial gas phase oxidation of precursor and will be the combination of distillation, rectifying, absorption, absorption, extraction, desorb, stripping, dispersion (distraction), (part) condensation, fractional condensation, membrane separating method such as pervaporation/evaporating-osmosis or these methods.
Especially will usually use distillation, rectifying, absorption, extraction, partial condensation, fractional condensation, desorb, stripping and/or dispersion.The pending liquid phase P of the present invention will usually obtain by reusing aforesaid method.
Under the simplest situation, the pending liquid phase P of the present invention can be for by classification listed C from least a this file
3Absorb in the product gas mixture of the heterogeneously catalysed partial gas phase oxidation of precursor and/or condensation is removed vinylformic acid and the absorbing material and/or partial condensation thing and/or the condensation product that obtain.Under the sort of situation, the present invention preferably is recycled to the mother liquor of absorption and/or condensation.
In the mode that is fit to, not unique and unique isolating combination of described use has and is used at least a outlet that comprises the materials flow of gathering methacrylic acid.The present invention advantageously, this is in a side of unique separation method not.Usually, the bottom liquid of knockout tower will be as this outlet, for example takes out via side-draw and/or via the top from the tower liquid phase P self here or the materials flow that will change into liquid phase P after a while.
Yet methacrylic acid exports also configurable or only is configured in the side that crystallization of the present invention is removed.In this case, outlet will be made up of the mother liquor that comprises the methacrylic acid that gathers.
When the present invention for example remove by according to EP-A 616998 dynamically and stationary crystallization combination when carrying out, the mother liquor that comprises the methacrylic acid that gathers exports and will be configured in the stationary crystallization zone.The latter does not especially have the situation when being recycled to not unique isolating mother liquor when using the inventive method.
When the pending liquid phase P of the present invention (for example by one of said procedure) comes from acrylic acid at least a C
3The product gas mixture of the partial oxidation of precursor based on the acrylic acid content of product gas mixture, comprises methacrylic acid with described content, and when comprising following component in addition, the inventive method is very favourable:
1-30 volume % vinylformic acid,
〉=0 or 0.005 to 10 volume % propylene,
〉=0 or 0.001 to 2 volume % propenal,
〉=0 or 0.001 to 2 volume % Methylacrylaldehydes,
〉=0 or 0.005 to 10 volume % molecular oxygens,
〉=0 or 0.005 to 3 volume % acetate,
〉=0 or 0.001 to 2 volume % propionic acid,
〉=0 or 0.001 to 2 volume % formaldehyde,
〉=0 or 0.001 to 2 other aldehyde of volume %,
With 10-98 volume % or 50-98 volume % (inertia) diluent gas.
Diluent gas can comprise:
The saturated C of 〉=0 or 0.005 to 90 volume %
1-C
6Hydrocarbon (especially propane, methane and/or ethane),
〉=0 or 0.05 to 30 volume % steams,
〉=0 or 0.05 to 15 volume % carbonoxide (CO and/or CO
2),
With 〉=0 or 1 to 90 volume % dinitrogens.
The partial oxidation products gaseous mixture especially can come from as document DE-A 10 2,004 032 129 and their corresponding foreign patent, DE-A 10245585, WO 03/076370, WO 01/96271, EP-A 117146, WO 03/011804, US-A 3161670, DE-A 3313573, DE-A 10316039 and WO 01/96270 described partial oxidation, originate in propylene and/or propane and originate as propylene, if suitable have dehydrogenating propane and/or oxydehydrogenation (if suitable, heterogeneous catalysis) as previous step of reaction.
The representative instance that this product gas mixture is formed (promptly only a possible example) is for to comprise the product gas mixture of following component (if all secondary components of listing have been the component of liquid phase P, then when using the inventive method, will remove them satisfactorily):
Volume %
Nitrogen 51.54
Oxygen 2.3
Propane 29.20
Propylene 0.110
Methane 0
Ethane 0.077
Normal butane 0.101
Trimethylmethane 0.236
N-butene 0
Iso-butylene 0.001
1,3-butadiene 0.009
Hydrogen 0.05
Carbon monoxide 0.596
Carbonic acid gas 1.72
Water 8.21
Propenal 0.09
Vinylformic acid 5.28
Acetate 0.240
Propionic acid 0.002
Formic acid 0.019
Formaldehyde 0.198
Phenyl aldehyde 0.005
Maleic anhydride 0.047
Methylacrylaldehyde 0.020
Methacrylic acid 0.011 He
Ethene 0.032.
The present invention advantageously, the pending liquid phase P of the present invention will be by the vinylformic acid condensation is gone out product gas mixture from above-mentioned C
3Obtain in the product gas mixture of acrylic precursor partial oxidation.The present invention advantageously, the condensation product that obtains directly forms liquid phase P.Advantageously, it is (if suitable that the vinylformic acid condensation is gone out product gas mixture, cooling in advance) (if suitable as fractional condensation, the extra additional water and/or the aqueous solution absorb to reduce the vinylformic acid loss on it) and carry out, for example such as document EP-A 1015410, WO 2004/035514, DE-A 10243625, EP-A 1015411, DE-A 10235847, EP-A 1159249, EP-A 1163201, EP-A 1066239 and EP-A 920408 detailed description.
In this condensation, if it is suitable, formerly directly and/or indirectly cooling (for example use according to EP-A 1066239 or according to EP-A 1163201 and use quench liquid) afterwards with product gas mixture suitable fractional condensation in having the knockout tower that separates internals, with side-draw remove vinylformic acid and self rising (it is preferably formed the pending liquid phase P of the present invention; If suitable, also crude acrylic acid rectifying and/or distillation are handled to obtain liquid phase P).
The liquid phase P that such condensation (and if suitable extra rectifying) can be obtained is according to the present invention and crystallization treatment then.For example, comprise the near small part of the mother liquor that gathers methacrylic acid of formation, preferably all be recycled to the vinylformic acid condensation is gone out product gas mixture according to the pattern of EP-A 920408 or WO 2004/035514.The methacrylic acid outlet will be arranged on below the crude acrylic acid side-draw.
Like this by part or all of condensation and/or additional water or aqueous solution absorption, if and suitable rectifying aftertreatment and obtaining and pending liquid phase P according to the present invention, remove based on the vinylformic acid that is comprised, outside specified (and be basic to the present invention) methacrylic acid content, also comprise:
65, or 75, or 85 to 99.5 weight % vinylformic acid,
〉=0, common 0.1-40 weight % water,
〉=0, common 0.001-5 weight % propenal,
〉=0, common 0.001-10 weight % Methylacrylaldehyde,
〉=0, common 0.01-5 weight % acetate,
〉=0, common 0.01-5 weight % propionic acid,
〉=0, common 0.001-5 weight % formaldehyde,
〉=0, usually other aldehyde of 0.001-5 weight % (every kind of aldehyde) and
〉=0, common 0.01-5 weight % toxilic acid.
The above-mentioned content of liquid phase P advantageously is:
93-98 weight % vinylformic acid,
1-5 weight % water,
0.001-3 weight % propenal,
0.001-3 weight % Methylacrylaldehyde,
0.1-3 weight % acetate,
0.01-3 weight % propionic acid,
0.001-3 weight % formaldehyde,
0.001-3 other aldehyde of weight % (every kind of aldehyde) and
0.01-3 weight % toxilic acid.
According to the specification sheets of WO 02/055469 and WO 03/078378, also can comprise 3 weight % protoanemonin at the most.
Liquid phase P of the present invention, the crystallization treatment of the liquid phase P that condensation especially in the above described manner and/or absorption and/or rectifying obtain comprises that the method (can use all to be described in detail in the method for mentioning of the prior art) of removing mother liquor from crystal is unrestricted in principle.
In other words, can in one or more stages, carry out continuously or in batches.Especially also can be used as fractional crystallization carries out.Usually, in fractional crystallization, the vinylformic acid crystalline stage that the liquid phase P that is provided purer (especially more not having methacrylic acid) is provided in all generations is called as purification phase and every other stripping stage.The contrary principle of passing through that multi-stage process is fit to is operated, wherein in each stage after the crystallization, crystal is removed from mother liquor, and these crystal of specified phase are infeeded with next highest purity, and the crystalline residue of specified phase is infeeded with next lowest purity.
Usually, the temperature of liquid phase P is-25 ℃ to+14 ℃ in the inventive method, especially 12 ℃ to-5 ℃.
For example, the inventive method can be used as layer crystallization and carries out (referring to DE-A 2606364, EP-A 616998, EP-A 648520 and EP-A 776875).In this crystallization, crystal freezes with the form of the strong adhesion layer of successive analyses.Sedimentary crystal relies on the simple outflow of remaining melts and separates from remaining remaining melts (mother liquor).In principle, the difference between extraction " static state " and " dynamically " layer crystallization method.The dynamic layer crystalline characteristic feature of liquid phase P is the forced convection of liquid phase P.This can be by introducing (for example according to EP-A 616998) with liquid phase P as the drip film or being undertaken by rare gas element being introduced in the liquid phase P or being made the liquid phase pumping circulation pass completely through pipe by pulsation.
In static method, liquid phase P is immobilized (for example in tube bank or a plate-type heat exchanger), and deposits in layer owing to the slow reduction of primary side temperature.Then, discharge remaining melts (mother liquor), more the high pollution cut is discharged from crystal layer by slow raising temperature, and pure products melts (referring to WO 01/77056) subsequently.
According to the present invention, yet under the situation of described all liquid phase P of presents, the inventive method will preferably be carried out as suspension crystallization according to the instruction of WO 01/77056, WO 02/055469 and WO 03/078378.
Usually, comprise suspension vinylformic acid crystalline crystal suspension by the liquid phase P cooling is obtained, the vinylformic acid crystal has the methacrylic acid content (relative, based on specific total amount) that the methacrylic acid content that is lower than the liquid phase P of waiting to purify and remaining melts (mother liquor) are kept above the liquid phase P of waiting to purify.The vinylformic acid crystal can be directly growth and/or in suspension as being deposited upon on the cooling stave, subsequently with they from cooling stave wipe off and resuspending in remaining melts (mother liquor).
According to the present invention, all suspension crystallization device and suspension crystallization methods that are described in detail among WO 01/77056, WO 02/055469 and the WO 03/078378 are useful.Usually, the solids content of the vinylformic acid crystal suspension of generation is 20-40 weight %.
In addition, the suspension crystal that all is suitable for forming of the method described in all above-mentioned WO publications separates (for example mechanical separation method such as centrifugation) with remaining mother liquor.According to the present invention, preferably in washing tower, separate.This preferably has the sedimentary vinylformic acid crystalline of forced conveyance washing tower.Crystal volume fraction reaches＞0.5 value usually in the bed of crystals.Washing tower is usually with the Value Operations of 0.6-0.75.Used washing liq advantageously is the vinylformic acid crystalline melts of purify in advance in the washing tower (removing).Washing common adverse current carries out.Therefore, the inventive method especially comprises the method for following processing step:
A) the vinylformic acid crystallization is gone out liquid phase P;
B) the vinylformic acid crystal is separated with remaining mother liquor (remaining melts, remaining liquid phase);
C) make the vinylformic acid crystal removed at least partial melting and
D) make fused vinylformic acid crystal to small part be recycled to step b) and/or step a).
Preferably by with remove in advance, fusion and the vinylformic acid crystal countercurrent washing that is recycled to step b) carry out step b).
According to the present invention, advantageously when using the inventive method, because the vinylformic acid crystal forms in the presence of water, according to the instruction of WO 01/77056 and WO 03/078378, liquid phase P comprises the particularly advantageous crystalline form of water generates and is used for subsequently crystal being separated from remaining mother liquor.When crystallization was carried out as suspension crystallization, this was especially true, when carrying out mother liquor subsequently when removing even all the more so in washing tower, when used washing liq during for the vinylformic acid crystalline melts of having purified in washing tower even all the more so.
In other words, the inventive method especially comprises the method that liquid phase P to be purified is changed into the crystal suspension of being made up of vinylformic acid crystal and remaining liquid phase (remaining melts) under the effect of cool condition, the part by weight of the methacrylic acid in the vinylformic acid crystal less than and the part by weight of the residue liquid phase (mother liquor) of methacrylic acid greater than the part by weight of the methacrylic acid in the liquid phase P, if it is suitable, a part is remained mother liquor machinery from crystal suspension removes, and making no vinylformic acid crystal in the washing tower that remains mother liquor, condition is
A) based on the vinylformic acid that wherein comprises, liquid phase P comprises 0.20-30 weight %, 20 weight % at the most often, usually at the most 10 weight % water and
B) used washing liq is the vinylformic acid crystalline melts of purifying in washing tower.
The inventive method comprises aforesaid method, and liquid phase P is especially wrapped 〉=80 weight % vinylformic acid, or 〉=90 weight % vinylformic acid or 〉=95 weight % vinylformic acid.Under every kind of situation, the mol ratio V in the liquid phase P to be purified can have all values described in the presents.
In addition, according to the present invention, the vinylformic acid that is comprised in based on liquid phase P, the water-content of when using the inventive method (or, very general) liquid phase P is 0.2 or 0.4 to 8 in said procedure, or to 10, or to 20, or to 30 weight %, or 0.6-5 weight %, or be favourable during 0.60-3 weight %.
Certainly, the inventive method also is applicable to all crude acrylic acids of WO 98/01414, and condition is that they additionally comprise methacrylic acid as secondary component.
Especially when washing tower when having forced conveyance vinylformic acid crystalline washing tower, especially when it be according to the waterpower of WO 01/77056 or machine washing tower and as when wherein describing operation in detail, all aforesaid methods are suitable for.
Especially when washing tower during according to the instruction of WO 03/041832 and WO 03/041833 design and operation, all are above-mentioned to be real.
Therefore, the inventive method allows in the following order with efficient way, only uses a crystallisation stage preparation to be suitable for the vinylformic acid of super-absorbent: at least a C
3The precursor portions oxidation, fractional condensation vinylformic acid from the product gas mixture of partial oxidation, make the vinylformic acid condensation product suspension crystallization of taking-up and use pure crystal melts (to be the cheap C that causes the methacrylic acid by product to form certainly, even when the starting raw material that is used for partial oxidation as taking out the suspension crystal in the residue mother liquor of washing liq from washing tower
3During the precursor raw material source, this vinylformic acid also can be used for WO 02/055469 and WO 03/078378 described all other purposes).
Certainly, all method stepss of describing in detail in this file carry out with resistance is poly-.Program can be as described in the listed prior art.The stablizer of fabulous state is envisioned for dibenzo-1 in whole available vinylformic acid method, 4-thiazine (PTZ), 4-hydroxyl-2,2,6,6-tetramethyl piperidine 1-oxygen base (4-OH-TEMPO) and p methoxy phenol (MEHQ), it can be separately or in pairs or as the mixture of the three kinds of materials part for the pending liquid phase P of the present invention.Usually, based on the total amount of vinylformic acid that is wherein comprised and methacrylic acid, the total amount that is included in the stopper in the liquid phase P is 0.001-2 weight %.
Owing to when staying liquid phase P separately, be not desirably formed acrylic acid oligomer (Michael adducts) in the liquid phase P, after producing liquid phase P, use the inventive method as far as possible rapidly.
According to the present invention in an advantageous manner, when using the inventive method, also will be included in other C in the liquid phase P
4(as butene-1, divinyl, normal butane etc.) subsequent portion oxidation products, for example Methylacrylaldehyde, butyric acid, butyraldehyde etc. are removed.Based on vinylformic acid, they can the amount identical with methacrylic acid be present in the liquid phase P (especially be present in presents all liquid phase P of clearly describing in detail in).Above-mentioned situation is equally applicable to propionic aldehyde and all C
5And C
6The subsequent portion oxidation products.
Embodiment and comparative example
Comparative example
The 430g methacrylic acid packed under 25 ℃ have in the chuck refrigerative stirred glass container (internal volume 11).Stirring is undertaken by the close clearance spiral stirrer.
Methacrylic acid comprises:
69.1 weight % methacrylic acid,
18.2 weight % water,
3.6 weight % acetate and
0.5 weight % vinylformic acid.
It by heterogeneous break gasification phase partial oxidation Methylacrylaldehyde and subsequently the fractional condensation product gas mixture obtain.Adding suppresses the methacrylic acid polymerization less than 200 ppm by weight (based on vinylformic acid and methacrylic acid sum) quinhydrones.
Under the rate of cooling of 0.5K/h, the temperature that reduces the cooling fluid of handling in the chuck (water/glycol or water/alcohol mixture) is 16 weight % until the solids content of the crystal suspension that produces (being suspended in the methacrylic acid crystal in the residue melts).Then a part of crystal suspension is taken out and under the 2000rpm in the sieve cup that is being equipped with the polypropylene filter cloth on the laboratory centrifuge centrifugal 30 seconds.This is centrifugal to go out great majority residue mother liquors.Subsequently, mother liquor remove by again described centrifugal 30 seconds and with 1: 1 weight ratio with methacrylic acid washing crystal (methacrylic acid content＞98 weight %, acrylic acid content＜0.1 weight %, temperature=25 of this washing methacrylic acid ℃) simultaneously.The residue crystal obtains following loss factor A with the analysis of the centrifugal mother liquor that falls in advance for the different secondary components that is included in the methacrylic acid:
| Secondary component | A |
| Water | 41.7 |
| Acetate | 33.3 |
| Vinylformic acid | 9.09 |
Opposite with water and acetate, vinylformic acid is mixed in the sedimentary methacrylic acid crystal.
Embodiment
Will the various vinylformic acid of about 1800g under every kind of situation pack into and stir in the metal tin (internal volume 2l, close clearance spiral stirrer).They by adding 100-200 ppm by weight quinhydrones monomethyl ether (MEHQ) and＜100 ppm by weight thiodiphenylamine (based on the vinylformic acid that is comprised) hinder and gather.
Under the rate of cooling of 1K/h, the solids content of the crystal suspension that the temperature of cooling liqs produces under every kind of situation in the reduction chuck (being suspended in the vinylformic acid crystal in the residue melts) is about 18 weight %.Then a part of crystal suspension is taken out and under the 2000rpm on as the laboratory centrifuge in the comparative example centrifugal 180 seconds, remain like this that mother liquor is complete basically centrifugally to be gone out.The residue crystal obtains following loss factor with the vinylformic acid (liquid phase P that the present invention is pending) that the analysis of the centrifugal mother liquor that goes out is polluted for the different secondary components owing to wherein comprising.Vinylformic acid originates in to come from and has little C
4The vinylformic acid of the propylene heterogeneous catalyzed gas phase partial oxidation of cut is by obtaining to wherein adding glacial methacrylic acid.Initial vinylformic acid comprises following component:
95.201 weight % vinylformic acid,
0.042 weight % methacrylic acid,
0.604 weight % phenyl aldehyde,
0.062 weight % propionic acid,
0.687 weight % furans-2-aldehyde,
0.663 weight % acetate,
0.004 weight % furans-3-aldehyde,
0.002 weight % vinylformic acid allyl ester,
0.009 weight % propenal and
2.20 weight % water.
This vinylformic acid is mixed once with 0.2 weight % methacrylic acid (sample 1), mix once with 1 weight % methacrylic acid (sample 2), mix once (every kind of situation is based on initial acrylic acid weight) with 5 weight % methacrylic acids (sample 3), and different samples is handled as described.Handle starting acid itself in the same way.For the secondary component that is included in various sample and the starting acid, the loss factor of mensuration is as follows:
| Secondary component | A (sample 1) | A (sample 2) | A (sample 3) | A (starting acid) |
| Methacrylic acid | 31.3 | 45.5 | 30.3 | In crystal, no longer can detect |
| Phenyl aldehyde | 31.3 | 45.4 | 31.2 | 31.2 |
| Propionic acid | 3.9 | 4.1 | 3.85 | 3.86 |
| Furans-2-aldehyde | 31.3 | 47.6 | 30.3 | 31.25 |
| Acetate | 5.8 | 6.4 | 5.59 | 5.85 |
Obviously, ratio is opposite with the situation of comparative example.When acetate and propionic acid here mixed, this was not the situation of methacrylic acid, situation that neither two kinds of aldehyde.
The US Provisional Patent Application Nos.60/668 of on April 5th, 2005 application, 60/656,877 of application on March 1st, 089 and 2005 is also introduced among the application as a reference.About above-mentioned instruction, a large amount of changes of the present invention and to derive be possible.Therefore, can imagine in the scope of the claim of enclosing, the present invention can carry out to be different from clear and definite described mode here.
Claims (22)
1. one kind from comprising vinylformic acid as the method for removing methacrylic acid main ingredient and target product and the liquid phase P of methacrylic acid as secondary component, it comprises by crystallization removes, vinylformic acid accumulate in the crystal of formation and methacrylic acid in remaining mother liquor.
2. according to the process of claim 1 wherein that described liquid phase P comprises vinylformic acid and methacrylic acid with at least 3: 2 the vinylformic acid and the mol ratio V of methacrylic acid.
3. according to the method for claim 1 or 2, the V in the wherein said liquid phase P is 3: 2-100000: 1.
4. according to each method among the claim 1-3, wherein said liquid phase P comprises at least 10 weight % vinylformic acid.
5. according to each method among the claim 1-3, wherein said liquid phase P comprises at least 65 weight % vinylformic acid.
6. according to each method among the claim 1-5, wherein based on wherein contained acrylic acid amount, described liquid phase P comprises 0.01-15 weight % methacrylic acid.
7. according to each method among the claim 1-6, wherein said liquid phase P comprises 65-99.5 weight % vinylformic acid.
8. according to each method among the claim 1-7, wherein based on wherein contained acrylic acid amount, described liquid phase P comprises 0.2-30 weight % water.
9. according to each method among the claim 1-8, wherein said liquid phase P comes from acrylic acid at least a C
3The product gas mixture of the heterogeneous catalyzed gas phase partial oxidation of precursor compound.
10. according to the method for claim 9, wherein said at least a C
3Precursor compound is a propane.
11. according to the method for claim 9, wherein said at least a C
3Precursor compound is a propylene.
12. according to the method for claim 9, wherein said at least a C
3Precursor compound is to be attended by the propylene of propane as inert composition.
13. according to the method for claim 12, wherein said propylene and the propane of following are the component of the product gas mixture of the part dehydrogenation of propane before the gas-phase partial oxidation and/or oxydehydrogenation.
14. according to each method among the claim 1-13, wherein said liquid phase P comes from acrylic acid at least a C
3The product gas mixture of the heterogeneous catalyzed gas phase partial oxidation of precursor compound and used at least a not unique separation method and therefrom obtain.
15. according to the method for claim 14, wherein said at least a not unique separation method comprises at least a separation method that comes self-absorption, partial condensation, fractional condensation, rectifying, stripping and desorb.
16. according to the method for claim 14 or 15, wherein make the mother liquor that comprises the methacrylic acid that gathers be recycled at least a not unique separation method one of at least in.
17., wherein make the mother liquor that comprises the methacrylic acid that gathers be recycled to acrylic acid at least a C according to the method for claim 16
3In the fractional condensation of the product gas mixture of the heterogeneous catalyzed gas phase partial oxidation of precursor compound.
18. according to each method among the claim 1-17, wherein said crystallization is removed by suspension crystallization and is undertaken.
19. according to the method for claim 18, wherein said suspension crystal is undertaken with residue separating by washing tower of mother liquor.
20. according to the method for claim 19, the vinylformic acid crystalline melts of wherein used washing liq in washing tower, removing in advance.
21. according to each method among the claim 1-20, it comprises following processing step:
A) the vinylformic acid crystallization is gone out liquid phase P;
B) the vinylformic acid crystal is separated with remaining mother liquor;
C) make the vinylformic acid crystal removed at least partial melting and
D) make fused vinylformic acid crystal to small part be recycled to step b) and/or step a).
22., the method with fusion of vinylformic acid crystal and the synthetic polymkeric substance of radical polymerization is arranged thereafter according to each method among the claim 1-21.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65687705P | 2005-03-01 | 2005-03-01 | |
| DE200510009890 DE102005009890A1 (en) | 2005-03-01 | 2005-03-01 | Separation of methracrolein from acrylic acid, comprises crystallizing and separating the acrylic acid, and leaving the methacrolein in a liquid phase of the mother liquor |
| DE102005009890.8 | 2005-03-01 | ||
| US60/656,877 | 2005-03-01 | ||
| US66808905P | 2005-04-05 | 2005-04-05 | |
| DE102005015639.8 | 2005-04-05 | ||
| US60/668,089 | 2005-04-05 | ||
| DE200510015639 DE102005015639A1 (en) | 2005-04-05 | 2005-04-05 | Removal of methacrylic acid from liquid phase comprising acrylic acid as main constituent involves performing crystallization to accumulate acrylic acid in the crystals formed and the methacrylic acid in the remaining mother liquor |
| PCT/EP2006/060354 WO2006092405A1 (en) | 2005-03-01 | 2006-03-01 | Method for the elimination of methacrylic acid from a liquid phase containing acrylic acid as a main component and target product and methacrylic acid as a secondary component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101133012A true CN101133012A (en) | 2008-02-27 |
| CN101133012B CN101133012B (en) | 2012-09-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800068559A Active CN101133012B (en) | 2005-03-01 | 2006-03-01 | Process for removing methacrylic acid from liquid phase comprising acrylic acid as a main constituent and target product, and methacrylic acid as a secondary component |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN101133012B (en) |
| DE (1) | DE102005009890A1 (en) |
| ZA (1) | ZA200708303B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471214A (en) * | 2009-06-30 | 2012-05-23 | 株式会社日本触媒 | Device for crystallizing acrylic acid and method for crystallizing acrylic acid using same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1018537A3 (en) | 2007-09-13 | 2011-03-01 | Basf Se | METHOD FOR OPERATING A CONTINUOUS SEPARATION OF TARGET PRODUCT X IN THE FORM OF A FINALLY DIVIDED CRYSTALLISATE |
| DE102007043758A1 (en) | 2007-09-13 | 2008-10-23 | Basf Se | Target product continuous separating operation in form of fine crystals from liquid phase, includes heat exchanger having secondary space and primary space |
| DE102007043748A1 (en) | 2007-09-13 | 2008-09-11 | Basf Se | Method for separating target product i.e. acrylic acid, methacrylic acid, p-xylene or N-vinylpyrrolidone in form of fine crystallized product, involves utilizing heat exchanger, where heat flow is gathered from heat exchanger |
| DE102007043759A1 (en) | 2007-09-13 | 2008-09-11 | Basf Se | Procedure for continuous separation of target product in the form of fine particle of crystallisate, comprises indirectly operating a heat exchanger having primary and secondary areas, which are spatially separated with one another |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW305830B (en) * | 1993-03-26 | 1997-05-21 | Sulzer Chemtech Ag | |
| DE19829477A1 (en) * | 1998-07-01 | 2000-01-05 | Basf Ag | Process for the purification of acrylic acid or methacrylic acid by crystallization and distillation |
-
2005
- 2005-03-01 DE DE200510009890 patent/DE102005009890A1/en not_active Withdrawn
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2006
- 2006-03-01 CN CN2006800068559A patent/CN101133012B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471214A (en) * | 2009-06-30 | 2012-05-23 | 株式会社日本触媒 | Device for crystallizing acrylic acid and method for crystallizing acrylic acid using same |
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| Publication number | Publication date |
|---|---|
| ZA200708303B (en) | 2009-04-29 |
| DE102005009890A1 (en) | 2006-09-07 |
| CN101133012B (en) | 2012-09-05 |
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