CN102351667A - Method for preparing isobutylaldehyde by performing selective hydrogenation on methylacrolein - Google Patents
Method for preparing isobutylaldehyde by performing selective hydrogenation on methylacrolein Download PDFInfo
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- CN102351667A CN102351667A CN2011102813101A CN201110281310A CN102351667A CN 102351667 A CN102351667 A CN 102351667A CN 2011102813101 A CN2011102813101 A CN 2011102813101A CN 201110281310 A CN201110281310 A CN 201110281310A CN 102351667 A CN102351667 A CN 102351667A
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- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 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
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 238000007654 immersion Methods 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
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- -1 NSC 6366 Chemical compound 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RGFNRWTWDWVHDD-UHFFFAOYSA-N isobutyl butyrate Chemical compound CCCC(=O)OCC(C)C RGFNRWTWDWVHDD-UHFFFAOYSA-N 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- PYLMCYQHBRSDND-UHFFFAOYSA-N 2-ethyl-2-hexenal Chemical compound CCCC=C(CC)C=O PYLMCYQHBRSDND-UHFFFAOYSA-N 0.000 description 1
- WBPAQKQBUKYCJS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxypropanoate Chemical compound CC(C)COC(=O)C(C)O WBPAQKQBUKYCJS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QSSMIHKTUJBVGO-UHFFFAOYSA-N C(C(C)C)O.C(CCCCCCCCC(=O)O)(=O)O Chemical compound C(C(C)C)O.C(CCCCCCCCC(=O)O)(=O)O QSSMIHKTUJBVGO-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000737241 Cocos Species 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- JSLCOZYBKYHZNL-UHFFFAOYSA-N isobutyric acid butyl ester Natural products CCCCOC(=O)C(C)C JSLCOZYBKYHZNL-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AGBVGLJAIGBYAD-UHFFFAOYSA-N tris(2-methylpropyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CC(C)COC(=O)CC(O)(C(=O)OCC(C)C)CC(=O)OCC(C)C AGBVGLJAIGBYAD-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing isobutylaldehyde by performing selective hydrogenation on methylacrolein. In the method, isobutylaldehyde is prepared by performing selective hydrogenation on methylacrolein under the catalytic action of a loaded Pd catalyst, wherein the content of Pd in the catalyst is 0.1-5 percent by weight; and a catalyst carrier is selected from one or more of a molecular sieve, a metal oxide, mesoporous silica, amorphous aluminum silicate, active carbon or a carbon nanotube. The method has a mild reaction condition, high catalyst activity and high selectivity, the conversion rate of the methylacrolein is more than or equal to 99 percent, the isobutylaldehyde selectivity is more than or equal to 95.4 percent, and the catalyst has continuously stable performance after over 1,000 hours of continuous reaction. The method is an effective measure for preparing the isobutylaldehyde by performing selective hydrogenation on the methylacrolein which is prepared by oxidizing isobutene or tertiary butanol serving as a C4 raw material with the air.
Description
Technical field
The present invention relates to a kind of Methylacrylaldehyde and select the method for hydrogenation preparing isobutyric aldehyde, be specifically related to a kind of loading type Pd catalyzer that adopts and make Methylacrylaldehyde select the method for hydrogenation preparing isobutyric aldehyde.
Background technology
Isobutyric aldehyde is a kind of important Organic Chemicals, can be used for producing Chemicals such as isopropylcarbinol, NSC 6366, isopropylformic acid, methylethylketone, and wherein NSC 6366 and isopropylcarbinol are topmost two kinds of derived product.Isopropylcarbinol is good solvent, also can be used for fields such as petroleum additive, inhibitor, frostproofer, viton, synthetic musk, fruit essential oil and synthetic drugs.From isopropylcarbinol; Can Synthetic 2; Ester derivatives such as 6-ditertbutylparacresol and diisobutyl phthalate, isobutyl acetate, isobutyl butyrate, isobutyl lactate, tri-iso-butyl citrate, sebacic acid isobutylate, hard acid isobutyl ester butyl ester are widely used in the production of coating, softening agent, synthetic lubricant, hydraulic pressure wet goods.NSC 6366 is typical neopentyl structure divalent alcohol, has good chemical reaction performance, can participate in number of chemical reactions such as esterification, condensation and oxidation fast, is widely used in to produce polyester resin, urethane, powder coating and ucon oil etc.
Industry is at present gone up isobutyric aldehyde and is mainly derived from that the propylene carbonyl compound is come of age, the by product of octanol.But improvement along with fourth octanol production technique; The positive isomery of butyraldehyde is increased to more than 10: 1 even 20: 1 than gradually in the product; Cause the source of isobutyric aldehyde to be restricted, output descends, and can't satisfy the demand that market, downstream increases day by day; Limit the development of derived product, therefore needed the new synthetic way line of exploitation isobutyric aldehyde badly.
At present, the mixed C that comes from petrochemical complex and Coal Chemical Industry
4Component does not also obtain good use, and most of component as LPG liquefied petroleum gas is used as fuel, is worth lower.And with mixed C
4Iso-butylene in the component is that raw material production Methylacrylaldehyde and methylacrylic acid have been realized industriallization, and it is C=C key hydrogenation and keep the C=O key that Methylacrylaldehyde is selected hydrogenation, can obtain isobutyric aldehyde; For the production of isobutyric aldehyde provides a new operational path, come source problem significant for what solve isobutyric aldehyde.
By the existing patent report of unsaturated aldehyde hydrogenation system saturated aldehyde, adopting with Ni mostly is the catalyzer of active ingredient, but the Ni activity of such catalysts is too high, is prone to make the complete hydrogenation of unsaturated aldehyde to generate saturated alcohol, causes the yield of saturated aldehyde lower, generally is no more than 90%.And, by cracking side-reaction produce-CO and Ni reaction generation nickle carbonoxide, will cause the inactivation of Ni catalyzer, reduced life of catalyst.Patent GB 1102796A employing sulfide makes the mode of Ni catalyst member poisoning, improves the selectivity of saturated aldehyde.When this catalyzer was used for the hydrogenation reaction of unsaturated aldehyde such as crotonic aldehyde, propenal, 2-ethyl hexenal, the selectivity of saturated aldehyde can be increased to more than 94%, but the space-time yield of saturated aldehyde is lower, unsaturated aldehyde volume space velocity 0.15～0.2h
-1, and reaction needs is carried out under the comparatively high temps more than 200 ℃.The Pd catalyzer that patent GB1065628A adopts auxiliary agent Cu, Co, Ni, Ag or Au to modify; Under 70～140 ℃ of lower temperature of reaction, unsaturated aldehyde transformation efficiency 99%, saturated aldehyde selectivity 90～96%; But the space-time yield of saturated aldehyde is also lower, unsaturated aldehyde volume space velocity 0.12～0.15h
-1, poor catalyst stability, the life-span is lower than 400 hours.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Methylacrylaldehyde to select the method for hydrogenation preparing isobutyric aldehyde; This method adopts with the loading type Pd catalyzer of Pd as active ingredient; Reaction conditions is gentle, and catalyst activity is high, selectivity is good, has satisfactory stability property; Solved the various problems that existing technology exists effectively, for used for preparing isobutylaldehyde provides a kind of new effective way.
The present invention realizes above-mentioned purpose through following technical scheme.
Described Methylacrylaldehyde is selected the method for hydrogenation preparing isobutyric aldehyde, adopts the loading type Pd catalyzer to carry out the Methylacrylaldehyde selective hydrogenation reaction and prepares isobutyric aldehyde, and described selective hydrogenation reaction can be still reaction or fixed bed reaction.
Among the above-mentioned preparation method; Described loading type Pd catalyzer is meant the soluble salt solution of Pd (like nitrate salt, vitriol, halogen, acetate etc.) and corresponding carrier is got the catalyzer precursor through immersion process for preparing; Then after 50～200 ℃ of temperature dryings and 300～600 ℃ of temperature roastings, with hydrogen or hydrogen-nitrogen mixture gas at pressure 0.2～10.0MPa, hydrogen gas space velocity 200～3000h
-1, 180～450 ℃ of reduction temperatures condition under reduced 4～48 hours, promptly make said loading type Pd catalyzer.
Wherein, the content of Pd is 0.1wt%～5wt% in the said catalyzer, preferred 0.2wt%～2wt%.
Said carrier is selected from one or more in molecular sieve, MOX, mesoporous silicon oxide, amorphous aluminum silicate, atlapulgite, zeyssatite, polynite, wilkinite, kaolin, hydrotalcite, activated carbon or the carbon nanotube.Wherein, said molecular screening one or more in ZSM-5, ZSM-22, ZSM-35, MCM-49, MCM-22, MCM-56, MCM-36, MCM-41, MCM-48, mordenite (MOR), β zeolite, Y zeolite, SAPO-34 or SAPO-11; Said MOX is selected from Al
2O
3, SiO
2, TiO
2, ZrO
2, among the MgO, SnO, CaO, BaO one or more; Said mesoporous silicon oxide is selected from one or more among SBA-15, MCM-41, MCM-48, HMS or the MSU.Described activated carbon is selected from coal-based activated carbon, cocos active carbon or conventional common activated carbon etc.
Said still reaction condition is: 40～200 ℃ of temperature of reaction, preferred 50～100 ℃; Reaction pressure 0.1～5.0MPa, preferred 0.2～2.0MPa; 1～24 hour reaction times, preferred 2～16 hours.
Said fixed bed reaction condition is: 40～200 ℃ of temperature of reaction, preferred 50～100 ℃; Reaction pressure 0.1～5.0MPa, preferred 0.2～2.0MPa; The mass space velocity of Methylacrylaldehyde is 0.2～5.0h
-1, preferred 0.2～3.0h
-1, H
2The mol ratio of/Methylacrylaldehyde is 1: 1～50: 1, preferred 2: 1～20: 1.
Beneficial effect:
The present invention adopts the loading type Pd catalyzer to carry out the Methylacrylaldehyde selective hydrogenation reaction to prepare isobutyric aldehyde; Reaction conditions is gentle, and catalyst activity is high, selectivity is good, wherein the transformation efficiency of Methylacrylaldehyde >=99%; Reach as high as 100%, the selectivity of isobutyric aldehyde >=95.4%.
And catalyzer of the present invention also has satisfactory stability property, but successive reaction efficiently solved the various problems that existing technology exists, for used for preparing isobutylaldehyde provides a kind of new effective way more than 1000 hours.Therefore, the present invention utilizes C
4The raw material iso-butylene or the trimethyl carbinol are suitable for scale operation through a kind of effective way of the Methylacrylaldehyde selection hydrogenation preparing isobutyric aldehyde of atmospheric oxidation preparation.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail, but said embodiment does not limit protection scope of the present invention.
One, Preparation of catalysts:
The preparation finite concentration contains the soluble salt aqueous solution of Pd; Flood than it is added in respective carrier according to metering, be prepared into the catalyzer precursor, then 110 ℃ dry 12 hours down; After the high-temperature roasting; Reduce to room temperature, in the reactor drum of packing into, with hydrogen or hydrogen-nitrogen mixture gas at pressure 1.0MPa, hydrogen gas space velocity 1000h
-1Reduction is handled under the condition, promptly makes loading type Pd catalyzer of the present invention.
Embodiment 1～20
The above-mentioned loading type Pd catalyzer that makes, the adjustment reaction conditions, charging is reacted.Wherein the carrier of catalyzer, Pd content and preparation condition, title product reaction conditions, reaction result are respectively referring to table 1, table 2 and table 3.
Table 1
Two, the reactive behavior evaluation of catalyzer:
1. the still reaction activity rating of catalyzer:
In 500 milliliters of stainless steel high pressure stirred autoclaves; Add a kind of in the catalyzer of the foregoing description 1～8 of 300 gram Methylacrylaldehydes and a certain amount of (are basic calculation with the reaction raw materials) respectively; Be warming up to temperature of reaction behind the hydrogen exchange reactor drum; 50～100 ℃ of control reaction pressure 0.5～10MPa, temperature of reaction, stirring velocity 500～2000 is changeed.Reaction conditions and reaction result concrete among the embodiment 1～8 are seen table 2.
Table 2
2. the fixed bed pipe reaction activity rating of catalyzer:
Catalyzer among the embodiment 9～20 100 grams are respectively charged into fixed-bed tube reactor, reduce according to the condition that table 1 is corresponding.Get into reactor reaction after Methylacrylaldehyde raw material and the hydrogen mixing preheating, reaction conditions and reaction result concrete among the embodiment 9～20 are seen table 3.
Table 3
Three, the stability test of catalyzer:
Embodiment 21～22
Catalyzer among the embodiment 2,5 100 grams are respectively charged into fixed-bed tube reactor, reduce according to the condition that table 1 is corresponding.Get into reactor reaction after Methylacrylaldehyde raw material and the hydrogen mixing preheating, investigate the stability of catalyzer, reaction conditions is identical with embodiment 2,5 respectively, and reaction result is seen table 4.
Table 4
Should be noted that at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement the technical scheme of invention; And not breaking away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (8)
1. the method for a Methylacrylaldehyde selection hydrogenation preparing isobutyric aldehyde is characterized in that, adopts the loading type Pd catalyzer to carry out Methylacrylaldehyde and selects the hydrogenation preparing isobutyric aldehyde;
Wherein, The content of Pd is 0.1wt%～5wt% in the said catalyzer, and support of the catalyst is selected from molecular sieve, MOX, mesoporous silicon oxide, amorphous aluminum silicate, atlapulgite, zeyssatite, polynite, wilkinite, kaolin, hydrotalcite, activated carbon or the carbon nanotube one or more;
The reactive mode of said selection hydrogenation is still reaction or fixed bed reaction.
2. method according to claim 1 is characterized in that, the content of Pd is 0.2wt%～2wt% in the said catalyzer.
3. method according to claim 1; It is characterized in that said molecular screening one or more in ZSM-5, ZSM-22, ZSM-35, MCM-49, MCM-22, MCM-56, MCM-36, MCM-41, MCM-48, mordenite MOR, β zeolite, Y zeolite, SAPO-34 or SAPO-11.
4. method according to claim 1 is characterized in that said MOX is selected from Al
2O
3, SiO
2, TiO
2, ZrO
2, among the MgO, SnO, CaO, BaO one or more.
5. method according to claim 1 is characterized in that said mesoporous silicon oxide is selected from one or more among SBA-15, MCM-41, MCM-48, HMS or the MSU.
6. method according to claim 1; It is characterized in that; Said loading type Pd Preparation of catalysts is following: soluble salt solution and the respective carrier of Pd are got the catalyzer precursor through immersion process for preparing; Then after 50～200 ℃ of temperature dryings and 300～600 ℃ of temperature roastings, with hydrogen or hydrogen-nitrogen mixture gas at pressure 0.2～10.0MPa, hydrogen gas space velocity 200～3000h
-1, 180～450 ℃ of reduction temperatures condition under reduced 4～48 hours, finally make the loading type Pd catalyzer.
7. method according to claim 1 is characterized in that, said still reaction condition is: 40～200 ℃ of temperature of reaction, reaction pressure 0.1～5.0MPa, 1～24 hour reaction times; Said fixed bed reaction condition is: the mass space velocity of 40～200 ℃ of temperature of reaction, reaction pressure 0.1～5.0MPa, Methylacrylaldehyde is 0.2～5.0h
-1, H
2The mol ratio of/Methylacrylaldehyde is 1: 1～50: 1.
8. method according to claim 1 is characterized in that, said still reaction condition is: 50～100 ℃ of temperature of reaction, reaction pressure 0.2～2.0MPa, 2～16 hours reaction times; Said fixed bed reaction condition is: the mass space velocity of 50～100 ℃ of temperature of reaction, reaction pressure 0.2～2.0MPa, Methylacrylaldehyde is 0.2～3.0h
-1, H
2The mol ratio of/Methylacrylaldehyde is 2: 1～20: 1.
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