CN101314133B - Process for trans-2-deneacetic acid catalytic hydrogenation for preparing hexanoic acid - Google Patents
Process for trans-2-deneacetic acid catalytic hydrogenation for preparing hexanoic acid Download PDFInfo
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- CN101314133B CN101314133B CN2008100905361A CN200810090536A CN101314133B CN 101314133 B CN101314133 B CN 101314133B CN 2008100905361 A CN2008100905361 A CN 2008100905361A CN 200810090536 A CN200810090536 A CN 200810090536A CN 101314133 B CN101314133 B CN 101314133B
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims description 8
- 239000002253 acid Substances 0.000 title abstract description 13
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 title abstract 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 claims abstract description 7
- NIONDZDPPYHYKY-UHFFFAOYSA-N Z-hexenoic acid Natural products CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 238000005516 engineering process Methods 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011799 hole material Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000005416 organic matter Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- -1 be diluted to 0.75ml Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002195 fatty ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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Abstract
The invention discloses a process for preparing hexanoic acid by hydrogenation of trans-2- hexenoic acid, which is carried out in a continuous flow reactor with a reaction temperature of 50-400 DEG C and a reaction pressure of 0.5-10.0 MPa. The process adopts an acid-resistant hydrogenation catalyst for the hydrogenation reaction, the hydrogenation reaction stops after the reaction conducts for a certain time, and the catalyst is subject to in situ reduction. The acid-resistant hydrogenation catalyst comprises a carrier and a main active component, wherein the carrier is a high silicone pore material with a silicon dioxide content more than 70wt%, regular pore structure and the size of the pore of 0.6-50nm; the main active component is nickel species or copper species and the content is more than 20wt% and less than or equal to 40wt%; the catalyst includes a reduction auxiliary agent of ruthenium, and the content is less than or equal to 0.1wt%.
Description
[technical field]
The present invention is relevant a kind of acid-fast hydrogenation catalysts and prepares the application in the technology of caproic acid at trans-2-hexenoic acid catalytic hydrogenation.
[background technology]
A lot of organic matter non-corrosiveness under the situation of individualism, but but show stronger corrosivity after some mixing among them; In addition, the carboxylic acid with higher molecular weight does not have corrosivity at normal temperatures, yet more than 300 ℃, all organic acids all show stronger corrosivity (No.11, September 19771637 for Analytical Chemistry, vol.49).In actual production process, the impure of raw material or product is unavoidable, and as previously mentioned, some organic matter can show stronger corrosivity after mixing; In addition, the reaction temperature of some reaction be about 300 ℃ or more than, the carboxylic acid that in this type reaction, has higher molecular weight will show stronger corrosivity.
Hydrogenation reaction (Hydrogenation) if in exist and to have material than severe corrosive; Such as the organic matter (acetate, propionic acid, butyric acid etc.) that promptly shows under the normal temperature than severe corrosive; Perhaps above-mentioned mention have a mixing organic matter than severe corrosive; Perhaps under higher reaction temperatures, show carboxylic acid with higher molecular weight than severe corrosive; The hydrogenation catalyst that just need have strong acid resistance, otherwise activity of such catalysts component and carrier run off because of having an effect with acid with regard to being easy to.Such as, when reactant has than severe corrosive, Ni/ γ-Al
2O
3(wherein, Ni is an active component to catalyst, γ-Al
2O
3Be carrier) in Ni and γ-Al
2O
3Loss is caused with the acid effect in the capital, causes life of catalyst to shorten.Obviously, the catalyst of acidproof ability has following shortcoming:
The first, acidic materials can cause catalyst loss with catalyst action, so the catalyst of acidproof ability can't be applied to continuous processing, such as fixed-bed process, trickle bed technology etc.
The second, life of catalyst has been shortened in the loss of catalyst, has increased cost.
The 3rd, serious catalyst loss will make the regeneration of catalyst nonsensical, further increase cost.
Exploitation has greater activity and selectivity, and the catalyst that possesses stronger acidproof ability simultaneously is the problem that catalysis field is being studied always.
Please join United States Patent (USP) No. 4524225, this patent has disclosed a kind of acid-resistant catalyst that is used for producing aliphatic acid or fatty ether hydrogenation fatty alcohol, and its active component is one or more of copper, chromium, ruthenium, platinum, palladium, rhenium, and its carrier is α-Al
2O
3, θ-Al
2O
3, aluminium titanates (titanated alumina), titanium oxide, aluminum phosphate one or more.
United States Patent (USP) discloses the dimerization processes that US20060135793 number (calling patent in the following text No. 793) disclosed a kind of levulic acid; The carrier of its catalyst is an acidic molecular sieve; Active component is known hydrogenation metal, under the atmosphere of hydrogen, carries out the dimerization reaction of levulic acid.
United States Patent (USP) discloses US20060162239 (calling patent in the following text No. 239) number and has disclosed a kind of some organic hydrogenation technique that is used for; The carrier of its catalyst is an acidic molecular sieve; Active component is known hydrogenation metal; And disclose when active component is base metal, preferable load ranges is 2-20%.
Finding through experiment, is carrier with the acidic molecular sieve, is the hydrogenation catalyst of main active component with base metal, when the carrying capacity of main active component less than 10% the time, catalyst is inactivation very easily.
[summary of the invention]
One side of the present invention provides a kind of acid-fast hydrogenation catalysts; This acid-fast hydrogenation catalysts comprises carrier and main active component, wherein said carrier be dioxide-containing silica greater than 70wt%, have the high silicon hole material that regular pore structure and hole are of a size of 0.6-50nm; Said main active component is that nickel species or copper species and its content are greater than 20wt% and smaller or equal to 40wt%; Said catalyst also comprises the reduction auxiliary agent, and this reduction auxiliary agent is a ruthenium, and its content is smaller or equal to 0.1wt%.
Described hydrogenation catalyst is meant the catalyst that is used for hydrogenation reaction, and described hydrogenation reaction is meant in hydrogen atmosphere, makes unsaturated compounds and hydrogen reaction become saturated or fractional saturation fully; Include but not limited to following reaction; Like the selective hydrogenation of unsaturated carboxylic acid or ester, the selective hydrogenation of unrighted acid or ester, the hydrogenation reaction of unsaturated hydrocarbons; The hydrogenation of the two keys of carbon oxygen is saturated in the organic matter, the hydrofinishing of biodiesel etc.
Further, said hydrogenation reaction is a selective hydrogenation, promptly mainly a certain or a few kinds of unsaturated bonds is carried out hydrogenation.
Wherein, said high silicon hole material has stronger acid resistance, is difficult for and the acidic materials effect, and therefore, its service life in sour environment is longer.
Further, said high silicon hole material can be Beta zeolite or modenite.
Further, preferred, the content of said main active constituent is greater than 20wt%, smaller or equal to 30wt%.
Further, preferred, main active component is the nickel species.
Further, said acid-fast hydrogenation catalysts can also comprise auxiliary agent, and auxiliary agent can be one or more in the transition metal such as molybdenum, tungsten, copper.
Further, the content of auxiliary agent is less than 25wt%, and is preferred, and the content of auxiliary agent is less than 10wt%.
Further, said acid-fast hydrogenation catalysts can also comprise second active component, can be one or more of noble metals such as a spot of platinum, palladium, iridium, rhodium, ruthenium, in order to promote the catalytic activity of catalyst.
Further, the content of said second active component is less than 0.5wt%, and is preferred, and its content is less than 0.1wt%.
Another aspect of the present invention provide a kind of trans-2-hexenoic acid catalytic hydrogenation prepares the technology of caproic acid, this technology is carried out in continuous flow reactor, reaction temperature is 50-400 ℃, reaction pressure is 0.5-10.0MPa.The foregoing acid-fast hydrogenation catalysts of said process using carries out hydrogenation reaction, and after hydrogenation reaction is carried out certain hour, stops reaction, and catalyst is carried out in-situ reducing.
Said continuous flow reactor comprises fixed bed reactors, trickle bed reactor etc.
Further, preferred, reaction temperature is 50-200 ℃, and is preferred, and reaction temperature is 50-160 ℃.
Further, preferred, reaction pressure is 2.0-5.0MPa.
Further, said unsaturated compounds process for selective hydrogenation also comprises the step of in-situ reducing, at a certain temperature, continues the regular hour toward the interior hydrogen that feeds of reactor, carries out the in-situ reducing of catalyst.
Further, the temperature control mode in the said in-situ reducing step can be with the certain speed intensification and on some temperature, keep the regular hour, also can be directly on a certain temperature, to keep certain hour.
Further, can be according to different catalyst, different reactions, different factors such as reaction time are adjusted the mode, pressure, the flow velocity of hydrogen, lasting conditions such as time of temperature in the said catalyst original position reduction step, intensification.
Further, said unsaturated compounds process for selective hydrogenation also can comprise the step of original position roasting, bubbling air or oxygen; At 450-600 ℃ of following calcined catalyst; The organic matter burning-off that is attached on the catalyst, more to optimize, sintering temperature is 550-600 ℃.
Further, said original position calcination steps carries out before the reduction step in position.
Further, described unsaturated compounds includes but not limited to unsaturated carboxylic acid or ester, unrighted acid or ester, and alkene, and aromatic hydrocarbons etc.
A kind of organic hydrogenation technique that contains the two keys of C=C adopts said acid-fast hydrogenation catalysts, and reaction temperature is 40-400 ℃, and reaction pressure is 0.5-10.0MPa.
Further, preferred, reaction temperature is 50-200 ℃, and is preferred, and reaction temperature is 50-160 ℃.
Further, preferred, reaction pressure is 2.0-5.0MPa.
Further, the organic matter of the two keys of the said C=C of containing is the acid organic matters that contain the two keys of C=C, such as the organic acid that contains the two keys of C=C, contain the mercaptan of the two keys of C=C etc.
Further, the organic matter of the two keys of the said C=C of containing is the organic acids that contain the two keys of C=C, such as crotonic acid, sorbic acid etc.
Further, said hydrogenation is that the C=C double-bond hydrogenation is made it to become the C-C key.
On the one hand; The carrying capacity of the main active component of catalyst of the present invention is greater than 20wt%; Smaller or equal to 40wt%, so, run off because of sour environment if be distributed in the main active component of part of carrier surface; The main active component that is positioned at the carrier structure corner can be replenished the main active component that carrier surface runs off, thereby has increased life of catalyst.
On the other hand, in the hydrogenation technique of unsaturated compounds of the present invention, activity of such catalysts and selectivity can be recovered through the in-situ reducing regeneration step completely, have further increased life of catalyst, have reduced cost.
At last, catalyst of the present invention can carry out selective hydrogenation to the two keys of C=C under the certain reaction condition, and does not influence other unsaturated bonds.
[description of drawings]
Fig. 1 is the crystalline phase at Ni/HBeta catalyst of the present invention.
Fig. 2 is under Ni/HBeta catalyst action of the present invention, trans-2-hexenoic acid catalytic hydrogenation prepare caproic acid reaction conversion ratio and selectivity in time with the graph of a relation of variations in temperature.
[preferred embodiment]
Embodiment one
The preparation of catalyst 30wt%Ni/HBeta
1) takes by weighing 20g through the HBeta after the roasting;
2) use the Ni (NO of 26ml concentration as 3.09mol/L
3)
2Solution impregnation HBeta evenly stirs, and is all absorbed by molecular sieve up to solution;
3) sample after will flooding places 120 ℃ baking oven oven dry 8 hours;
4) the 550 ℃ of roastings 3 hours in Muffle furnace of the sample after will drying make the 30wt%Ni/HBeta catalyst.
5) catalyst of preparation is XRD respectively and characterizes (result please join Fig. 1) and BET (specific area) sign (result please join following table 1).
Table 1
| Sample | S(m 2/g) |
| HBeta | 572 |
| Ni/HBeta | 404 |
Trans-reaction that 2-hexenoic acid catalytic hydrogenation prepares caproic acid
Catalyst reduction:
Take by weighing the 0.5g catalyst, be diluted to 0.75ml, catalyst is packed in the single tube trickle bed reaction unit, the quartz sand of catalyst upper strata filling 2cm with quartz sand.Before beginning reaction, catalyst is at 400 ℃, and in-situ reducing is 4 hours under the hydrogen flow rate condition of 200ml/min.
Hydrogenation reaction:
Reaction pressure 2.0MPa, H
2Flow velocity 50ml/min, liquid charging stock flow velocity 5 μ l/min, WHSV=0.5h
-1Reaction is carried out under 50 ℃ earlier, and when reacting 26 hours, the conversion ratio of reaction is near 100%, and selectivity is that conversion ratio begins to descend gradually after 100%, 26 hour.
During reaction to 54 hour, catalyst is carried out in-situ reducing, in-situ reducing is accomplished continued and under 50 ℃, is reacted, and conversion ratio rises near 100% again, and selectivity continues to keep 100%, and reaction proceeds to 80 hours conversion ratios and begins once more to descend; Reaction to 128 hour promotes reaction temperature to 55 ℃, and conversion ratio begins to rise; Reaction to 140 hour promotes reaction temperature to 60 ℃, and conversion ratio continues to rise; Reaction to 152 hour promotes reaction temperature to 65 ℃, and conversion ratio continues to rise near 100%, and reaction was to 170 hours, and conversion ratio begins to descend; In-situ reducing is carried out in reaction to 207 hour once more, reduces reaction temperature to 50 ℃, and conversion ratio rises once more, and reaction was to 225 hours, and conversion ratio descends once more.
Wherein, the step of said in-situ reducing is following:
1) stop reaction-ure feeding, reaction pressure is reduced to normal pressure, hydrogen flow rate is debugged to 200ml/min;
2) temperature of reactor is risen to 120 ℃ of constant temperature 2 hours with the heating rate of 5 ℃/min, the heating rate with 3 ℃/min rises to 220 ℃ of constant temperature 2 hours with temperature then, and the heating rate with 3 ℃/min rises to 400 ℃ of constant temperature reduction 4 hours with temperature then;
3) after reduction finishes, cool the temperature to reaction temperature.
Further, the pressure in the in-situ reducing step can suitably promote or reduce.
Further, the flow velocity of hydrogen can adjust according to concrete demand, such as 50ml/min, 100ml/min, 150ml/min, 250ml/min or the like.Certainly, the flow velocity of hydrogen is high more, and the cost of reaction is also high more.
Product adopts Agilent 6890 gas-chromatographies that the FFAP capillary column is housed to analyze.
Reaction result proves that acid-fast hydrogenation catalysts of the present invention has fabulous acid resistance, and the life-span in sour environment is longer, has very high selectivity and conversion ratio simultaneously, and can under lower temperature, realize catalytic hydrogenation reaction.
Claims (9)
1. trans-2-hexenoic acid catalytic hydrogenation prepares the technology of caproic acid, in continuous flow reactor, carries out, and reaction temperature is 50-400 ℃; Reaction pressure is 0.5-10.0MPa, it is characterized in that, a kind of acid-fast hydrogenation catalysts of said process using carries out hydrogenation reaction; And after hydrogenation reaction is carried out certain hour, stop reaction, catalyst is carried out in-situ reducing, wherein said acid-fast hydrogenation catalysts comprises carrier and main active component; Said carrier is that dioxide-containing silica is greater than 70wt%; Have regular pore structure and hole and be of a size of the high silicon hole material of 0.6-50nm, said main active component be nickel species or copper species and its content greater than 20wt% and smaller or equal to 40wt%, said catalyst also comprises the reduction auxiliary agent; This reduction auxiliary agent is a ruthenium, and its content is smaller or equal to 0.1wt%.
2. technology as claimed in claim 1 is characterized in that, described in-situ reducing is carried out with the mode of temperature programming.
3. technology as claimed in claim 1 is characterized in that it also comprises the original position calcination steps, bubbling air or oxygen, and at 450-600 ℃ of following calcined catalyst, the original position calcination steps carried out before said in-situ reducing step.
4. technology as claimed in claim 1 is characterized in that, the main active component of said acid-fast hydrogenation catalysts is the nickel species.
5. technology as claimed in claim 1 is characterized in that, the carrier of said acid-fast hydrogenation catalysts is the Beta zeolite.
6. technology as claimed in claim 1 is characterized in that said acid-fast hydrogenation catalysts also comprises auxiliary agent, and this auxiliary agent comprises one or more in molybdenum, tungsten, the copper.
7. technology as claimed in claim 6 is characterized in that the content of said auxiliary agent is less than 10wt%.
8. technology as claimed in claim 1 is characterized in that said acid-fast hydrogenation catalysts also comprises second active component, and this second active component is one or more in platinum, palladium, iridium, the rhodium.
9. technology as claimed in claim 8 is characterized in that, the content of said second active component is less than 0.1wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100905361A CN101314133B (en) | 2007-06-01 | 2008-03-27 | Process for trans-2-deneacetic acid catalytic hydrogenation for preparing hexanoic acid |
Applications Claiming Priority (3)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453553A (en) * | 1992-04-03 | 1995-09-26 | Council Of Scientific & Industrial Research | Process for the production of linear alkylbenzenes |
| CN1276408A (en) * | 1999-03-12 | 2000-12-13 | 阿吉佩罗里股份公司 | Catalyst composition for upgrading hydrocarbon mixture |
| CN1733667A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | Method for 3- hydroxyl propionaldehyde hydrogenation to produce 1,3-propanediol |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453553A (en) * | 1992-04-03 | 1995-09-26 | Council Of Scientific & Industrial Research | Process for the production of linear alkylbenzenes |
| CN1276408A (en) * | 1999-03-12 | 2000-12-13 | 阿吉佩罗里股份公司 | Catalyst composition for upgrading hydrocarbon mixture |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN1733667A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | Method for 3- hydroxyl propionaldehyde hydrogenation to produce 1,3-propanediol |
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