CN101121129A - Method for preparing unsaturated nitrile catalyst using with ammoxidation method - Google Patents
Method for preparing unsaturated nitrile catalyst using with ammoxidation method Download PDFInfo
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- CN101121129A CN101121129A CNA2006100299470A CN200610029947A CN101121129A CN 101121129 A CN101121129 A CN 101121129A CN A2006100299470 A CNA2006100299470 A CN A2006100299470A CN 200610029947 A CN200610029947 A CN 200610029947A CN 101121129 A CN101121129 A CN 101121129A
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- Prior art keywords
- catalyst
- ammoxidation
- unsaturated nitrile
- preparation
- acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 3
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 229960001051 dimercaprol Drugs 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- -1 polyoxyethylene nonylphenol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052732 germanium Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000000126 substance 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241001347978 Major minor Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a preparation method of an unsaturated nitrile catalyst, which is produced by an ammoxidation. The present invention mainly solves the problems in the prior art that in the ammoxidation, an ammonia conversion rate is low; the remnants ammonia is high; carbonyl by-products, such as acrolein etc, are high. The present invention solves the problems well by a technical proposal that SiO2 is used as a carrier, and the catalyst consists of a combination is adopted which contains active components and which is expressed by the following general formula: in the formula of Mo12BiaFebNicXdYeZfOx, the X is selected from at least one of Mg, Co, Ca, Cu, Zn, Pb, Mn, Cr, Nb, Zr, Ti, Sn or Ru; the Y is selected from at least one of La, Ce, Sm or Ge; the Z is selected from at least one of K, Rb, Na, Cs, In, Tl or Ag, and at least one of an organic compound which contains active-oh and can mutually react with a silica sol is added into an initial material in the process of the catalyst preparation. The present invention can be used for the industrial production of unsaturated nitrile, which is produced by an olefin ammoxidation.
Description
Technical field
The present invention relates to a kind of alkene alkene ammonia oxidation and produce the preparation method of unsaturated nitrile catalyst.
Background technology
The ammoxidation of alkene prepares α, in the exploitation sixties in last century, the core technology of this technology is to use a kind of active component to contain the catalyst of Mo, Bi to beta unsaturated nitrile technology by BP company.Through constantly improving, the Mo-Bi series catalysts is very ripe at present, is widely used by preparing acrylonitrile by allylamine oxidation technology industrial.The improvement of catalyst is in the past mainly carried out from activity of such catalysts and stable aspect, as adding transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element and improve redox ability; Add elements such as Na, P to improve the wearability of catalyst; Add elements such as Fe, Co, Ni to suppress the distillation of Mo, improve stability of catalyst or the like.Research improvement to such catalyst in recent years mainly is conceived to the optimization of reaction condition, as attempts to reduce sky ratio, the ammonia ratio of reaction.Lower ammonia ratio and empty than the production capacity that more helps improving device, and reduce be used in and the consumption of the sulfuric acid of unreacted ammonia, reduce the generation of sulphur ammonium, to reducing production costs and control environment pollution, realize the cleaner production of acrylonitrile, crucial meaning is all arranged.
Patent CN 99119905.7, CN 99119906.5, CN 97106771.6 and CN 96101529.2 have all introduced the improved Mo-Bi catalyst that is used for propylene, isobutene ammonia oxidizing system unsaturated nitrile catalyst, the advantage of these catalyst has oxidation-reduction stability and reaction yield preferably preferably, and reacting ammonia is lower than empty ratio and reaction temperature.
Patent CN 01113194.2, CN 01113193.4 and CN 01113192.6 introduced in catalyst preparation process, get part metals and organic ligand, chelating agent or surfactant separately the method for preparation improve catalyst at low ammonia than the performance under the reaction condition.
Patent CN 03151170.8 and CN 03151169.4 have introduced in the catalyst preparation process, and the solid silica that adds 2～25% grain diameter and be 5～100 nanometers in carrier starting material Ludox improves catalyst performance.
Summary of the invention
Technical problem to be solved by this invention is in the prior art ammoxidation reaction process, the problem of carbonyl by-product object heights such as the ammonia conversion ratio is low, residual ammonia is high, methacrylaldehyde provides a kind of new preparation method who is used for propylene, isobutene ammonia oxidizing legal system unsaturated nitrile catalyst.The catalyst that makes with this method is compared with the prior art catalyst to have and is more suitable in move reacting ammonia conversion ratio height, the characteristics that residual ammonia is low, the methacrylaldehyde growing amount is low than under the condition at lower ammonia.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of ammoxidation method to manufacturing unsaturated nitrile catalyst, and with SiO
2Be carrier, the active constituent composition that catalyst contains is by following general formula:
Mo
12Bi
aFe
bNi
cX
dY
eZ
fO
x
Wherein:
X is selected from least a among Mg, Co, Ca, Cu, Zn, Pb, Mn, Cr, Nb, Zr, Ti, Sn or the Ru;
Y is selected from least a among La, Ce, Sm or the Ge;
Z is selected from least a among K, Rb, Na, Cs, In, Tl or the Ag;
A=0.1～6, b, c, d, e=0.1～10, f is＞0～0.7, x satisfies the required oxygen atom sum of other element valence; The starting material of required active component is corresponding water soluble salt, make mixed salt solution after the active component starting material dissolved in the desired amount, and make slurry with coprecipitation with carrier starting material Ludox, the aging back of slurry spray-drying, dried particles temperature be 500～610 ℃ of following roastings 0.5～8 hour required catalyst, wherein in starting material, add at least a can with the interactional organic compound that contains active hydroxyl of Ludox.
The organic compound preferred version is selected from least a in acetic acid, formic acid, trichloroacetic acid, benzoic acid, triethanolamine, ascorbic acid, dimercaprol dimercaptopropanol, tartaric acid, sulfonic group phenol, polyvinyl alcohol, polyoxyethylene nonylphenol ether, citric acid, sweet mellow wine, ethylene glycol or the glycerine in the such scheme.Organic compound addition preferable range is 0.01～20% of a vehicle weight, and more preferably scope is 0.1～10% of a vehicle weight, and optimum range is 0.1～5% of a vehicle weight.
It is generally acknowledged, reduce the residual ammonia of ammoxidation reaction, and keep catalyst that acrylonitrile yield and propylene conversion are preferably arranged simultaneously, must solve several problems.The burning of first ammonia; It two is the influences to the major-minor product of the residual volume of ammonia.In ammoxidation tail gas, the existence of a certain proportion of free ammonia must be arranged, this is in order to guarantee carrying out smoothly of catalytic cycle on the one hand, and the further secondary oxidation of organic product under the excess of oxygen condition that on the other hand can inhibitory reaction reduces secondary oxidation accessory substance such as CO
2, CO, methacrylaldehyde and acrylic acid generation, the improvement of catalyst performance can be controlled at the amount of residual ammonia a lower level and still can suppress secondary oxidation reaction.
Find through a large amount of tests, utilize some organic compound that carrier is carried out modification, can change the redox ability of catalyst physics and chemical property and catalyst, thereby make catalyst under the condition of low residual ammonia, to possess superior reactivity worth.The compound that adds can be removed by high-temperature roasting in the Preparation of Catalyst subsequent handling.Compared with the prior art; effect of the present invention is very tangible; the catalyst of gained has redox ability preferably; can receive than obtaining higher product list under the condition at lower sky ratio and ammonia; and reaction temperature is lower; help prolonging the service life of catalyst; lower ammonia ratio and residual ammonia help environmental protection; improve working condition; a kind of cleaning procedure of acrylonitrile process can be provided, and under identical investigation condition, residual ammonia is low; methacrylaldehyde is low, has obtained better technical effect.
In the following embodiment that provides, be to the investigation appreciation condition of catalyst:
Reactor: fluidized-bed reactor, 38 millimeters of internal diameters
Catalyst filling amount: 550 grams
Reactor top pressure: 0.084MPa (gauge pressure)
Reaction temperature: 430 ℃
Reaction time: 4 hours
Raw material ratio: propylene/ammonia/air=1/1.2/9.5
WWH:0.06 hour
-1
Product absorbs with 0 ℃ of diluted acid, with gas-chromatography and chemical analysis binding analysis product.And the calculating Carbon balance, when Carbon balance is valid data during at (95～105) %.
Propylene conversion, acrylonitrile yield and optionally be defined as:
The present invention is further elaborated below by embodiment.
The specific embodiment
[comparative example 1]
With 441.4 gram (NH
4)
6Mo
7O
244H
2O joins in the warm water of 70 ℃ of 330 grams, stirs and makes its whole dissolvings, and the Ludox that adds 1400 grams 40% (weight) is made material A.
With 213.1 gram Fe (NO
3)
39H
2O adds in 70 ℃ of hot water of 150 grams, adds 201.8 gram Bi (NO after the stirring and dissolving again
3)
35H
2O, 274.8 gram Ni (NO
3)
36H
2O, 96.3 gram Mg (NO
3)
36H
2O, 72.5 gram La (NO
3)
33H
2O, 18.6 gram Sm (NO
3)
33H
2O and 15.3 gram H
7P (W
2O
7)
63H
2Make material B after the O stirring and dissolving.
In 20 gram water, add 1.1 gram KNO
3, 0.9 the gram NaNO
3With 2.0 gram CsNO
3To form material C among its adding material B after the dissolving.
Material C is dripped in material A under stirring fast, form catalyst pulp.In 70 ℃ of spray-dryings after aging 3 hours, with the particle of gained in rotary calciner in 580 ℃ of following roastings 3 hours, finished catalyst.The catalyst general formula is Mo
12Bi
2.0Fe
2.5Ni
4.5Mg
1.8La
0.8Sm
0.2K
0.05Cs
0.05Na
0.05W
0.3P
0.03+ 50%SiO
2
[embodiment 1～15]
The same comparative example of embodiment method for preparing catalyst just adds following compounds in material A:
Embodiment 1,2 gram trichloroacetic acids
2,50 milliliters of acetic acid of embodiment
2,50 milliliters of acetic acid of embodiment
3,25 milliliters of formic acid of embodiment
Embodiment 4,20 gram sulfonic group phenol
Embodiment 5,10 gram sweet mellow wine
Embodiment 6,30 gram citric acids
Embodiment 7,22 gram tartaric acid
Embodiment 8,30 gram ethylene glycol
Embodiment 9,15 gram oxalic acid
Embodiment 10,100 gram glycerine
Embodiment 11,70 gram benzoic acid
Embodiment 12,150 gram polyoxyethylene nonylphenol ethers
Embodiment 13,60 gram polyvinyl alcohol
Embodiment 14,10 gram dimercaprol dimercaptopropanol
Embodiment 15,5 gram ascorbic acid+20 gram tartaric acid
Finished catalyst is investigated by above-mentioned investigation appreciation condition, and it the results are shown in Table 1.
Table 1 embodiment evaluation result
| Single-pass yield of acrylonitrile (%) | Acrylonitrile selectivity (%) | Propylene conversion (%) | Residual ammonia (%) | The methacrylaldehyde list is received (%) | |
| Comparative example 1 | 76.2 | 81.1 | 94.0 | 12.2 | 2.5 |
| Embodiment 1 | 76.4 | 81.4 | 93.9 | 3.3 | 1.3 |
| Embodiment 2 | 76.8 | 79.4 | 96.7 | 4.3 | 1.5 |
| Embodiment 3 | 77.3 | 79.3 | 97.5 | 7.8 | 0.5 |
| Embodiment 4 | 79.1 | 80.5 | 98.2 | 5.5 | 0.1 |
| Embodiment 5 | 78.5 | 80.3 | 97.7 | 5.7 | 0.6 |
| Embodiment 6 | 76.7 | 79.2 | 96.8 | 6.1 | 1.6 |
| Embodiment 7 | 80.9 | 81.5 | 99.3 | 2.8 | 1.5 |
| Embodiment 8 | 77.8 | 80.5 | 96.7 | 4.6 | 2.1 |
| Embodiment 9 | 79.7 | 80.4 | 99.1 | 5.2 | 0.4 |
| Embodiment 10 | 81.4 | 82.1 | 99.1 | 5.0 | 0.2 |
| Embodiment 11 | 79.4 | 80.4 | 98.7 | 4.5 | 0.5 |
| Embodiment 12 | 79.5 | 81.0 | 98.1 | 2.8 | 0.8 |
| Embodiment 13 | 78.6 | 80.4 | 97.8 | 4.7 | 1.3 |
| Embodiment 14 | 83.0 | 83.9 | 98.9 | 6.3 | 0.3 |
| Embodiment 15 | 77.5 | 80.1 | 96.8 | 3.2 | 0.1 |
Claims (5)
1. the preparation method of an ammoxidation method to manufacturing unsaturated nitrile catalyst is with SiO
2Be carrier, catalyst contains the active component composition by following general formula:
Mo
12Bi
aFe
bNi
cX
dY
eZ
fO
x
Wherein:
X is selected from least a among Mg, Co, Ca, Cu, Zn, Pb, Mn, Cr, Nb, Zr, Ti, Sn or the Ru;
Y is selected from least a among La, Ce, Sm or the Ge;
Z is selected from least a among K, Rb, Na, Cs, In, Tl or the Ag;
A=0.1～6, b, c, d, e=0.1～10, f is＞0～0.7, x satisfies the required oxygen atom sum of other element valence; The starting material of required active component element is corresponding water soluble salt, make mixed salt solution after the active component starting material dissolved in the desired amount, and make slurry with coprecipitation with carrier starting material Ludox, the aging back of slurry spray-drying, dried particles temperature be 500～610 ℃ of following roastings 0.5～8 hour required catalyst, it is characterized in that in starting material, adding at least a can with the interactional organic compound that contains active hydroxyl of Ludox.
2. the preparation method of ammoxidation method to manufacturing unsaturated nitrile catalyst according to claim 1 is characterized in that organic compound is selected from least a in acetic acid, formic acid, trichloroacetic acid, benzoic acid, triethanolamine, ascorbic acid, dimercaprol dimercaptopropanol, tartaric acid, sulfonic group phenol, polyvinyl alcohol, polyoxyethylene nonylphenol ether, citric acid, sweet mellow wine, ethylene glycol or the glycerine.
3. the preparation method of prepared by ammoxidation unsaturated nitrile catalyst according to claim 1 is characterized in that the organic compound addition is 0.01～20% of a vehicle weight.
4. the preparation method of ammoxidation method to manufacturing unsaturated nitrile catalyst according to claim 3, the addition that it is characterized in that the organic matter compound is 0.1～10% of a vehicle weight.
5. the preparation method of ammoxidation method to manufacturing unsaturated nitrile catalyst according to claim 4, the addition that it is characterized in that the organic matter compound is 0.1～5% of a vehicle weight.
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