CN104549340A - Fluidized bed Catalyst for preparation of unsaturated nitrile by ammonium oxidation - Google Patents
Fluidized bed Catalyst for preparation of unsaturated nitrile by ammonium oxidation Download PDFInfo
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- CN104549340A CN104549340A CN201310512192.XA CN201310512192A CN104549340A CN 104549340 A CN104549340 A CN 104549340A CN 201310512192 A CN201310512192 A CN 201310512192A CN 104549340 A CN104549340 A CN 104549340A
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- mole
- catalyst
- stirring
- unsaturated nitrile
- span
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 title abstract description 3
- 238000007254 oxidation reaction Methods 0.000 title abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims description 149
- 238000003756 stirring Methods 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 18
- 239000011733 molybdenum Substances 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 13
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- 239000011777 magnesium Substances 0.000 description 29
- 230000032683 aging Effects 0.000 description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 238000005507 spraying Methods 0.000 description 16
- 229910052701 rubidium Inorganic materials 0.000 description 15
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 7
- 239000011133 lead Substances 0.000 description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- OTKOPKDCLGDHFV-UHFFFAOYSA-N azane;2-methylprop-1-ene Chemical compound N.CC(C)=C OTKOPKDCLGDHFV-UHFFFAOYSA-N 0.000 description 2
- -1 butene nitrile Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a fluidized bed catalyst for preparation of unsaturated nitrile by ammonium oxidation, and mainly aims to solve the problem of low yield of unsaturated nitrile caused by propene conversion rate reduction under a high-load condition in the prior art. The problem can be well solved by adopting a technical scheme that the catalyst comprises an active ingredient as shown in the general formula Mo12BiaFebNicXdYeRbfOx and takes SiO2 as a carrier, and the catalyst can be used in industrial production of acrylonitrile production by propylene ammmoxidation.
Description
Technical field
The present invention relates to the fluid catalyst of a kind of fluid catalyst of prepared by ammoxidation unsaturated nitrile, preparation method and application, particularly propylene in unsaturated hydrocarbons prepared by ammoxidation unsaturated nitrile, butylene preparing acrylonitrile by ammoxidation, butene nitrile.
Background technology
The prepared by ammoxidation of alkene is developed sixties last century in last century by BP company for α, beta unsaturated nitrile technique, and the core technology of this technique is the catalyst using a kind of active component to contain Mo, Bi.Through constantly improving, current Mo-Bi series catalysts is very ripe, is industrially widely used by preparing acrylonitrile by allylamine oxidation technique.The improvement of catalyst in the past is mainly carried out from the activity of catalyst and stability aspect by the design of catalyst formulation, and as added transition metal to improve activity in active constituent, the list increasing product is received; Add rare earth element and improve redox ability; Add the elements such as Na, P to improve the wearability of catalyst; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, improve stability of catalyst etc.
Patent CN 99119905.7, CN 99119906.5, CN 97106771.6 and CN 96101529.2 all describe the Mo-Bi catalyst for propylene, isobutene ammonia oxidizing unsaturated nitrile catalyst of improvement, the advantage of these catalyst has good oxidation-reduction stability and reaction yield preferably, reacting ammonia than empty than and reaction temperature lower.
Patent CN 01113194.2, CN 01113193.4 and CN 01113192.6 describe and in catalyst preparation process, to get method that part metals and organic ligand, chelating agent or surfactant prepared separately to improve catalyst at low ammonia than the performance under reaction condition.
Patent CN 03151170.8 and CN 03151169.4 describes in catalyst preparation process, and the grain diameter adding 2 ~ 25% in carrier starting material Ludox is that the solid silica of 5 ~ 100 nanometers is to improve catalyst performance.
Above patented technology is to the conversion ratio improving catalyst under underload or conventional load, and reduce the discharge of ammonia ratio and then minimizing amine wastewater of sulphuric acid in course of reaction, there has been certain effect the aspects such as the life-span of extending catalyst; But up to now, prior art exists under high loads, propylene conversion declines the problem causing acrylonitrile yield low.
Summary of the invention
One of technical problem to be solved by this invention is that in prior art, under high load capacity, propylene conversion declines, and causes the problem that unsaturated nitrile yield is low, provides a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation.This catalyst is used for the reaction of unsaturated hydrocarbons prepared by ammoxidation unsaturated nitrile, has the advantage that unsaturated nitrile yield is high.
Two of technical problem to be solved by this invention is preparation methods of the described catalyst of one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is that the described catalyst of one of above-mentioned technical problem is in the application in olefin ammoxidation unsaturated nitrile.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: unsaturated nitrile fluid catalyst prepared by ammoxidation, with SiO
2for carrier, the active component containing following general formula represents:
Mo
12Bi
aFe
bNi
cX
dY
eRb
fO
x
Wherein:
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Zr;
Y is at least one be selected from La, Ce, Pr, Nd or Sm;
The span of a is 0.1 ~ 6.0;
The span of b is 0.1 ~ 10.0;
The span of c is 0.1 ~ 10.0;
The span of d is 0.1 ~ 10.0;
The span of e is 0.1 ~ 5.0;
The span of f is >0 and below 0.5;
X is for meeting the oxygen atom sum needed for other element valence.
In technique scheme, the preferred span of e is 0.1 ~ 3.0; More preferably span is 0.1 ~ 2.0.The consumption preferable range of carrier is the mol ratio of element silicon and described active component is 50 ~ 140; More preferably 80 ~ 120.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of the catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the following steps:
(1) get the Ludox needed for carrier, stir, obtain material A;
(2) material B is obtained by water-soluble for the water soluble compound of aequum molybdenum;
(3) under stirring, material B is added in material A and obtain material C;
(4) material D is obtained by water-soluble for the water soluble compound of aequum Bi, Fe, Ni, X and Y;
(5) compound water solution of aequum Rb is added in material D form material E;
(6) material E is dripped under fast stirring in material C, obtain catalyst pulp;
(7) mist projection granulating;
(8) roasting obtains described catalyst.
In technique scheme, the temperature of step (8) described roasting is preferably 520 ~ 660 DEG C; More preferably 550 ~ 640 DEG C.The time of step (8) described roasting is preferably 20 ~ 180 minutes; More preferably 50 ~ 90 minutes.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the application of catalyst according to any one of the technical scheme of one of above-mentioned technical problem in unsaturated hydrocarbons prepared by ammoxidation unsaturated nitrile.
In technique scheme, described unsaturated hydrocarbons preferred alkenes or alkyl-substituted aromatic hydrocarbon; More preferably low-carbon alkene or methyl substituted aromatic hydrocarbons.Described low-carbon alkene can be C
3~ C
4alkene, wherein preferred example has propylene, butylene, isobutene etc.The preferred example of described methyl substituted aromatic hydrocarbons has toluene, dimethylbenzene.Concrete example is ammoxidating propylene to prepare acrylonitrile, isobutene ammonia oxidizing methacrylonitrile, toluene prepared by ammoxidation benzonitrile etc.
The catalyst of the present invention and comparative example adopts following condition to evaluate:
Reactor: fluidized-bed reactor, internal diameter 38 millimeters
Catalyst filling amount: 400 grams
Reactor top pressure: 0.084 MPa (gauge pressure)
Reaction temperature: 430 DEG C
Reaction time: 4 hours
Material molar ratio: propylene/ammonia/air=1/1.1/9.5,
WWH: 0.085 hour
-1
Product 0 DEG C of diluted acid absorbs, with gas-chromatography and chemical analysis binding analysis product.And calculate Carbon balance, be valid data when Carbon balance is at (95 ~ 105) %.
Propylene conversion, acrylonitrile yield and be optionally defined as:
Propylene conversion (%)=1-(unreacting propylene C molal quantity/all product C molal quantitys) × 100%
Single-pass yield of acrylonitrile (%)=(generating acrylonitrile C molal quantity/all product C molal quantitys) × 100%
Acrylonitrile selectivity (%)=(single-pass yield of acrylonitrile/propylene conversion) × 100 %
The propylene conversion (routine evaluations condition is WWH=0.060) under the high load capacity appreciation condition of WWH=0.085 of catalyst is increased to about 98.0% of embodiment by 94.5% of comparative example 1, acrylonitrile selectivity is increased to about 84.0 ~ 85.0% of embodiment by 83.3% of comparative example 1, single-pass yield of acrylonitrile is then increased to by 78.7% and is up to 83.8%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated:
Detailed description of the invention
comparative example 1
Will containing the 40%(weight of 16.8 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.5 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.4 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.9 mole of nickel element
3)
36H
2o, containing the Mg (NO of 0.36 mole of magnesium elements
3)
36H
2o, containing the La (NO of 0.16 mole of lanthanum element
3)
33H
2o, containing the Sm (NO of 0.04 mole of samarium element
3)
33H
2o, makes material D after stirring and dissolving.
The KNO containing 0.016 molar potassium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 60 minutes at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the composition of catalyst is listed in table 1, the evaluation result of catalyst is listed in table 2.
embodiment 1
Will containing the 40%(weight of 16.8 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.5 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.4 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.9 mole of nickel element
3)
36H
2o, containing the Mg (NO of 0.36 mole of magnesium elements
3)
36H
2o, containing the La (NO of 0.16 mole of lanthanum element
3)
33H
2o, containing the Sm (NO of 0.04 mole of samarium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.016 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 60 minutes at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 2
Will containing the 40%(weight of 14.4 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.42 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.06 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.96 mole of nickel element
3)
36H
2o, containing the Mg (NO of 0.42 mole of magnesium elements
3)
36H
2o, containing the La (NO of 0.36 mole of lanthanum element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.03 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 200 minutes at 530 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 3
Will containing the 40%(weight of 19.2 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.4 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.1 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.3 moles of nickel elements
3)
36H
2o, containing the Mg (NO of 0.38 mole of magnesium elements
3)
36H
2o, containing the Nd (NO of 0.48 mole of neodymium element
3)
33H
2o, containing the Sm (NO of 0.08 mole of samarium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.06 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 150 minutes at 550 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 4
Will containing the 40%(weight of 21.6 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.3 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.08 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.9 mole of nickel element
3)
36H
2o, containing the Co (NO of 0.64 mole of cobalt element
3)
36H
2o, containing the Pr (NO of 0.3 mole of praseodymium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.16 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 20 minutes at 660 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 5
Will containing the 40%(weight of 24 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.44 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.3 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.0 moles of nickel elements
3)
36H
2o, containing the Mg (NO of 0.36 mole of magnesium elements
3)
36H
2o, containing the La (NO of 0.16 mole of lanthanum element
3)
33H
2o, containing the Pr (NO of 0.28 mole of praseodymium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.056 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 160 minutes at 560 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 6
Will containing the 40%(weight of 12 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.56 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.48 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.06 moles of nickel elements
3)
36H
2o, containing the Mn (NO of 0.14 mole of manganese element
3)
2solution, containing the Ca (NO of 0.04 mole of calcium constituent
3)
24H
2o, containing the Nd (NO of 0.08 mole of neodymium element
3)
33H
2o, containing the Ce (NO of 0.16 mole of Ce elements
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.14 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 70 minutes at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 7
Will containing the 40%(weight of 9.6 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.9 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.16 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.7 mole of nickel element
3)
36H
2o, containing the Pb (NO of 0.04 mole of lead element
3)
2, containing the Nd (NO of 0.28 mole of neodymium element
3)
33H
2o, containing the Ce (NO of 0.24 mole of Ce elements
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.06 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 60 minutes at 590 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 8
Will containing the 40%(weight of 26.4 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.5 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.5 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.12 moles of nickel elements
3)
36H
2o, containing the Pb (NO of 0.24 mole of lead element
3)
2, containing the Pr (NO of 0.08 mole of praseodymium element
3)
33H
2o, containing the Ce (NO of 0.14 mole of Ce elements
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.036 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 70 minutes at 630 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 9
Will containing the 40%(weight of 16.8 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.6 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.2 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.9 mole of nickel element
3)
36H
2o, containing the Mg (NO of 0.42 mole of magnesium elements
3)
36H
2o, containing the Zr (NO of 0.006 mole of zr element
3)
44H
2o, containing the La (NO of 0.06 mole of lanthanum element
3)
33H
2o, containing the Nd (NO of 0.08 mole of praseodymium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.05 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 50 minutes at 610 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 10
Will containing the 40%(weight of 19.2 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.52 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.04 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.3 moles of nickel elements
3)
36H
2o, containing the Cu (NO of 0.24 mole of copper element
3)
33H
2o, containing the Ce (NO of 0.02 mole of Ce elements
3)
33H
2o, containing the Nd (NO of 0.1 mole of neodymium element
3)
33H
2o, containing the Nd (NO of 0.08 mole of praseodymium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.01 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 55 minutes at 600 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 11
Will containing the 40%(weight of 21.6 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.36 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.66 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.86 mole of nickel element
3)
36H
2o, containing the Mg (NO of 0.64 mole of magnesium elements
3)
36H
2o, containing the Nd (NO of 0.3 mole of neodymium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.01 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 40 minutes at 600 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 12
Will containing the 40%(weight of 19.2 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.34 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.28 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.96 mole of nickel element
3)
36H
2o, containing the Zn (NO of 0.48 mole of Zn-ef ficiency
3)
36H
2o, containing the La (NO of 0.04 mole of lanthanum element
3)
33H
2o, containing the Sm (NO of 0.08 mole of samarium element
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.07 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 55 minutes at 600 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 13
Will containing the 40%(weight of 24 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.56 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.14 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.12 moles of nickel elements
3)
36H
2o, containing the Mn (NO of 0.3 mole of manganese element
3)
2solution, containing the La (NO of 0.016 mole of lanthanum element
3)
33H
2o, containing the Pr (NO of 0.08 mole of praseodymium element
3)
33H
2o, containing the Ce (NO of 0.1 mole of Ce elements
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.08 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 60 minutes at 600 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 14
Will containing the 40%(weight of 14.4 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.32 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.36 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 0.96 mole of nickel element
3)
36H
2o, containing the Mg (NO of 0.24 mole of magnesium elements
3)
36H
2o, containing the Ce (NO of 0.1 mole of Ce elements
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.014 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 65 minutes at 610 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
embodiment 15
Will containing the 40%(weight of 21.6 moles of element silicons) Ludox, stir 0.5 hour, obtain material A.
By (the NH containing 2.4 moles of molybdenum elements
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By the Fe (NO containing 0.34 moles iron element
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds the Bi (NO containing 0.12 mole of bismuth element after stirring and dissolving again
3)
35H
2o, containing the Ni (NO of 1.04 moles of nickel elements
3)
36H
2o, containing the Mg (NO of 0.4 mole of magnesium elements
3)
36H
2o, containing the Nd (NO of 0.16 mole of neodymium element
3)
33H
2o, containing the Pr (NO of 0.28 mole of praseodymium element
3)
33H
2o, containing the Ce (NO of 0.12 mole of Ce elements
3)
33H
2o, makes material D after stirring and dissolving.
The RbNO containing 0.056 mole of rubidium element is added in 10 grams of water
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 50 minutes at 620 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
Table 1, catalyst
| Catalyst forms | |
| Comparative example 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.08O x+84SiO 2 |
| Embodiment 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2Rb 0.08O x+84SiO 2 |
| Embodiment 2 | Mo 12Bi 0.3Fe 2.1Ni 4.8Mg 2.1La 1.8Rb 0.15O x+72SiO 2 |
| Embodiment 3 | Mo 12Bi 0.5Fe 2.0Ni 6.5Mg 1.9Sm 0.4Nd 2.4Rb 0.3O x+96SiO 2 |
| Embodiment 4 | Mo 12Bi 0.4Fe 1.5Ni 4.5Co 3.2Pr 1.5Rb 0.8O x+108SiO 2 |
| Embodiment 5 | Mo 12Bi 1.5Fe 2.2Ni 5.0Mg 1.8La 0.8Pr 1.4Rb 0.28O x+120SiO 2 |
| Embodiment 6 | Mo 12Bi 2.4Fe 2.8Ni 5.3Mn 0.7Ce 0.8Nd 0.4Ca 0.2Rb 0.7O x+60SiO 2 |
| Embodiment 7 | Mo 12Bi 0.8Fe 4.5Ni 3.5Mg 0.4Pb 0.2 Ce 1.2Nd 1.4Rb 0.3O x+48 SiO 2 |
| Embodiment 8 | Mo 12Bi 2.5Fe 2.5Ni 5.6Pb 1.2Ce 0.7Pr 0.4Rb 0.18O x+132SiO 2 |
| Embodiment 9 | Mo 12Bi 1.0Fe 3.0Ni 4.5Mg 2.1La 0.3Nd 0.4Rb 0.25Zr 0.03O x+84SiO 2 |
| Embodiment 10 | Mo 12Bi 0.2Fe 2.6Ni 6.5Cu 1.2Ce 0.1Pr 0.4Nd 0.5Rb 0.05O x+96SiO 2 |
| Embodiment 11 | Mo 12Bi 3.3Fe 1.8Ni 4.3Mg 3.2Nd 1.5Rb 0.05O x+108SiO 2 |
| Embodiment 12 | Mo 12Bi 1.4Fe 1.7Ni 4.8Zn 2.4La 0.2Sm 0.4Rb 0.35O x+96SiO 2 |
| Embodiment 13 | Mo 12Bi 0.7Fe 2.8Ni 5.6Mn 1.5Ce 0.5La 0.08Pr 0.4Rb 0.4O x +120SiO 2 |
| Embodiment 14 | Mo 12Bi 1.8Fe 1.6Ni 4.8Mg 1.2Ce 0.5Rb 0.07O x+72SiO 2 |
| Embodiment 15 | Mo 12Bi 0.6Fe 1..7Ni 5.2Mg 2.0Ce 0.6Nd 0.8Pr 1.4Rb 0.28O x+108SiO 2 |
Note: SiO in table
2front coefficient represents SiO
2with the mol ratio of described active constituent.
Table 2, evaluating catalyst result
| Single-pass yield of acrylonitrile (%) | Acrylonitrile selectivity (%) | Propylene conversion (%) | |
| Comparative example 1 | 78.7 | 83.3 | 94.5 |
| Embodiment 1 | 81.3 | 84.5 | 96.2 |
| Embodiment 2 | 80.2 | 82.8 | 96.9 |
| Embodiment 3 | 81.1 | 83.2 | 97.5 |
| Embodiment 4 | 81.8 | 84.8 | 96.5 |
| Embodiment 5 | 82.8 | 84.0 | 98.6 |
| Embodiment 6 | 82.6 | 85.1 | 97.1 |
| Embodiment 7 | 83.1 | 84.9 | 97.9 |
| Embodiment 8 | 83.2 | 84.3 | 98.7 |
| Embodiment 9 | 83.4 | 85.3 | 97.8 |
| Embodiment 10 | 83.8 | 85.3 | 98.2 |
| Embodiment 11 | 83.3 | 84.2 | 98.9 |
| Embodiment 12 | 83.3 | 84.6 | 98.5 |
| Embodiment 13 | 83.8 | 84.6 | 99.0 |
| Embodiment 14 | 83.8 | 85.1 | 98.5 |
| Embodiment 15 | 83.0 | 84.4 | 98.4 |
Claims (9)
1. unsaturated nitrile fluid catalyst prepared by ammoxidation, with SiO
2for carrier, the active component containing following general formula represents:
Mo
12Bi
aFe
bNi
cX
dY
eRb
fO
x
Wherein:
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Zr;
Y is at least one be selected from La, Ce, Pr, Nd or Sm;
The span of a is 0.1 ~ 6.0;
The span of b is 0.1 ~ 10.0;
The span of c is 0.1 ~ 10.0;
The span of d is 0.1 ~ 10.0;
The span of e is 0.1 ~ 5.0;
The span of f is >0 and below 0.5;
X is for meeting the oxygen atom sum needed for other element valence.
2. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the span of e is 0.1 ~ 3.0.
3. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 2, is characterized in that the span of e is 0.1 ~ 2.0.
4. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the consumption of carrier be the mol ratio of element silicon and described active component is 50 ~ 140.
5. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 4, is characterized in that the consumption of carrier be the mol ratio of element silicon and described active component is 80 ~ 120.
6. the preparation method of the catalyst described in claim 1, comprises the following steps:
(1) get the Ludox needed for carrier, stir, obtain material A;
(2) material B is obtained by water-soluble for the water soluble compound of aequum molybdenum;
(3) under stirring, material B is added in material A and obtain material C;
(4) material D is obtained by water-soluble for the water soluble compound of aequum Bi, Fe, Ni, X and Y;
(5) compound water solution of aequum Rb is added in material D form material E;
(6) material E is dripped under fast stirring in material C, obtain catalyst pulp;
(7) mist projection granulating;
(8) roasting obtains described catalyst.
7. preparation method according to claim 6, is characterized in that the temperature of step (8) described roasting is 520 ~ 660 DEG C.
8. preparation method according to claim 6, is characterized in that the time of step (8) described roasting is 20 ~ 180 minutes.
9. the application of catalyst according to any one of claim 1 to 5 in unsaturated hydrocarbons prepared by ammoxidation unsaturated nitrile.
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| CN1121321A (en) * | 1993-08-10 | 1996-04-24 | 旭化成工业株式会社 | Ammoxidation catalyst composition and method for producing acrylonitrile or methacrylonitrile using it |
| CN1172689A (en) * | 1996-08-06 | 1998-02-11 | 中国石油化工总公司 | Acrylonitrile fluidized bed containing rare earth metal catalyst |
| JP2000344724A (en) * | 1999-03-26 | 2000-12-12 | Mitsubishi Rayon Co Ltd | Unsaturated nitrile production method |
| US20040110978A1 (en) * | 2002-12-02 | 2004-06-10 | Christos Paparizos | Catalyst for the manufacture of acrylonitrile |
| CN101121131A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst |
| CN101147869A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile by ammonia oxidizing method |
| CN101534945A (en) * | 2006-10-26 | 2009-09-16 | 大野绿水株式会社 | Fluidized-bed catalyst for the production of acrylonitrile and process for the production of acrylonitrile |
| CN101811058A (en) * | 2009-02-19 | 2010-08-25 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation |
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2013
- 2013-10-28 CN CN201310512192.XA patent/CN104549340B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121321A (en) * | 1993-08-10 | 1996-04-24 | 旭化成工业株式会社 | Ammoxidation catalyst composition and method for producing acrylonitrile or methacrylonitrile using it |
| CN1172689A (en) * | 1996-08-06 | 1998-02-11 | 中国石油化工总公司 | Acrylonitrile fluidized bed containing rare earth metal catalyst |
| JP2000344724A (en) * | 1999-03-26 | 2000-12-12 | Mitsubishi Rayon Co Ltd | Unsaturated nitrile production method |
| US20040110978A1 (en) * | 2002-12-02 | 2004-06-10 | Christos Paparizos | Catalyst for the manufacture of acrylonitrile |
| CN101121131A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst |
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