CN1751790A - Fluidized bed catalyst for prodn. of acrylonitrile - Google Patents
Fluidized bed catalyst for prodn. of acrylonitrile Download PDFInfo
- Publication number
- CN1751790A CN1751790A CNA2004100666220A CN200410066622A CN1751790A CN 1751790 A CN1751790 A CN 1751790A CN A2004100666220 A CNA2004100666220 A CN A2004100666220A CN 200410066622 A CN200410066622 A CN 200410066622A CN 1751790 A CN1751790 A CN 1751790A
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- CN
- China
- Prior art keywords
- catalyst
- acrylonitrile
- span
- propylene
- described production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 29
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052792 caesium Inorganic materials 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000011734 sodium Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000011651 chromium Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- -1 propylene nitrile Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
A fluidized-bed catalyst for preparing acrylonitrile by ammoxidizing propene is composed of SiO2 as carrier and the composition AaBbCcNidFeeBifM012Ox, where A is chosen from Li, Na, K, Rb and Cs, B is chosen from W, P, B, Ga, Cr, Sb, Al, Ge, Nb and V, and C is chosen from Ag, Cu and their mixture. Its advantages are high power to bear high reaction pressure and propene load, and high conversion rate and output rate.
Description
Technical field
The present invention relates to a kind of fluid catalyst of producing acrylonitrile, particularly about a kind of fluid catalyst of ammoxidating propylene to produce acrylonitrile.
Background technology
Acrylonitrile is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to the catalyst activity composition, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of acrylonitrile once through yield, and the raising of producing load.
Ammonia oxidation is produced acrylonitrile through 40 years of development, and the production capacity of factory and the market demand are near balance.The main development trend of acrylonitrile process is built the technological transformation that new equipment turns to original factory by emphasis, further to cut down the consumption of raw materials and to increase production capacity at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technology, the production capacity of acrylonitrile might improve 50～80%, and required investment only is 20～30% of a new device, economic benefit is very huge.
Can produce two problems during factory transforms: 1. the reaction pressure of fluidized-bed reactor will rise; 2. the useful load of catalyst can not be too many.Require the catalyst use instead should be able to long-time running under higher propylene load and higher reaction pressure for this reason, and keep higher acrylonitrile yield.
The WWH that improves catalyst in theory should increase the adsorption activation ability of catalyst to propylene, but at present still in the catalyst-free certain element can improve report to propylene adsorption activation ability.The catalyst of following composition has been proposed in document CN1021638C:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hM
iMo
jO
x
Wherein A is potassium, rubidium, caesium, samarium, thallium; B is manganese, magnesium, strontium, calcium, barium, lanthanum, rare earth element; C is phosphorus, arsenic, boron, antimony, chromium; M is tungsten, vanadium.
Above-mentioned catalyst can obtain higher single-pass yield of acrylonitrile, but the propylene of catalyst load is lower, and single-pass yield of acrylonitrile descends bigger under higher reaction pressure.
Introduced the catalyst that a kind of catalyst that uses molybdenum, bismuth, iron, nickel, magnesium, potassium and caesium system carries out preparing acrylonitrile by allylamine oxidation among document US 5093299 and the US5212137.Introduce in this patent, its catalyst can be operated under lower slightly usually reaction temperature, and it has advantages of high catalytic activity and advantages of excellent oxidation-reduction stability, thereby compares conditional operation applicable to lower air/propylene.But it should be noted that magnesium is the basic element during catalyst is formed in the above-mentioned patent.The investigation condition of embodiment is a fixed bed simultaneously, and 430 ℃ of reaction temperatures are not mentioned reaction pressure concrete in the experimental implementation and operational load situation data.This fixed bed investigation condition is difficult to reflect the truth of fluidized bed process.
Introduced a kind of manufacture method of acrylonitrile among the flat 8-27089 of document.It adopts the catalyst of molybdenum, bismuth, iron, magnesium and tungsten system to carry out the ammoxidation of propylene reaction, and the investigation condition among the document embodiment is a normal pressure, does not mention the situation data under high pressure, high-load condition.
Summary of the invention
Technical problem to be solved by this invention is to overcome the catalyst that exists in the above-mentioned document not relate to problem than high-response pressure and operational load, and a kind of fluid catalyst of new production acrylonitrile is provided.This catalyst has can adapt under usually lower slightly reaction temperature, lower air/propylene mol ratio, higher reaction pressure and higher loading condiction to be operated, and can keep the characteristics of higher single-pass yield of acrylonitrile and higher propylene conversion.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of fluid catalyst of producing acrylonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cNi
dFe
eBi
fMo
12O
x
A is selected from least a among Li, Na, K, Rb or the Cs in the formula;
B is selected from least a among W, P, B, Ga, Cr, Sb, Al, Ge, Nb or the V;
C is selected from least a among Ag or the Cu;
The span of a is 0.01～2.0;
The span of b is 0.01～5.0;
The span of c is 0.01～2.0;
The span of d is 0.1～12.0;
The span of e is 0.1～7.0;
The span of f is 0.05～5.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst.
The value preferable range of a is 0.01～1.0 in the technique scheme, the value preferable range of b is 0.01～3.5, the value preferable range of c is 0.01～1.0, the value preferable range of d is 0.1～10.0, the value preferable range of e is 0.1～5.0, the value preferable range of f is 0.05～3.0, and the consumption preferable range of carrier silica is 40～60% by weight percentage in the catalyst.
The manufacture method of catalyst of the present invention there is no specific (special) requirements, can be undertaken by well-established law.At first the catalyst each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyst is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyst of the present invention is:
Molybdenum component in the catalyst is with molybdenum oxide or ammonium molybdate.
The most handy corresponding acids of phosphorus in the catalyst and boron or its ammonium salt; Germanium can be used germanium oxide; The most handy corresponding oxide of tungsten and antimony or its ammonium salt; The most handy nitrate of niobium, hydroxide and oxide; The most handy chromium trioxide of chromium, chromic nitrate or the mixture of the two; The most handy its nitrate of all the other components, hydroxide maybe can be decomposed into the salt of oxide.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silica.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 47～55% back spray-dryings that the prepared slurry heating is concentrated to solid content.Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyst of making has good size distribution with centrifugal better.
The roasting of catalyst can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air,, and prevent that catalyst is by over reduction with generation catalytic activity phase.
Adopt the specification of catalyst manufacturing acrylonitrile of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propylene is 8～10.5, is preferably 9.0～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had significant impact.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fluidized-bed reactor, reaction temperature was 410～470 ℃, was preferably 420～440 ℃.Catalyst of the present invention is a kind of usually lower slightly reaction temperature that is applicable to, high pressure, high load capacity catalyst, and therefore reaction pressure can be more than 0.08MPa in process units, for example, 0.08～0.18MPa.Also do not have any adverse effect if reaction pressure is lower than 0.08MPa, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.06～0.15 hour
-1, be preferably 0.08～0.12 hour
-1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.
The product of making acrylonitrile with catalyst of the present invention reclaims process for refining, and available existing production technology need not done any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid gets high-purity propylene nitrile product through extractive distillation after dehydrogenation cyanic acid and the processed.
The surface of catalyst has been modified in the existence of catalyst C dvielement of the present invention; Improved propylene conversion; Category-B element and iron synergy in the component, quicken gas phase oxygen and entered caltalyst phase and the body diffusion of oxygen mutually, make the oxidation rapidly of reacted catalyst, again recover active, thereby helping keeping reacting is in good redox cycle, makes that catalyst has at usually lower slightly reaction temperature (430 ℃), low air/propylene mol ratio (9.5: 1), (WWH is 0.11 hour than high-response pressure (0.14MPa), higher load
-1) operational capacity under the condition, and the acrylonitrile once through yield reached about 81%, obtained effect preferably.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 400 grams, 430 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.5, the propylene load (WWH) of catalyst is 0.11 hour
-1
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
1.80 gram cesium nitrates, 3.19 gram sodium nitrate are mixed with 2.25 gram potassium nitrate, add water 30 grams and the dissolving of heating back, obtain material (A); 9.36 gram chromium trioxides are dissolved in the 15 gram water, get material (B); 392.4 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (C); 67.4 gram bismuth nitrates, 9.39 gram silver nitrates, 0.96 gram germanium oxide, 408.1 gram nickel nitrates and 302.4 gram ferric nitrates are mixed, add water 250 grams, after the heating for dissolving as material (D); Take by weighing phosphoric acid solution 4.35 grams as material (E).
With material (A) and 1280 gram weight concentration is that 40% Ludox mixes, under agitation add material (C), (B), (D) and (E) successively, after fully stirring, get slurry, according to well-established law the slurry of making is carried out the framboid moulding in spray dryer, it is 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 600 ℃ of roastings 2.0 hours, make and consist of:
50％Mo
12Bi
0.75Fe
4.0Ni
7.5Ag
0.3Na
0.29K
0.1Cs
0.05Cr
0.5P
0.1Ge
0.05O
x+50％SiO
2。
[embodiment 2～6 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and under following reaction condition, carry out the reaction that ammoxidation of propylene generates acrylonitrile, the results are shown in Table 1 with prepared catalyst.
The reaction condition of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
430 ℃ of reaction temperatures
Reaction pressure 0.14MPa
Loaded catalyst 400 grams
Catalyst propylene load (WWH) 0.11 hour
-1
Raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.5
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % | Acrylonitrile selectivity % | Propylene conversion % |
| Embodiment 1 | Mo 12Bi 0.75Fe 4.0Ni 7.5Ag 0.3Na 0.29K 0.1Cs 0.05Cr 0.5Ge 0.05O x | 80.8 | 81.2 | 99.5 |
| Embodiment 2 | Mo 12Bi 0.75Fe 4.0Ni 7.5Cu 0.3Na 0.29K 0.1Cs 0.05Cr 0.5Ge 0.05O x | 82.1 | 82.1 | 100 |
| Embodiment 3 | Mo 12Bi 0.75Fe 4.0Ni 7.5Ag 0.8Na 0.29K 0.1Cs 0.05W 1.0P 0.25O x | 81.2 | 81.5 | 99.6 |
| Embodiment 4 | Mo 12Bi 1.25Fe 4.0Ni 7.5Na 0.29K 0.1Cs 0.05Cr 0.5Cu 0.3Ag 0.3Ge 0.05O x | 81.4 | 82.0 | 99.3 |
| Embodiment 5 | Mo 12Bi 1.25Fe 4.0Ni 7.5Na 0.29K 0.1Cs 0.05Cr 0.5Cu 0.3V 0.5P 0.5O x | 81.3 | 81.5 | 99.7 |
| Embodiment 6 | Mo 12Bi 1.0Fe 4.0Ni 7.5K 0.05Cs 0.2Ge 0.3Na 0.29Ag 0.3Sb 0.5O x | 81.1 | 81.4 | 99.7 |
| Embodiment 7 | Mo 12Bi 0.75Fe 4.0Ni 7.5Na 0.29K 0.1Cs 0.05Ag 0.3W 1.0P 0.25O x | 81.5 | 81.7 | 99.8 |
| Embodiment 8 | Mo 12Bi 0.75Fe 4.0Ni 7.5Na 0.29K 0.1Cs 0.05W 0.1V 0.3Cu 0.1Sb 0.5O x | 79.8 | 80.5 | 99.1 |
| Comparative example 1 | Mo 12Bi 0.9Fe 4.0Ni 7.5Na 0.15Cr 0.45K 0.17Cs 0.05O x | 78.6 | ||
| Comparative example 2 | Mo 12Bi 0.9Fe 4.0Ni 7.5Na 0.15Cr 0.45K 0.21O x | 78.9 | ||
| Comparative example 3 | Mo 12Bi 0.9Fe 4.0Ni 7.5Na 0.15W 0.45K 0.15Cs 0.07O x | 79.4 | ||
| Comparative example 4 | Mo 12Bi 0.9Fe 4.0Ni 7.5Na 0.15W 0.45Cs 0.09O x | 77.9 |
Claims (8)
1, a kind of fluid catalyst of producing acrylonitrile, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cNi
dFe
eBi
fMo
12O
x
A is selected from least a among Li, Na, K, Rb or the Cs in the formula;
B is selected from least a among W, P, B, Ga, Cr, Sb, Al, Ge, Nb or the V;
C is selected from least a among Ag or the Cu;
The span of a is 0.01～2.0;
The span of b is 0.01～5.0;
The span of c is 0.01～2.0;
The span of d is 0.1～12.0;
The span of e is 0.1～7.0;
The span of f is 0.05～5.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst.
2, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that a is 0.01～1.0.
3, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that b is 0.01～3.5.
4, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that c is 0.01～1.0.
5, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that d is 0.1～10.0.
6, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that e is 0.1～5.0.
7, according to the fluid catalyst of the described production acrylonitrile of claim 1, the span that it is characterized in that f is 0.05～3.0.
8, according to the fluid catalyst of the described production acrylonitrile of claim 1, the consumption that it is characterized in that carrier silica in the catalyst is 40～60% by weight percentage.
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| CN102658167A (en) * | 2012-05-08 | 2012-09-12 | 营口市向阳催化剂有限责任公司 | Catalyst for use in preparation of acrylonitrile by performing ammonia oxidation on propylene |
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| CN1130261C (en) * | 1999-11-03 | 2003-12-10 | 中国石油化工集团公司 | Propylene ammonoxidizing fluid bed catalyst |
| CN1102576C (en) * | 2000-02-24 | 2003-03-05 | 中国石油化工集团公司 | Fluidized bed catalyst for ammoxidating propylene to prepare acrylonitrile |
| CN1160316C (en) * | 2001-10-22 | 2004-08-04 | 中国石油化工股份有限公司 | Fluidized-bed catalyst for preparing acrylonitrile by allylamine oxidation |
| CN1160315C (en) * | 2001-10-22 | 2004-08-04 | 中国石油化工股份有限公司 | Fluidized-bed catalyst for preparing acrylonitrile |
| CN1157370C (en) * | 2001-11-14 | 2004-07-14 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile by propene ammoxidation |
| CN1152009C (en) * | 2001-11-14 | 2004-06-02 | 中国石油化工股份有限公司 | Method for prepn. of fluidized catalyst for prodn. of acrylonitrile |
| CN1212188C (en) * | 2002-12-17 | 2005-07-27 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing acrylonitrile |
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