CN104549344A - Unsaturated nitrile fluidized bed catalyst and preparation method thereof - Google Patents
Unsaturated nitrile fluidized bed catalyst and preparation method thereof Download PDFInfo
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- CN104549344A CN104549344A CN201310512659.0A CN201310512659A CN104549344A CN 104549344 A CN104549344 A CN 104549344A CN 201310512659 A CN201310512659 A CN 201310512659A CN 104549344 A CN104549344 A CN 104549344A
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- sosoloid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 13
- 239000004480 active ingredient Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 164
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 239000003945 anionic surfactant Chemical group 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 40
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract description 2
- AMGNHZVUZWILSB-UHFFFAOYSA-N 1,2-bis(2-chloroethylsulfanyl)ethane Chemical compound ClCCSCCSCCCl AMGNHZVUZWILSB-UHFFFAOYSA-N 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
- 239000013081 microcrystal Substances 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
- 238000003756 stirring Methods 0.000 description 108
- 238000005507 spraying Methods 0.000 description 38
- 239000002245 particle Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000013078 crystal Substances 0.000 description 21
- 230000032683 aging Effects 0.000 description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 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
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- OTKOPKDCLGDHFV-UHFFFAOYSA-N azane;2-methylprop-1-ene Chemical compound N.CC(C)=C OTKOPKDCLGDHFV-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray 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
- 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
- 238000001238 wet grinding Methods 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a fluidized bed catalyst for preparation of unsaturated nitrile by ammoxidation, a preparation method of the catalyst and application of the catalyst in unsaturated nitrile synthesis, and mainly aims to solve the problem of low acrylonitrile yield caused by low propene conversation, low selectivity of acrylonitrile and quick reduction of acrylonitrile catalyst in the prior art. The problem can be well solved by adopting a technical scheme that SiO2 is used as a carrier and the catalyst comprises an active ingredient as shown in the formula Mo12BiaFebNicXdYeKfZgQhOx, wherein Z is rare-earth element or a mixture thereof; and z and Fe form nano-solid solution microcrystal under the action of a template agent Q to prepare the catalyst. The catalyst can be used in industrial production of acrylonitrile preparation by propylene ammoxidation.
Description
Technical field
The present invention relates to the fluid catalyst of prepared by ammoxidation unsaturated nitrile, and preparation method thereof, and the application of described catalyzer in unsaturated nitrile synthesis.
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 catalyzer using a kind of active ingredient 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 catalyzer in the past is mainly carried out from the activity of catalyzer 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 wear resistance of catalyzer; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, improve stability of catalyzer etc.
Patent CN 99119905.7, CN 99119906.5, CN 97106771.6 and CN 96101529.2 all describe the Mo-Bi catalyzer for propylene, isobutene ammonia oxidizing unsaturated nitrile catalyst of improvement, the advantage of these catalyzer has good oxidation-reduction stability and reaction yield preferably, reacting ammonia than empty than and temperature of reaction 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, sequestrant or tensio-active agent prepared separately to improve catalyzer at low ammonia than the performance under reaction conditions.
Patent CN 03151170.8 and CN 03151169.4 describes in catalyst preparation process, and the grain diameter adding 2 ~ 25% in carrier initiator silicon sol is that the solid silica of 5 ~ 100 nanometers is to improve catalyst performance.
Above patented technology is to the transformation efficiency improving catalyzer, and reduce the discharge of ammonia ratio and then minimizing amine wastewater of sulphuric acid in reaction process, there has been certain effect the aspects such as the life-span of extending catalyst; But patent report up to now, all there is acrylonitrile catalyst crystal grain excessive, and be easy to sintering gathering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and declines fast, causes the problem that acrylonitrile yield is low.
Summary of the invention
One of technical problem to be solved by this invention is that in prior art, propylene conversion is low at the reaction temperatures, and acrylonitrile selectivity is low, and declines fast, causes the problem that acrylonitrile yield is low, provides a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation.This catalyzer has the high advantage of acrylonitrile yield.
Two of technical problem to be solved by this invention is preparation methods of the catalyzer corresponding to one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is the application in unsaturated nitrile synthesis of the described catalyzer of one of above-mentioned technical problem.
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 ingredient containing following general formula represents:
Mo
12bi
afe
bni
cx
dy
ek
fz
go χ, wherein:
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one be selected from Rb, Li or Cs;
Z 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 and≤0.5;
The span of f is >0 and≤0.2;
The span of g is 0.1 ~ 3;
χ is for meeting the Sauerstoffatom sum needed for other element valence;
It is characterized in that, after the sosoloid that Z and Fe is first formed under template Q effect, be prepared into catalyzer again;
Wherein said template Q is selected from least one in di-n-propylamine, Diisopropylamine, tetramethyleneimine, quadrol, n-Butyl Amine 99, diethylamine, triethylamine, hexahydroaniline, polyoxyethylene glycol and methylcellulose gum, polyvinylpyrrolidone, quaternary cationics and anion surfactant; The mol ratio of Z and template Q is 1 ~ 100; Described template Q preferably includes quaternary cationics and anion surfactant;
Described quaternary cationics has the structure shown in formula I:
(formula I);
R
1c
14~ C
18alkyl, R
2, R
3and R
4independently take from C
1~ C
4alkyl, J is selected from chlorine or bromine;
Wherein said anion surfactant has the structure shown in formula II:
(formula II);
R
5be selected from C
8~ C
18alkyl.
In technique scheme, R
1, R
2, R
3and R
4be preferably alkyl.The mol ratio of Z and template Q is preferably 5 ~ 20.The consumption of carrier is preferably 30 ~ 70% of catalyst weight; The consumption of carrier is more preferably 40 ~ 60% of catalyst weight.
In order to solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of the catalyzer described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
(1) salt of aequum Z and Fe and template device Q are dissolved in the water obtain material 1;
(2) material 1 drying, roasting obtain sosoloid 2;
(3) be dissolved in water by the ammonium molybdate of aequum and the water-soluble cpds of Y and K, the silicon sol then adding carrier aequum forms material 3;
(4) Bi, Ni of aequum and the water-soluble cpds that is selected from X are dissolved in water form material 4;
(5) under agitation, material 3 and sosoloid 2 are added in material 4 and mix, obtain catalyst pulp 5;
(6) spray-dried, the roasting of catalyst pulp 5 obtains described catalyzer.
In technique scheme, the concrete mode of the drying described in step (2) is not key point of the present invention, but the material obtained due to spray-dired mode is powdery, is conducive to the operation of step (5), therefore the preferred spray pattern of drying of step (2) carries out.The temperature of step (2) described roasting is preferably 700 ~ 900 DEG C, more preferably 750 ~ 850 DEG C; Roasting time was preferably 0.2 ~ 4 as a child, more preferably 0.5 ~ 2 hour.The temperature of step (6) described roasting is preferably 520 ~ 660 DEG C, and roasting time is preferably 0.2 ~ 4 hour; The temperature of step (6) described roasting is more preferably 550 ~ 640 DEG C, and roasting time is more preferably 0.5 ~ 2 hour.In order to step (6) spraying dry preferably, the median size of the sosoloid 2 described in step (5) is the smaller the better, therefore the sosoloid 2 that step (2) obtains needs through extra pulverising step to obtain required powder material, superfine grinding mode common in prior art all can be used for the present invention, such as ball milling, comminution by gas stream etc., the median size of step (5) described sosoloid is generally ﹥ 0 and is less than 20 microns.
In order to step (6) spraying dry preferably, first sosoloid 2 is crushed to except suitable particle size except being selected in before material 3 and sosoloid 2 add material 4, material 3 and sosoloid 2 can also be added wet-milling after in material 4, make granularity reach the degree being applicable to spraying.
In technique scheme, spray-dired actual conditions is not key of the present invention, as long as can obtain dry pulverulent material.
In the following embodiment that provides and comparative example, to the investigation appreciation condition of catalyzer be:
Reactor: fluidized-bed reactor, internal diameter 38 millimeters
Catalyst filling amount: 400 grams
Reactor top pressure: 0.084 MPa (gauge pressure)
Temperature of reaction: 430 DEG C
Reaction times: 4 hours
Material molar ratio: propylene/ammonia/air=1/1.1/9.5,
WWH: 0.085 hour
-1
Reaction 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 mole number/all product C mole numbers) × 100%
Single-pass yield of acrylonitrile (%)=(generating vinyl cyanide C mole number/all product C mole numbers) × 100%
Acrylonitrile selectivity (%)=(single-pass yield of acrylonitrile/propylene conversion) × 100 %
The present invention makes catalyzer after passing through the Nano Solid Solution crystallite first formed under template Q effect at acrylonitrile catalyst formula rare earth elements and Fe, due to the guide effect of template structure, achieve the crystal transformation of compound hydrocarbyl oxide to sosoloid, and cause lattice distortion because of the difference of rare earth and Fe cation radius, catalyzer crystal grain diminishes, promote that the oxidation one of body phase oxygen is reduced, thus enhancing redox property, propylene conversion obviously rises under high loads, increase the selective oxidation reaction of propylene and lattice oxygen, and then also significantly increase acrylonitrile selectivity, acrylonitrile yield significantly improves.As shown in table 2 result: catalyzer grain size drops to 4.3 ~ 12.2nm of embodiment by the 26.4nm of comparative example 1, decline more than 1 times, Be very effective; Acrylonitrile selectivity is increased to about 84 ~ 86% of embodiment by 83.3% of comparative example 1, and propylene conversion is increased to about 97% of embodiment by 94.7% of comparative example 1, and single-pass yield of acrylonitrile is then increased to by 78.9% and is up to 84.2%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated:
Embodiment
comparative example 1
(1) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(2) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(3) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 77 grams, adds 164.6 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o, 78.3 grams of Mg (NO
3)
36H
2o, 53.9 grams of La (NO
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2material D is made after O stirring and dissolving.
(4) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(5) 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 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 1
(1) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 53.9 grams of La (NO after stirring and dissolving
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2o and 36.4 gram cetyl trimethylammonium bromide, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 780 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(5) by 164.6 grams of Bi (NO
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o and 78.3 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 2
(1) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 53.9 grams of La (NO after stirring and dissolving
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2o and 34.3 gram of Witco 1298 Soft Acid ammonium, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 780 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(5) by 164.6 grams of Bi (NO
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o and 78.3 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 3
(1) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 53.9 grams of La (NO after stirring and dissolving
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2o, 30.3 grams of cetyl trimethylammonium bromides and 5.7 grams of Witco 1298 Soft Acid ammoniums, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 780 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(5) by 164.6 grams of Bi (NO
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o and 78.3 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 4
(1) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 53.9 grams of La (NO after stirring and dissolving
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2o, 7.1 grams of cetyl trimethylammonium bromides and 28.6 grams of Witco 1298 Soft Acid ammoniums, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 780 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(5) by 164.6 grams of Bi (NO
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o and 78.3 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 5
(1) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 53.9 grams of La (NO after stirring and dissolving
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2o, 36.4 grams of cetyl trimethylammonium bromides and 34.3 grams of Witco 1298 Soft Acid ammoniums, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 780 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(5) by 164.6 grams of Bi (NO
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o and 78.3 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 6
(1) by 173.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 53.9 grams of La (NO after stirring and dissolving
3)
33H
2o, 15.4 grams of Sm (NO
3)
33H
2o, 14.6 grams of cetyl trimethylammonium bromides and 13.7 grams of Witco 1298 Soft Acid ammoniums, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 780 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 359.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 294 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.
(5) by 164.6 grams of Bi (NO
3)
35H
2o, 224.2 grams of Ni (NO
3)
36H
2o and 78.3 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.57 gram of KNO is added
3, 0.3 gram of NaNO
3with 1.64 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
As can be seen from comparative example 1 and embodiment 1 to embodiment 6 relatively in, in raising acrylonitrile selectivity and propylene conversion, quaternary cationics and anion surfactant have synergy, achieve unforeseeable technique effect.
embodiment 7
(1) by 259.8 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 15 grams, adds 18.9 grams of Sm (NO after stirring and dissolving
3)
33H
2o, 7.6 grams of triethylamines and 2.3 grams of hexahydroaniline, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 900 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 438.7 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 359 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.
(5) by 20.1 grams of Bi (NO
3)
35H
2o, 152.1 grams of Ni (NO
3)
36H
2o and 201.8 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.4 gram of KNO is added
3with 2.0 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2 hours at 620 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 8
(1) by 173.7 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 32.1 grams of Ce (NO after stirring and dissolving
3)
33H
2o, 7.3 grams of La (NO
3)
33H
2o, 8.0 grams of Pr (NO
3)
33H
2o, 16.8 grams of Sm (NO
3)
33H
2o, 15.9 grams of Nd (NO
3)
33H
2o, 10.0 grams of polyvinylpyrrolidones and 2.9 grams of methylcellulose gum, stirring reaction is spraying dry after 0.5 hour, by the roasting 2 hours at 850 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 392 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 321 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.
(5) by 53.9 grams of Bi (NO
3)
35H
2o, 304.4 grams of Ni (NO
3)
36H
2o and 60.5 gram of Ca (NO
3)
24H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.6 gram of KNO is added
3with 1.8 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 1.5 hours at 600 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 9
(1) by 71 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 10 grams, adds 7.5 grams of Pr (NO after stirring and dissolving
3)
33H
2o, 1.1 grams of Diisopropylamines and 0.5 gram of hexahydroaniline, stirring reaction is spraying dry after 0.5 hour, by the roasting 1.5 hours at 810 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1300 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 368.6 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 302 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.
(5) by 135 grams of Bi (NO
3)
35H
2o, 332.3 grams of Ni (NO
3)
36H
2o and 89.2 gram of Mg (NO
3)
36H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 1.4 grams of KNO are added
3with 4.4 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2 hours at 590 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 10
(1) by 245.6 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 16 grams, adds 26.1 grams of Ce (NO after stirring and dissolving
3)
33H
2o, 17.3 grams of Nd (NO
3)
33H
2o, 6.3 grams of di-n-propylamines, stirring reaction is spraying dry after 0.5 hour, by the roasting 3 hours at 750 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1175 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 424.9 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 348 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.
(5) by 38.9 grams of Bi (NO
3)
35H
2o, 388.9 grams of Ni (NO
3)
36H
2o and 9.5 gram of Ca (NO
3)
24H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 2 grams of KNO are added
3, 3.89 grams of CsNO
3with 0.7 gram of LiNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2.5 hours at 585 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 11
(1) by 131.8 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 16 grams, adds 8.7 grams of Ce (NO after stirring and dissolving
3)
33H
2o, 17.4 grams of Nd (NO
3)
33H
2o, 14.3 grams of polyoxyethylene glycol and 1.0 grams of triethylamines, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 840 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1200 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 427.5 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 350 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.
(5) by 68.5 grams of Bi (NO
3)
35H
2o, 302.4 grams of Ni (NO
3)
36H
2o and 175.9 gram of Mg (NO
3)
26H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.7 gram of KNO is added
3with 3.9 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2 hours at 600 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 12
(1) by 150.6 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 16 grams, adds 8 grams of Ce (NO after stirring and dissolving
3)
33H
2o, 1.6 grams of Nd (NO
3)
33H
2o, 0.8 gram of tetramethyleneimine and 17.1 grams of polyoxyethylene glycol, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 830 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 390.9 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 320 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.
(5) by 134.3 grams of Bi (NO
3)
35H
2o, 244 grams of Ni (NO
3)
36H
2o and 151.4 gram of Mg (NO
3)
26H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 1 gram of KNO is added
3, 1.4 grams of RbNO
3with 1.8 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 1 hour at 630 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 13
(1) by 112.8 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 19 grams, adds 7.3 grams of La (NO after stirring and dissolving
3)
33H
2o, 7.9 grams of Pr (NO
3)
33H
2o, 16.8 grams of Sm (NO
3)
33H
2o, 2.6 grams of PVP and 2.8 gram ADBS, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 860 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1275 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 390.4 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 319 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.
(5) by 143 grams of Bi (NO
3)
35H
2o, 146.2 grams of Ni (NO
3)
36H
2o and 212.6 gram of Mg (NO
3)
26H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 1.5 grams of KNO are added
3with 2.5 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2.5 hours at 590 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 14
(1) by 127.9 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 15 grams, adds 117.5 grams of Sm (NO after stirring and dissolving
3)
33H
2o, 15.9 grams of polyoxyethylene glycol and 1.5 grams of hexahydroaniline, stirring reaction is spraying dry after 0.5 hour, by the roasting 2 hours at 830 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 390.5 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 320 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.
(5) by 26.8 grams of Bi (NO
3)
35H
2o, 324.9 grams of Ni (NO
3)
36H
2o and 118.1 gram of Mg (NO
3)
26H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 1.9 grams of KNO are added
3with 1.8 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2 hours at 610 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 15
(1) by 186.2 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 17 grams, adds 8.2 grams of Pr (NO after stirring and dissolving
3)
33H
2o, 1.7 grams of Sm (NO
3)
33H
2o, 0.5 gram of quadrol, stirring reaction is spraying dry after 0.5 hour, by the roasting 1 hour at 820 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 402.7 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 329 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.
(5) by 73.8 grams of Bi (NO
3)
35H
2o, 296 grams of Ni (NO
3)
36H
2o, 101 grams of Mn (NO
3)
2with 9 grams of Ca (NO
3)
24H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 1.4 grams of KNO are added
3with 3.3 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2.5 hours at 615 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 16
(1) by 168.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 15 grams, adds 1.8 grams of Ce (NO after stirring and dissolving
3)
33H
2o, 0.8 gram of La (NO
3)
33H
2o, 1.9 grams of Sm (NO
3)
33H
2o, 0.7 gram of quadrol and 0.7 gram of CTAB, stirring reaction is spraying dry after 0.5 hour, by the roasting 3 hours at 760 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1250 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 436.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 357 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.
(5) by 40 grams of Bi (NO
3)
35H
2o, 332.8 grams of Ni (NO
3)
36H
2o and 42.2 gram of Mg (NO
3)
26H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 0.8 gram of KNO is added
3, 2.1 grams of RbNO
3with 3.2 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 560 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
embodiment 17
(1) by 165.4 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 15 grams, adds 24 grams of Ce (NO after stirring and dissolving
3)
33H
2o, 7.3 grams of La (NO
3)
33H
2o, 7.9 grams of Pr (NO
3)
33H
2o, 15.9 grams of Nd (NO
3)
33H
2o, 0.7 gram of triethylamine and 1.5 grams of quadrols, stirring reaction is spraying dry after 0.5 hour, by the roasting 2 hours at 770 DEG C in rotary calciner of the particle of gained, obtains sosoloid 1.
(2) with ball mill, sosoloid 1 being crushed to median size is 15 microns, obtains sosoloid 2.
(3) by 1275 grams of 40%(weight) silicon sol, stir 0.5 hour, obtain material A.
(4) by 390.3 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 319 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.
(5) by 26.8 grams of Bi (NO
3)
35H
2o, 405.9 grams of Ni (NO
3)
36H
2o and 23.6 gram of Mg (NO
3)
26H
2o adds in 70 DEG C of hot water of 60 grams, makes material D after stirring and dissolving.
(6) in 10 grams of water, 1.8 grams of KNO are added
3with 2.9 grams of CsNO
3added after dissolving in material D and formed material E.
(7) sosoloid 2 and material E are added in material C fast, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 2 hours at 620 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
For ease of comparing, the mol ratio of catalyzer composition, template Q composition, Z and template Q, catalyzer crystal grain and evaluating catalyst be the results are shown in table 1.
Table 1 (continued)
| Catalyzer forms | Template Q composition/mol ratio | |
| Comparative example 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x+50wt%SiO 2 | Nothing |
| Embodiment 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x +50wt%SiO 2 | CTAB/ |
| Embodiment 2 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x +50wt%SiO 2 | ADBS/ |
| Embodiment 3 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x +50wt%SiO 2 | CTAB+ ADBS /1:0.2 |
| Embodiment 4 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x +50wt%SiO 2 | CTAB+ ADBS /1:5 |
| Embodiment 5 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x +50wt%SiO 2 | CTAB+ ADBS /1:1 |
| Embodiment 6 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05 Cs 0.05Na 0.05O x +50wt%SiO 2 | CTAB+ ADBS /1:1 |
| Embodiment 7 | Mo 12Bi 0.2Fe 3.5Ni 2.5Mg 3.8Sm 0.2K 0.05Cs 0.05O x +50%SiO 2 | Triethylamine+hexahydroaniline/3:1 |
| Embodiment 8 | Mo 12Bi 0.6Fe 2.3Ni 5.6Ca 1.5Ce 0.4La 0.1Pr 0.1Sm 0.2Nd 0.2 K 0.11Cs 0.05 O x +50wt%SiO 2 | PVP+ methylcellulose gum/1:9 |
| Embodiment 9 | Mo 12Bi 1.6Fe 1.0Ni 6.5Mg 2.0Pr 0.1K 0.12Cs 0.13O x +52wt%SiO 2 | Diisopropylamine+hexahydroaniline/2:1 |
| Embodiment 10 | Mo 12Bi 0.4Fe 3.0Ni 6.6Ca 0.2Ce 0.3Nd 0.2 K 0.15Cs 0.1Li 0.05O x +47wt%SiO 2 | Di-n-propylamine |
| Embodiment 11 | Mo 12Bi 0.7Fe 1.6Ni 5.1Mg 3.4Pr 0.1Nd 0.2K 0.05Cs 0.1O x +48wt%SiO 2 | Polyoxyethylene glycol+triethylamine/1:20 |
| Embodiment 12 | Mo 12Bi 1.5Fe 2.0Ni 4.5Mg 3.2Ce 0.1Nd 0.02K 0.08Rb 0.05Cs 0.05O x +50wt%SiO 2 | Tetramethyleneimine+polyoxyethylene glycol/20:1 |
| Embodiment 13 | Mo 12Bi 1.6Fe 1.5Ni 2.7Mg 4.5La 0.1Pr 0.1Sm 0.2 K 0.12Cs 0.07O x +51wt%SiO 2 | PVP+ ADBS/1:30 |
| Embodiment 14 | Mo 12Bi 0.3Fe 1.7Ni 6.0Mg 2.5Sm 1.4K 0.15Cs 0.05O x +50wt%SiO 2 | Polyoxyethylene glycol+hexahydroaniline/1:10 |
| Embodiment 15 | Mo 12Bi 0.8Fe 2.4Ni 5.3Mn 1.5Ca 0.2Sm 0.02Pr 0.1K 0.11Cs 0.09O x +50wt%SiO 2 | Quadrol |
| Embodiment 16 | Mo 12Bi 0.4Fe 2.0Ni 5.5Mg 0.8Ce 0.02La 0.01Sm 0.02K 0.06Rb 0.07Cs 0.08O x +50wt%SiO 2 | Quadrol+CTAB/8:1 |
| Embodiment 17 | Mo 12Bi 0.3Fe 2..2Ni 7.5Mg 0.5Ce 0.3La 0.1Pr 0.1Nd 0.2 K 0.14Cs 0.12O x +51wt%SiO 2 | Triethylamine+quadrol/1:5 |
Note: in table, CTAB represents cetyl trimethylammonium bromide; ADBS represents Witco 1298 Soft Acid ammonium; PVP represents polyvinylpyrrolidone
Table 1(continues)
Claims (10)
1. unsaturated nitrile fluid catalyst prepared by ammoxidation, with SiO
2for carrier, the active ingredient containing following general formula represents:
Mo
12bi
afe
bni
cx
dy
ek
fz
go χ, wherein:
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one be selected from Rb, Li or Cs;
Z 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 and≤0.5;
The span of f is >0 and≤0.2;
The span of g is 0.1 ~ 3;
χ is for meeting the Sauerstoffatom sum needed for other element valence;
It is characterized in that, after the sosoloid that Z and Fe is first formed under template Q effect, be prepared into catalyzer again;
Wherein said template Q is selected from least one in di-n-propylamine, Diisopropylamine, tetramethyleneimine, quadrol, n-Butyl Amine 99, diethylamine, triethylamine, hexahydroaniline, polyoxyethylene glycol and methylcellulose gum, polyvinylpyrrolidone, quaternary cationics and anion surfactant; The mol ratio of Z and template Q is 1 ~ 100;
Described quaternary cationics has the structure shown in formula I:
(formula I);
R
1c
14~ C
18alkyl, R
2, R
3and R
4independently take from C
1~ C
4alkyl, J is selected from chlorine or bromine;
Wherein said anion surfactant has the structure shown in formula II:
(formula II);
R
5be selected from C
8~ C
18alkyl.
2. catalyzer according to claim 1, is characterized in that R
1, R
2, R
3and R
4for alkyl.
3. catalyzer according to claim 1, is characterized in that the mol ratio of Z and template Q is 5 ~ 20.
4. catalyzer according to claim 1, is characterized in that the consumption of carrier is 30 ~ 70% of catalyst weight.
5. the preparation method of the catalyzer described in claim 1, comprises the steps:
(1) salt of aequum Z and Fe and template device Q are dissolved in the water obtain material 1;
(2) material 1 drying, roasting obtain sosoloid 2;
(3) be dissolved in water by the ammonium molybdate of aequum and the water-soluble cpds of Y and K, the silicon sol then adding carrier aequum forms material 3;
(4) Bi, Ni of aequum and the water-soluble cpds that is selected from X are dissolved in water form material 4;
(5) under agitation, material 3 and sosoloid 2 are added in material 4 and mix, obtain catalyst pulp 5;
(6) spray-dried, the roasting of catalyst pulp 5 obtains described catalyzer.
6. preparation method according to claim 5, is characterized in that the drying described in step (2) adopts spray-dired mode.
7. preparation method according to claim 5, it is characterized in that the temperature of step (2) described roasting is 700 ~ 900 DEG C, roasting time is 0.2 ~ 4 hour.
8. preparation method according to claim 5, it is characterized in that the temperature of step (6) described roasting is 520 ~ 660 DEG C, roasting time is 0.2 ~ 4 hour.
9. preparation method according to claim 5, is characterized in that the median size of step (5) described sosoloid is ﹥ 0 and is less than 20 microns.
10. the application of catalyzer according to any one of Claims 1-4 in the synthesis of fluidized bed process unsaturated nitrile.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195165A (en) * | 2015-10-23 | 2015-12-30 | 中国海洋石油总公司 | Ammoxidation of olefin to unsaturated nitrile fluid catalyst and preparation method thereof |
| CN116618060A (en) * | 2023-04-24 | 2023-08-22 | 北京高新利华科技股份有限公司 | Acrylonitrile catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988359A (en) * | 1974-02-09 | 1976-10-26 | Nitto Chemical Industry Co., Ltd. | Catalyst for use in and process for preparing acrylonitrile |
| JP3117265B2 (en) * | 1992-02-07 | 2000-12-11 | 三井化学株式会社 | Method for producing α, β-unsaturated nitrile |
| CN1736592A (en) * | 2005-06-03 | 2006-02-22 | 营口市向阳催化剂有限责任公司 | Fluidized-bed catalyst for ammoxidation of propylene or isobutylene |
| CN101121129A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing unsaturated nitrile catalyst using with ammoxidation method |
| CN101284237A (en) * | 2008-05-31 | 2008-10-15 | 吉化集团吉林市星云工贸有限公司 | Preparation method of catalyst for acrylonitrile fluid bed |
-
2013
- 2013-10-28 CN CN201310512659.0A patent/CN104549344B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988359A (en) * | 1974-02-09 | 1976-10-26 | Nitto Chemical Industry Co., Ltd. | Catalyst for use in and process for preparing acrylonitrile |
| JP3117265B2 (en) * | 1992-02-07 | 2000-12-11 | 三井化学株式会社 | Method for producing α, β-unsaturated nitrile |
| CN1736592A (en) * | 2005-06-03 | 2006-02-22 | 营口市向阳催化剂有限责任公司 | Fluidized-bed catalyst for ammoxidation of propylene or isobutylene |
| CN101121129A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing unsaturated nitrile catalyst using with ammoxidation method |
| CN101284237A (en) * | 2008-05-31 | 2008-10-15 | 吉化集团吉林市星云工贸有限公司 | Preparation method of catalyst for acrylonitrile fluid bed |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195165A (en) * | 2015-10-23 | 2015-12-30 | 中国海洋石油总公司 | Ammoxidation of olefin to unsaturated nitrile fluid catalyst and preparation method thereof |
| CN116618060A (en) * | 2023-04-24 | 2023-08-22 | 北京高新利华科技股份有限公司 | Acrylonitrile catalyst and preparation method and application thereof |
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