MXPA98001659A - Procedures for the elaboration of acrolein apparatus of propylene by oxidation reaction reduction and use of a solid composition of mixed oxides as an oxidation system in such reacc - Google Patents
Procedures for the elaboration of acrolein apparatus of propylene by oxidation reaction reduction and use of a solid composition of mixed oxides as an oxidation system in such reaccInfo
- Publication number
- MXPA98001659A MXPA98001659A MXPA/A/1998/001659A MX9801659A MXPA98001659A MX PA98001659 A MXPA98001659 A MX PA98001659A MX 9801659 A MX9801659 A MX 9801659A MX PA98001659 A MXPA98001659 A MX PA98001659A
- Authority
- MX
- Mexico
- Prior art keywords
- propylene
- oxidation
- solid
- acrolein
- solid composition
- Prior art date
Links
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 58
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000008247 solid mixture Substances 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 8
- 239000007787 solid Substances 0.000 claims abstract description 44
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000006479 redox reaction Methods 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- -1 propylene - Chemical class 0.000 claims description 2
- 238000010405 reoxidation reaction Methods 0.000 claims description 2
- 230000001590 oxidative Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 239000007924 injection Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000003197 catalytic Effects 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N Potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910052803 cobalt Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N Ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N Cobalt(II) nitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IZYSFFFJIOTJEV-UHFFFAOYSA-P diazanium;dioxido(dioxo)tungsten Chemical compound [NH4+].[NH4+].[O-][W]([O-])(=O)=O IZYSFFFJIOTJEV-UHFFFAOYSA-P 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000000977 initiatory Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L Molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N Nickel(II) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N Silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910002850 SnCl2 Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L Tin(II) chloride Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 241001125929 Trisopterus luscus Species 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L Tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- VSOYJNRFGMJBAV-UHFFFAOYSA-O [NH4+].[Mo+4] Chemical compound [NH4+].[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N nicotinic acid Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- KKHJTSPUUIRIOP-UHFFFAOYSA-I tetrachlorostannane;hydroxide Chemical compound [OH-].Cl[Sn](Cl)(Cl)Cl KKHJTSPUUIRIOP-UHFFFAOYSA-I 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The present invention relates to the use of a solid mixed oxide composition of the formula: Mo12WaBibFecCodNiaSifKgSnhOx wherein 0 < - a < - 5, 0.5 < - b < - 5.0.1 < - c < - 10, 0.5 < - d < - 10.0 < - e < -10.0 < - f < - 15,0 < - g < - 1, 0 < - h < - 2 and x is the amount of oxygen bound to the other elements and depends on their oxidation states, in the production of acrolein oxidizing propylene, said solid composition reacting with propylene according to the oxidation-reduction reaction: solid + propylene - solid extruded + acrolein, for the preparation of acrolein, comprising passing the gaseous propylene over a solid composition of the formula (I), to conduct the oxidation-reduction reaction (1) working at a temperature of 200 to 600 ° C, at a pressure from 1.01 x 104 to 1.01 x 106 Pa (0.1 to 10 atmospheres) and with a residence time from 0.01 second to 90 seconds, in the absence of molecular oxygen
Description
PROCEDURES FOR THE ELABORATION OF ACROLEIN FROM
PROPYLENE FOR OXIDATION REACTION-REDUCTION AND USE OF A
SOLID COMPOSITION OF MIXED OXIDES AS AN OXIDATION SYSTEM
IN ICHA REACTION
DESCRIPTIVE MEMORY
The present invention relates to the preparation of acrolein from propylene by oxidation according to an oxidation-reduction reaction. The invention also relates to the use of a solid composition of mixed oxides as an oxidation-reduction system in said reaction. Currently, acrolein is produced industrially by catalytic oxidation of propylene in the vapor phase. All attempts to improve this process have so far been related to the development of catalysts that produce the highest possible conversion of propylene and the highest possible selectivity of the desired acrolein. In this way, French Patent No. 2 093 773 describes the preparation of acrolein by catalytic oxidation of propylene in vapor phase, with molecular oxygen, in the presence of an oxide catalyst in which the composition of the catalytic elements, expressed as Atomic ratio, is the following: C02.0-20.0 Ugly. i-1o. oBio .1-10.0W0.5-10.0M02.0-11.5
YES0.5-15.0Z0.005-1.0 with W + Mo = 12.0 and Z denoting an alkali metal. This catalyst can be prepared by mixing aqueous solutions of ammonium molybdenum and ammonium paratungstate, adding solutions of cobalt nitrate, iron nitrate and bismuth nitrate to the aqueous mixture and then adding an aqueous solution of metal hydroxide or carbonate. alkaline and then colloidal silica as a source of silicon, molding the obtained substance and calcining it at 350-600 ° C in a stream of air. The Patent of E.U.A. No. 3 855 308 describes the preparation of acrolein by catalytic oxidation of propylene in vapor phase, with molecular oxygen, in the presence of an oxide catalyst in which the composition of the catalytic elements, expressed in atomic ratio, is as follows: C? 2.0-20. oFeo.1-10. oBio.1-10.0W0.5-10.0M02.0-11.5
YES0.S-15.0TI0.005-3.0Z0-3.0 where W + Mo = 12.0 and Z denoting an alkali metal or an alkaline earth metal. The starting materials used to form the catalyst may be the oxides of the various metals, but also, depending on the circumstances, the nitrates, carbonates or hydroxides. In the case of Mo and W, the salts of acids, such as ammonium olibdate and ammonium tungstate, are recommended. In this way, in accordance with this patent of E.U.A. a catalyst is prepared by mixing aqueous solutions of ammonium molybdate and ammonium paratungstate, respectively, by adding solutions of cobalt nitrate, iron nitrate and bismuth nitrate, respectively, and then an aqueous solution of alkali metal hydroxide or carbonate and then colloidal silica as a source of silicon, concentrating the system by evaporation, adding a support if necessary and continuing with the evaporation, the mixing of the resulting substance and the calcination at 350-600 ° C. Japanese Patent Showa 45-125 359 discloses a vapor phase process for the preparation of acrolein by catalytic oxidation of propylene with air or oxygen in the presence of a catalyst of the formula: NiaC? B Fec Bid MeB Hh M? F0g in which : - a = 0-2b, b = 0-20, where a + b is between 0.5 and 20, - c = 0.5-8, d = 0.1-7.0 < e < 2, h = 0-0.3, f = 12,
- g = 36-90; - I am one of between Sn, Zn, W, Cr, Mn and Ti; and - H is at least one of K, Rb and Cs. To prepare this catalyst, aqueous solutions of the compounds of Ni, Co, Fe, K (and / or Rb, Cs), Bi and Me can be added to an aqueous solution of a molybdenum compound (ammonium molybdate, olibic acid or molybdenum oxide), and then it is added to a support such as alumina, silicon carbide and silica (silica sol or silica gel) and the resulting mixture is then heated to dryness, calcined at approximately 500 ° C and conveit to pills.
The Applicant Company has now discovered that acrolein can be made by gas phase oxidation of propylene in the absence of molecular oxygen by passing propylene over a particular mixed solid oxide composition that acts as an oxidation-reduction system and supplies the necessary oxygen for the reaction. The advantages of this new process are the following: the limitation of the over-oxidation of the formed products, which takes place in the presence of molecular oxygen; according to the present invention, since the operation is carried out in the absence of molecular oxygen, the formation of C0 is reduced? (carbon monoxide and carbon dioxide) and degradation products, and this allows the selectivity of acrolein to be increased, as hereinafter shown by Comparative Examples 4, 8, 12 and 16; the selectivity of acrolein continues to be appropriate when the degree of reduction of the solid composition is increased; once it has experienced the reduction and gradual loss of its activity, the solid composition can be easily regenerated by heating it in the presence of oxygen or an oxygen-containing gas after a certain period of use. After regeneration the solid recovers its initial activity and can be used in a new reaction cycle; the separation of the steps of reducing the solid composition and its regeneration makes it possible to: - increase the selectivity of acrolein; e - increasing the partial pressure of propylene, no longer being limited to such a partial pressure of propylene supply by the existence of an explosive region of the mixture of propylene plus oxygen. The subject of the present invention is therefore firstly the use of a solid composition of mixed oxides of the formula (I): M012 W.Bib FecC? D NitSifKgSnhOx (I) in which: - a is from 0 and 5, including the limits - b is between 0.5 and 5, including the limits - c is between 0.1 and 10, including the limits - d is between 0.5 and 10, including the limits - e is between 0 and 10 , including the limits - f is between 0 and 15, including the limits - g is between 0 and 1, including the limits - h is between 0 and 2, including the limits, and - x is the amount of oxygen bound to the other elements and depends on their oxidation states, in the preparation of acrolein by propylene oxidation, said solid composition reacting with propylene according to the oxidation-reduction reaction (1): solidoxide gives a + propylene - > educted leaving + acrolein (1). The oxides of the various metals that are part of the mixed oxide composition of the formula (I) can be used as starting materials in the preparation of this composition, but the starting materials are not restricted to the oxides; Other starting materials that can be mentioned are: - in the case of molybdenum, ammonium molybdate and molybdic acid and, in the case of tungsten, ammonium tungstate and tungstic acid, - in the case of cobalt, bismuth, nickel and iron , nitrates, carbonates and hydroxides, such as cobalt nitrate, bismuth nitrate, nickel nitrate and ferric nitrate, - in the case of tin, tin chloride and tin hydroxide, and - in the case of potassium, hydroxide, carbonate or potassium nitrate, and, in general, any compounds capable of forming an oxide by calcination, especially metal salts of organic acids, metal salts of inorganic acids, complex metal compounds, organometallic compounds and the like. The silicon source generally consists of colloidal silica. The subject of the present invention is a process for the preparation of acrolein from propylene, a process according to which gaseous propylene is passed over a solid composition of the formula (I) as defined above, to drive the reaction of oxide-reduction (1) as indicated above, while working at a temperature of 200 to 600 ° C, especially 250 to 450 ° C, at a pressure of 1.01 x 10 * at 1.01 x 10ß Pa (0.1 to 10 atmospheres), especially from 5.05 x 10 * to 5.05 x 105 Pa (0.5-5 atmospheres), and with a residence time from 0.01 second to 90 seconds, especially from 0.1 second to 30 seconds, in the absence of molecular oxygen. According to the particular embodiments of the present invention, gaseous propylene can be introduced as a mixture with an inert gas, such as nitrogen and / or with water (water vapor). During the oxide-reduction reaction (1) the solid composition undergoes reduction and progressive testing of its activity. That is why, once the solid composition has changed to the reduced state, the regeneration of said solid composition is conducted according to the reaction (2): SOLIDOR produced + 02 ~ >; SOLIDITY x i ad o (2) Heating in the presence of an excess of oxygen or a gas containing oxygen at a temperature of 250 to 500 ° C, during the time necessary for the reoxidation of the solid composition. After regeneration, which can be carried out under conditions of temperature and pressure which are identical to or different from the oxidation-reduction reaction, the solid composition recovers the initial activity and can be used in a new reaction cycle. The oxidation-reduction reaction can be conducted
(1) and regeneration in a two-stage device, ie a reactor and a regenerator that operates simultaneously and in which two charges of solid composition alternate periodically; it is also possible to know the oxidation-reduction reaction (1) and the regeneration in the reactor by alternating the reaction and regeneration periods. The preparation of acrolein according to the invention is carried out according to a stechymetric and non-catalytic reaction. The following examples illustrate the present invention without, however, limiting its scope. In the formulas shown in these examples, x is the amount of oxygen bound to the other elements and depends on their oxidation states. It refers to conversions, selectivities and returns, as follows:
Number of moles of propylene reacted Conversion (%) = - x 100 Number of moles of propylene introduced Number of moles of acid Selectivity (%) acrylic formed from acrolein = x 100 Number of moles of propylene reacted moles of acid Selectivity (%) acetic formed from acetic acid = x 100 Number of moles of propylene reacted
EXAMPLE 1 (a) Preparation of a Solid of the Formula Moi 2 COA .7Bi1Ni2.6Fe3.7Wo.5Sno.sSi Ko.08Ox
Dissolve 618 g of Co (N03) 2 «6H-20, 343 g of Ni (N03) 2« 6H2 ?, 674 g of Fe (N03) 3 * 9H20 and 3.8 g of KNO3 in 1250 ml of distilled water at room temperature ambient. 230 g of Bi (N03) 3 * 5H2 are dissolved, also at room temperature, in 300 ml of distilled water acidified with 50 ml of HNO3 at a concentration of 68% by volume. Dissolve 53 g of SnCl2 »2H2? in 60 ml of distilled water, also at room temperature. Dissolve 956.2 g of (N U) ß? 7? «H Ü in 260 ml of distilled water at 40 ° C. The solution containing the bismuth and the one containing the tin is poured, stirring, to the solution containing Co, Ni, Fe, and K. The resulting solution is then poured, still stirring, into the solution containing the molybdenum. . Then 71 g of colloidal silica (at a concentration of 40% by mass) and 55.6 g of WO3 are sprinkled thereto. The resulting mixture is heated at 90 ° C for 1.5 hours and then dried for 12 hours at 140 ° C. The solid obtained is calcined for 6 hours at 500 ° C in air. The various metals are present in this solid in the atomic relationships shown in the title of this example.
(b) Preparation of Acrolein from Propylene by Oxidation-Reduction Reaction
200 mg of this solid is introduced into a tubular reactor at 40 ° C and then purged with a continuous stream of 12 ml / min of helium. 2.3 x 10 ~ 6 moles of propylene is injected onto the solid. The conversion of propylene is 91.5%, with the selectivities of acrolein and acrylic acid of 80.0% and 4.0%, respectively.
EXAMPLE 2
After the reaction of Example 1 (b) has been conducted, the same solid is subjected again to 4 successive injections of propylene under the same test conditions as in Example 1. The yields obtained are presented in Table 1.
TABLE 1
EXAMPLE 3
After the reduction treatment of Example 2, the solid is regenerated for 1 hour in air at 400 ° C and then replaced under a flow of helium. It is directed to four successive new injections of 2.3 x 10-6 moles of propylene on the solid. The yields obtained are presented in Table 2.
TABLE 2
EXAMPLE 4 (Comparative)
200 mg of a solid prepared according to Example 1 is introduced into a tubular reactor at 400 ° C and then purged with a continuous flow of 12 ml / min of air. 2.3 x 10 ~ 6 moles of propylene is injected onto the solid. The conversion of propylene is 92.9%, with the selectivities of acrolein and acrylic acid of 70.4% and 3.4%, respectively.
EXAMPLE 5 (a) Preparation of a Solid of the Formula Moi2C03.5 Bii. i NÍ2. ß Ugly. sWo .5 Sm. To Sii Ko. o50?
Dissolve 60.9 of Co (N? 3) 2 * 6H2? in 20 ml of distilled water. Also dissolve 20.2 Fe (N03) 3 «9H20 in 15 ml of distilled water and 31.2 of Bi (N03) 3» 5H2? in 30 ml of distilled water acidified with 6 ml of HNO3 at a concentration of 68% by volume. Dissolve 127.4 of (NH4) e? 7? 24 »4H2? separately and 150 ml of water by heating while stirring and then 7.4 g of WO3 is added. The aqueous solution containing cobalt is introduced, drop by drop for 30 minutes, to the aqueous solution of the ammonium salts. The ferric solution is then introduced for 10 min and then the solution containing the bismuth for 15 min. A solution is added which is obtained by dissolving 0.2 g of KOH and 12.8 g of colloidal silica (at a concentration of 40% by mass) in 15 ml of water for 10 min to the resulting gel. The gel thus obtained is mixed for 1 hour at room temperature and then for 1 hour at 70 ° C. The gel is then dried for 18 hours at 130 ° C.
The solid obtained is calcined for 9 hours at 540 << > C in air. The various metals are present in this solid in the atomic relationships as shown in the example title.
Cb) Preparation of Acrolein to Propylene by Oxidation-Reduction Reaction
200 mg of this solid is introduced into a tubular reactor at 400 ° C and is purged with a continuous flow of 12 ml / min of helium. 2.3 x 10-6 moles of propylene are injected onto the solid. The conversion of propylene is 82.8%, with the selectivities of acrolein and acrylic acid of 77.7% and 5.1%, respectively.
EXAMPLE 6
After the reaction of Example 5 has been conducted
(b), the same solid is again subjected to 4 successive injections of propylene in the same test solutions as in Example 5. The yields obtained are presented in Table 3.
TABLE 3
EXAMPLE 7 After the reduction treatment of Example 6, the solid is regenerated for 1 hour in air at 400 ° C and then replaced with a flow of helium. It is directed 4 new injections of 2.3 x 10- * moles of propylene on the solid. The yields obtained are presented in Table 4.
TABLE 4
EXAMPLE 8 (Comparative)
200 mg of a solid prepared according to Example 5 is introduced into a tubular reactor and purged with a continuous flow of 12 ml / min of air. 2.3 x 10-6 moles of propylene are injected onto the solid. The conversion of propylene is 84.9%, with the selectivities of acrolein and acrylic acid being 66.1% and 5.0%, respectively.
EXAMPLE 9 (a) Preparation of a Solid of the Formula Moi2C? 3.5Bi. Ugly sWo. sSii. To Ko. osOx
The above solid is prepared in the same manner as in Example 5 but with the 7.4 g of WO3 replaced by 8.1 g of ammonium paratungstate.
(b) Preparation of Acrolein from Propylene by Oxidation-Reduction Reaction
This solid is used for the reaction of Example 5 with the following results: the conversion of propylene is 92.1%, with the selectivities of acrolein and acrylic acid of 72.7% and 8.0%, respectively.
EXAMPLE 10
After the reaction of Example 9 has been conducted, the same solid is again subjected to four successive injections of propylene under the same test conditions as in Example 9. The yields obtained are presented in Table 5.
TABLE 5
80. 5 70.7 6.3
EXAMPLE 11
After the reaction treatment of Example 10, the solid is regenerated for 1 hour in air at 400 ° C and then replaced under a flow of helium. It is directed to four successive new injections of 2.3 x 10-6 moles of propylene on the solid. The yields obtained are presented in Table 6.
TABLE 6
Injection Conversion of the selectivity Selectivity No. propylene of the acid (%) acrolein (%) acrylic (%)
90. 7 73.4 7.8
87. 2 74.3 7.1
83. 3 72.4 6.5
80. 3 70.7 6.2
EXAMPLE 12 (Comparative)
200 mg of a solid prepared according to Example 9 is introduced into a tubular reactor at 400 ° C and then purged with a continuous flow of 12 ml / min of air. 2.3 x 10 ~ 6 moles of propylene is injected onto the solid. The conversion of propylene is 91.3%, with the selectivities of acrolein and acrylic acid being 61.0% and 6.9%, respectively.
EXAMPLE 13 (a) Preparation of a Solid of the Formula MOl2 ?? t8BÍ? T2FeQt? W? T? Si? I5KQtQ5 ??
The above solid is prepared in the same manner as in Example 5.
(b) Preparation of Acrolein from Propylene by Oxidation-Reduction Reaction
This solid is used for the reaction of Example 5 with the following results: the conversion of propylene is 90.4%, with the selectivities of acrolein and acrylic acid being 78.1% and 6.3%, respectively.
EXAMPLE 14
After the reaction of the
Example 13 (b), the same solid is again subjected to four successive injections of propylene under the same test conditions as in Example 13. The yields are presented in Table 7.
TABLE 7
EXAMPLE 15
After the reduction treatment of Example 14, the solid is regenerated for 1 hour in air at 400 ° C and then replaced under helium flow. It is directed four new injections of 2.3 x 10-6 mmoles propylene on the solid. The yields obtained in Table 8 are presented.
TABLE 8
Injection Conversion of the selectivity Selectivity No. propylene of the acid (%) acrolein (%) acrylic (%)
91. 3 78.1 7.7
88. 7 79.6 6.3
84. 6 78.2 5.3
80. 2 78.3 4.8
EXAMPLE 16 (Comparative)
200 mg of a solid prepared according to Example 9 is introduced into a tubular reactor at 400 ° C and then purged with a continuous flow of 12 ml / min of air. 2.3 x lo-6 moles of propylene are injected onto the solid. The conversion of propylene is 91.8%, with the selectivities of acrolein and acrylic acid being 71.0% and 6.6%, respectively.
Claims (9)
1. - Use of a mixed oxide solid composition of the formula (I): Moi2WaBihFecC? DNifSif KgSnhOx (I) in which: a is between 0 and 5, including the limits, b is between 0.5 and 5, including the limits , c is between 0.1 and 10, including the limits, d is between 0.5 and 10, including the limits, e is between 0 and 10, including the limits, f is between 0 and 15, including the limits, g is between 0 and 1, including the limits, h is between 0 and 2, including the limits, and x is the amount of oxygen bound to the other elements and depends on their oxidation states, in the preparation of acrolein by oxidation of propylene, said solid composition reacting with propylene, according to the oxidation-reduction reaction (1): solid oxide + propylene - > solid to acidole + acrolein (1).
2. Process for the preparation of acrolein from propylene, characterized in that propylene gaseous is passed over a solid composition of the formula (I) defined in claim 1, to drive the reduction-oxide reaction (1) indicated in claim 1, while working at a temperature of 200 to 600 ° C, at a pressure of 1.01 x 10 * to 1.01 x 106 Pa (0.1 to 10 atmospheres) and with a dwell time of 0.01 second to 90 seconds, in the absence of molecular oxygen.
3. Method according to claim 2, characterized in that the gaseous propylene is introduced as a mixture with an inert gas such as nitrogen and / or with water.
4. Method according to any of claims 2 and 3, characterized in that the oxidation-reduction reaction (1) is conducted at a temperature of 250 to 450 ° C.
5. Method according to one of claims 2 to 4, characterized in that the oxide-reduction reaction (1) is conducted at a pressure of 5.05 x 10 * -5.05 x 105 Pa (0.5-5 atmospheres).
6. Method according to one of claims 2 to 5, characterized in that the oxidation-reduction reaction (1) is conducted with a residence time of 0.1 second to 30 seconds.
7. Method according to one of claims 2 to 6, characterized in that, once the solid composition has changed to the reduced state, the regeneration of said solid composition is conducted according to the reaction (2): SOLIDID adducted + 02 - > SOLID X i d d or (2) heating in the presence of an excess of oxygen or of an oxygen-containing gas at a temperature of 250 to 500 ° C, during the time necessary for the reoxidation of the solid composition.
8. Method according to claim 7, characterized in that the oxidation-reduction reaction (1) and the regeneration are conducted in a two-stage device, namely a reactor and a regenerator operating simultaneously and in which both charges of the solid composition alternate periodically.
9. Method according to claim 7, characterized in that the oxidation-reduction reaction (1) and the regeneration are conducted in the same reactor alternating the reaction and regeneration periods.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9702343 | 1997-02-27 | ||
FR9702343A FR2760008A1 (en) | 1997-02-27 | 1997-02-27 | PROCESS FOR MANUFACTURING ACROLEIN FROM PROPYLENE BY REDOX REACTION AND USE OF A SOLID COMPOSITION OF MIXED OXIDES AS A REDOX SYSTEM IN THE SAID REACTION |
Publications (3)
Publication Number | Publication Date |
---|---|
MX9801659A MX9801659A (en) | 1998-12-31 |
MXPA98001659A true MXPA98001659A (en) | 1999-02-01 |
MX202425B MX202425B (en) | 2001-06-15 |
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