CN1005248B - Acrylonitrile fluidized bed sodium-containing catalyst - Google Patents
Acrylonitrile fluidized bed sodium-containing catalyst Download PDFInfo
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- CN1005248B CN1005248B CN87103455.7A CN87103455A CN1005248B CN 1005248 B CN1005248 B CN 1005248B CN 87103455 A CN87103455 A CN 87103455A CN 1005248 B CN1005248 B CN 1005248B
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- Prior art keywords
- catalyst
- sodium
- gram
- acrylonitrile
- ammonia
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011734 sodium Substances 0.000 title claims description 50
- 229910052708 sodium Inorganic materials 0.000 title claims description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052792 caesium 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
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000008119 colloidal silica Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 20
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 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 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000035987 intoxication Effects 0.000 description 2
- 231100000566 intoxication Toxicity 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910000632 Alusil Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- -1 propylene nitrile Chemical class 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention is one kind of fluidized bed catalyst for preparing acrylonitrile by means of propylene ammoxidation process. It is composed of a silicon dioxide carrier and a composition with the following chemical formula: a. theaＢbＣ↓［ｃ］ＮｉdＣｏeＮａfＦｅgＢｉhＭｏ12Ｏx(A is K, Pb, Cs or a mixture thereof; B is Mn, Mg, Ca, Sr, Ba or a mixture thereof; and C is P, As, B, Sb, Cr or a mixture thereof.) by using the composite catalyst, the activity, the selectivity and the abrasion resistance of the catalyst can be improved, and the loss of the catalyst can be reduced. But also has the advantages of low reaction temperature, large catalyst load and the like, and can completely meet the requirement of the fluidized bed for producing acrylonitrile.
Description
The present invention is a kind of fluid catalyst that propylene, ammonia and molecular oxygen reaction generate acrylonitrile that is used for, and is made up of silica supports and the following composition of chemical formula:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hMo
12O
x
In the formula: A is alkali metal (K, Rb, Cs) or their mixture; B is diad (Mn, Mg, Ca, Sr, Ba) or their mixture; C is acid element (P, As, B, Sb, Cr) or their mixture.
A is 0.01-1, and the best is 0.03-0.3; B is 0.1-3, and the best is 0.5-2; C is 0.01-2, and the best is 0.1-1.5; D is 0.01-8, and the best is 0.5-5; E is 0.01-12, and the best is 0.5-8; F is 0.2-0.7, and the best is 0.3-0.5; G is 0.01-8, and the best is 0.1-4; H is 0.01-6, and the best is 0.1-4.
X is the summation that satisfies other element valence requisite oxygen atomicities in the catalyst.
Fluid catalyst feature of the present invention is that the carrier combinations of having introduced an amount of component sodium and other each component and silica forms.When the preparation catalyst, component sodium can be added in the carrier in advance, reach and improve activity of such catalysts and selectivity, also increased the wearability of catalyst, can make reaction temperature reduce to 380-480 ℃ from 400-500 ℃.
Confirm in molybdenum bismuth system catalyst, to add alkali metal already and can improve activity of such catalysts and selectivity, but in the catalyst example that foreign patent provided, the alkali metal that the overwhelming majority selects for use is potassium, rubidium and caesium, without sodium.The United States Patent (USP) 3907713(1975 that is delivering for example), 3956181(1976), 3993680(1976), 4123453(1978), 4139552(1979), 4156660(1979), 4162234(1979), 4167494(1979), 4190556(1980), 4192776(1980), 4323703(1982), 4327037(1982), 4377534(1982) and 4397771(1983) in, though mentioning alkali metal is a component in the catalyst, does not all add sodium in its all examples, also not proposing sodium element is the essential component of catalyst.
It is generally acknowledged that sodium has intoxication to molybdenum bismuth system catalyst, so the alkali metal in most catalyst is all without sodium.But study discovery in great detail through us, catalyst of the present invention contains suitable sodium element, not only can not produce intoxication to catalyst, can improve selection of catalysts on the contrary.Supposition is to lose the over oxidation ability owing to sodium ion makes on the catalyst surface some over oxidation activated centre be poisoned, and carbon dioxide production is descended, thereby improved selection of catalysts.Result of study shows, this sodium combination catalyst that contains, and its wearability is better than catalyst in the past.
For example also propose to add the sodium component among Japan Patent 54-12913 and the 58-2232 in indivedual patents.It is said that the adding of sodium component mainly is to prevent molybdenum component distillation causing loss in the catalyst.This is that activity is lower, must react under higher reaction temperature, so the distillation of molybdenum is serious because its catalyst is formed has obviously differently with the present invention, influences catalyst service life.Its sodium is with compd B i simultaneously
0.5Na
0.5MoO
4Form is present in the catalyst, so the content of sodium is higher.
By the data that Japan Patent 58-2232 example 5 provides, in the small-sized fluidized bed reactor, reaction temperature is 460 ℃, and the acrylonitrile once through yield is 80.5%.If the atomic ratio with molybdenum is 12 calculating, then the atomic ratio of sodium is 1.2 in the catalyst.And catalyst of the present invention, in diameter is 2 meters large-scale fluidized bed reactor, only 430 ℃ of reaction temperatures, the once through yield of acrylonitrile can reach more than 81%, and the sodium atom in its catalyst is 0.4 than only.Because the reaction temperature of catalyst of the present invention is very low, need not worry the volatilization of molybdenum.Therefore, the present invention contains the sodium combination catalyst, mainly is to improve activity of such catalysts and selectivity, rather than solves the volatilization problem of molybdenum.
Catalyst manufacture method of the present invention can be undertaken by well-established law.At first with each component of catalyst, carrier and water are mixed into slurry, and the spray-dried microspheroidal that is shaped to adds thermal bake-out at last and makes catalyst.
The compound method of its slurry can be carried out the aqueous solution and the carrier of each component of catalyst by the illustrated order of example of the present invention.Also some metallic element and molybdenum compound can be given and be mixed and made into molybdate earlier, mix with other components again.Because catalyst of the present invention has good wearability, it is mentioned need not resemble some patent, carrier is divided add in the catalyst for several times, has so just simplified manufacturing process.
The used component sodium of catalyst of the present invention can sodium nitrate, NaOH, and sodium metasilicate or any sodium compound that can decompose are raw material.Be added to order no standard in the slurry as for the sodium component, can be added to ammonium molybdate solution, in nitrate solution or the ammonia stabilized colloidal silica as carrier.Also can require Ludox factory to give and earlier component sodium is added in the ammonia stabilized colloidal silica, but require SiO
2/ Na
2The O weight ratio should be 150-550, and the best is 200-400.
The compound that the available oxide of alkali metal (potassium, rubidium, caesium) maybe can be decomposed into oxide is a raw material, the most handy nitrate or hydroxide.
The salt that category-B element in bismuth, iron, cobalt, nickel and the chemical formula, available oxide maybe can be decomposed into oxide is a raw material.Used salt is preferably water miscible, as nitrate.
C element phosphor in the chemical formula, boron, the most handy corresponding acids of arsenic, also available its ammonium salt.The most handy chromium trioxide of chromium component (Cr VI) or chromic nitrate (trivalent chromium) or its mixture are raw material.Halide and antimony colloidal sol that the antimony component can hydrolysis generate antimony oxide with antimony oxide, antimony pentoxide are raw material.
Report was once arranged, and the catalyst of no carrier added has very high activity.And the present invention is a kind of catalyst that is used for fluid bed, needs to add a certain proportion of carrier, makes the catalyst of making have good flowability and suitable physical property.The present invention simultaneously contains the sodium combination catalyst and is made up of some special elements, therefore still can keep the high activity of its catalyst.
Carrier for catalyst of the present invention can be used silica, aluminium oxide or Alusil etc., the most handy silica, and adopt Ludox more convenient as the raw material of silica.Its Ludox can be used no sodium, the stable Ludox of ammonia, and dioxide-containing silica is in 40%(weight) about.If, for ease of Preparation of catalysts, wish the sodium component is added in the ammonia stabilized colloidal silica in advance, also can require Ludox manufactory the requirement of carrier to be produced the Ludox product of specific standard by the present invention, general dioxide-containing silica is 40% o'clock, and sodium content should be less than 1000PPm.
Prepared slurry need be carried out heat treated.In heat treatment process, the viscosity of slurry, PH, uniformity, solids content all will change, and help improving spray-dired production capacity, can strengthen the uniformity of catalytic component, improve the scuff resistance of catalyst.
Slurry after heat treatment promptly carries out spray drying forming.Spray dryer available pressure formula, two streamings and centrifugal turntable formula etc., but better with the centrifugal turntable formula, can guarantee that the catalyst of making has good particle size distribution.
The roasting of catalyst is divided into two stages: each element decomposition of salts and high-temperature roasting in the catalyst.Its catabolic phase temperature is 200-400 ℃, and the time is 0.5-2 hour, and sintering temperature is 500-800 ℃, preferably 600-700 ℃.Decomposition and roasting are carried out respectively in two roasters, also can divide two stages to carry out in a roaster, perhaps will decompose in the continous way rotary roasting furnace with roasting and carry out simultaneously.But in catalyst decomposes and roasting process, noting in the roaster to have an amount of circulation of air.
Adopt catalyst of the present invention to make the required propylene of acrylonitrile, the specification of ammonia and molecular oxygen is identical with other catalyst of use, for example the low-molecular-weight saturated hydrocarbon content in the raw material propylene is to the reaction did not influence, but considers from economic point of view, and density of propylene should be greater than the 85%(mole).Ammonia can be used fertilizer grade liquefied ammonia.React required molecular oxygen from the available pure oxygen of technological standpoint, oxygen-enriched air, but from economy, resource is convenient considers, and is still more reasonable as source of molecular oxygen with air.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is stoichiometric proportion 1: 1, and reality can change between 0.8: 1 to 2: 1, but the molal quantity of ammonia is preferably in 0.9 to 1.3 scope.If the ammonia mol ratio is lower than at 0.9 o'clock, the growing amount of accessory substance methacrylaldehyde can obviously rise, and unfavorable acrylonitrile reclaims refining.Otherwise, though excess ammonia have no adverse effect for the generation of acrylonitrile, the oxygen in can consumed cabin air, and make acrylonitrile reclaim in sulfuric acid consumption rise.
Entering the oxygen of fluidized-bed reactor and the mol ratio of propylene is stoichiometric proportion 1.5: 1, and reality can change between 1: 1 to 4: 1, was preferably between 1.5: 1 to 3: 1.The source of molecular oxygen available air needn't can directly be used " humid air " that contain saturated vapor under atmospheric pressure through dehydrating as previously mentioned.
Add water vapour in the unstripped gas and help improving the selectivity of reaction and improving the acrylonitrile once through yield, but reduced the production capacity of reactor, and also influential slightly to the intensity of catalyst, for this reason, need not add water vapour during catalyst of the present invention is raw materials used.As adding water vapour, the mol ratio of its water and propylene is preferably between 0.1: 1 to 3: 1.
Because the catalyst activity of the present invention's combination is very high, therefore can react under lower temperature.General reaction temperature is 400-500 ℃, adopts the catalyst reaction temperatures of the present invention's combination can reduce to 380-480 ℃, is preferably 400-450 ℃.
Reaction pressure is relevant with the acrylonitrile once through yield, the pressure height, and yield descends, and is generally the 1-5 atmospheric pressure, is preferably the 1-2 atmospheric pressure.
Catalyst loading (WWH) is an important parameter that characterizes catalyst activity.It is defined as:
WWH=propylene feed weight/catalyst weight hourage
Because catalyst of the present invention has very high activity, so the WWH value is bigger, can change in the 0.05-0.25 scope, is preferably 0.06-0.15.
The product recovery process for refining of making acrylonitrile with catalyst of the present invention is identical with conventional method, and promptly the fluidized-bed reactor eluting gas is removed unreacted ammonia through neutralizing tower, and water absorbs whole organic matters in the absorption tower again.Absorption liquid obtains crude acetonitrile through the desorber distillation, obtains the high-purity propylene nitrile through a series of purification operations again.In addition, the desorber still water of discharging returns the absorption tower and recycles.
Because catalyst of the present invention has good selectivity, the growing amount of accessory substance methacrylaldehyde seldom, so polymer concentration is very low in the recirculated water.In the past, polymer concentration can reach 1% in the general recirculated water, polluted very serious to heat exchanger.But polymer concentration only is 0.2-0.3% in the recirculated water of the present invention.Therefore, unnecessary employing such as United States Patent (USP) 4,166,008(1979); 4,334,965(1982) wait the method for polymer in the reduction recirculated water recommended.
Below be the embodiment of catalyst of the present invention, wherein conversion ratio, once through yield and optionally be defined as follows:
Propylene molal quantity/propylene feed molal quantity * 100 of conversion ratio (%)=reaction
Once through yield (%)=generation acrylonitrile molal quantity/propylene feed molal quantity * 100
Propylene molal quantity * 100 of selectivity (%)=generation acrylonitrile molal quantity/reaction
(example 1) adds the catalyst containing sodium that sodium is made again by the composition of example 3 in the United States Patent (USP) 3746657.
Produce the stable sodium Ludox with Shanghai reagent two factories, contain silica 25-27%(weight), contain sodium and be about 5000PPm, remove whole sodium through strong-acid ion exchange resin and obtain sodium-free silica sol, being concentrated to dioxide-containing silica again is 40%(weight) as support material.
With 2.25 gram concentration is that 45% the KOH aqueous solution mixes with 307 gram water, and adding 386 restrains (NH
4)
6Mo
7O
244H
2O stirs and makes its whole dissolvings, gets material (I).
With the silica that 1250 grams are made as stated above, adding 5.52 gram concentration is 40%(weight) the NaOH aqueous solution, stir evenly material (II).
Again with 223 gram Fe(NO
3)
39H
2O, 88.6 gram Bi(NO
3)
35H
2O, 244 gram Co(NO
3)
26H
2O and 134 gram Ni(NO
3)
26H
2O and 66.8 the gram water mixes, add thermal agitation make whole dissolve material (III).
At last, material (I), (II), (III) and 10.4 grams, 85% phosphoric acid fully mixed makes slurry, and heating concentrate make that solids content reaches 48%(weight in the slurry), in spray dryer, carry out drying and moulding by usual method then.Place φ 89 * 1700mm rotary roasting furnace in 670 ℃ of roastings 1 hour at last, the catalyst of making consists of Na
0.3K
0.1Ni
2.5Co
4.5Fe
3Bi
1P
0.5Mo
12O
X+ 50%SiO
2
It is 38 millimeters fluidized-bed reactor that the catalyst of making is put into internal diameter, 435 ℃ of reaction temperatures, reaction pressure is a normal pressure, propylene: ammonia: air=1: 1.2: the 10(mole), WWH carries out activity rating 0.045 time, the result is as follows: acrylonitrile once through yield 79.8%, propylene conversion 96.4%, acrylonitrile selectivity 82.8%.Catalyst abrasion rate 2.00%.
(comparative example 1) presses the catalyst of the composition manufacturing of example 3 in the United States Patent (USP) 3746657.
Manufacture method is except not adding the NaOH, and is identical with example 1.The catalyst of making consists of K
0.1Ni
2.5CO
4.5Fe
3Bi
1P
0.5Mo
12Ox+50%SiO
2
Press example 1 similarity condition and investigate activity, the acrylonitrile once through yield is 77.4%, catalyst abrasion rate 7.92%.
(comparative example 2) presses example 1 composition, and the 40%NaOH5.52 gram is used 14.72 grams instead, uses with quadrat method and makes catalyst, consists of Na
0.8K
0.1Ni
2.5Co
4.5Fe
3Bi
1P
0.5Ox+50%SiO
2Press the condition of example 1 and investigate activity, the acrylonitrile once through yield 73.9% as a result.
(example 2) prepares catalyst by the following method.With the 0.94 gram 45%KOH aqueous solution and 2.17 gram 40%NaOH aqueous solution, add 1.75 gram cesium nitrates and 500 grams, 40% ammonia stabilized colloidal silica, as (I).
33.3 the gram bismuth nitrate, 28 gram ferric nitrates, 91.7 gram cobalt nitrates, 56.4 gram nickel nitrates, 20 milliliters of dissolvings of mixing and water adding add 22 milliliter of 70% manganese nitrate solution again and mix, as (II).
159 gram ammonium molybdates are added in (I), stir and make its dissolving, add (II) then and mix.Add 3.5 gram chromic anhybrides again.Stir, below make catalyst by example 1 method.It consists of Cs
0.1K
0.1Ni
2.3Co
4.1Fe
0.9Mn
0.9Bi
0.9Cr
0.45Na
0.3Mo
12Ox+50%SiO
2By example 1 condition but reactor pressure changes 0.85 kilogram of gauge pressure into, to investigate actively, the acrylonitrile once through yield is 77.0%.
(comparative example 3) presses the composition of example 2, makes catalyst but do not add sodium, presses the condition of example 2 and investigates activity, and the acrylonitrile once through yield is 73.8%, and the wear-resisting intensity of catalyst is 6.8%.
(comparative example 4) presses the composition of example 2, but do not add sodium and caesium is made catalyst.Press the condition of example 2 and investigate activity, the acrylonitrile once through yield is 71%.
(example 3) makes following composition catalyst by example 2 methods:
Cs
0.04K
0.09Ni
2.3Co
4.1Fe
1.8Mn
0.9Bi
0.9Cr
0.45Na
0.3P
0.2Mo
12Ox+50%SiO
2
With 2.1 gram 45%KOH and 5.36 gram 40%NaOH aqueous solution, be added in 1250 grams, the 40% ammonia stabilized colloidal silica, as (I).
33.8 the gram chromic nitrate, 139.3 gram ferric nitrates, 82.9 bismuth nitrates, 223.8 gram cobalt nitrates, 125.5 gram nickel nitrates, 45.58 milliliter of 50% manganese nitrate and 15.5 milliliter of 10% cesium nitrate mix, and are (II).
396.9 gram ammonium molybdates are added in (I) stirring and dissolving.Add (II) and 4.9 grams, 85% phosphoric acid again.Below make catalyst by example 1 method, press example 2 conditions and investigate actively, the acrylonitrile once through yield is 77.2%.
(example 4) made following catalyst by example 3 methods and consisted of:
Cs
0.04K
0.09Ni
2.3Co
4.1Fe
1.8Mn
0.7Bi
0.9Cr
0.45Na
0.3P
0.2Mo
12Ox+50%SiO
2。But the addition of manganese nitrate changes 42.57 milliliters into, and replaces chromic nitrate with 8.63 gram chromic anhybrides.Press example 2 conditions and investigate activity, the acrylonitrile once through yield is 77.7%.
(example 5) makes the catalyst of following composition:
Cs
0.05K
0.1Ni
2.5Co
4.5Fe
2Mn
1Bi
1Cr
0.5Na
0.4Mo
12Ox+50%SiO
2Catalyst.
Carrier is with 40% ammonia stabilized colloidal silica, and requires manufactory to regulate wherein sodium content to 1100PPm, as the raw material of making catalyst.
15.3 gram ammonium molybdates are dissolved in 50 ml waters, and 83.2 gram bismuth nitrates are dissolved in 100 milliliters of 1: 1 nitric acid.Both mix a kind of solution, be (I).
139.8 the gram ferric nitrate, 224.6 cobalt nitrates, 125.9 gram nickel nitrates, 46.7 milliliter of 50% manganese nitrate, 16.9 milliliter of 10% cesium nitrate and 8.7 gram chromic anhybrides mix, and add 60 ml waters and make it dissolving, are (II).
351.3 the gram ammonium molybdate is dissolved in 300 ml waters, adds 1250 gram above-mentioned raw materials Ludox.Add 2.1 gram 45%KOH, (I) liquid and (II) liquid again.Below make catalyst by the method for example 1.
Press the condition of example 2 and investigate activity, the acrylonitrile once through yield is 75.4%.
(example 6) makes the catalyst of following composition
Cs
0.1K
0.2Ni
2.5Co
4.5Fe
2Mn
1Bi
1Cr
0.5Na
0.4Mo
12Ox+50%SiO
2。
45.3 gram ammonium molybdates are dissolved in 530 milliliters of hot water, and 83.2 gram bismuth nitrates are dissolved in the solution of 29 milliliters of red fuming nitric acid (RFNA)s and 230 ml waters.Both mix, and regulating PH with ammoniacal liquor is 2.8, get a kind of white precipitate, are (I).
139.8 the gram ferric nitrate, 224.6 gram cobalt nitrates, 125.9 gram nickel nitrates, 46.7 milliliter of 50% manganese nitrate, 33.8 milliliter of 10% cesium nitrate and 33.8 gram chromic nitrates mix, and add 50 ml waters and make it dissolving, are (II).
321.3 the gram ammonium molybdate is dissolved in 300 ml waters, adds the raw silicon colloidal sol of 1250 gram examples 5, adds 4.2 gram 45%KOH solution again and mixes.Add (I) suspension and (II) later on respectively and make slurry.Below make catalyst by the method for example 1.Press the condition of example 2 and investigate activity, the acrylonitrile once through yield is 76.9%.
(example 7) pressed the method for example 6 and made catalyst, but with 44.4 gram magnesium nitrates replacements manganese nitrate wherein, catalyst consists of: Cs
0.1K
0.2Ni
2.5Co
4.5Fe
2Mg
1Bi
1Cr
0.5Na
0.4Mo
12Ox+50%SiO
2Press the condition of example 2 and investigate activity, the acrylonitrile once through yield is 75.1%.
(example 8) pressed the method for example 6 and made catalyst, but with 40.9 calcium nitrate replacement manganese nitrate wherein, catalyst consists of:
Cs
0.1K
0.2Ni
2.5Co
4.5Fe
2Ca
1Bi
1Cr
0.5Na
0.4Mo
12Ox+50%SiO
2。Press the condition of example 2 and investigate activity, acrylonitrile once through yield 74.7%.
(example 9) makes catalyst with the method for example 6, investigates its activity in 2 meters of diameters large-scale fluidized bed.Reaction temperature 425-430 ℃, reaction pressure 0.5kg/cm
2(table), linear speed 0.58 meter per second, WWH0.085, propylene: ammonia: air=1: 1.15: the 10.6(mol ratio).
Mean value as a result in 30 days is as follows:
Acrylonitrile once through yield 82.1%, propylene conversion 99.8%, acrylonitrile selectivity 82.3%.
The accessory substance once through yield: acetonitrile is 3.6%, HCN5.1%, CO
27.5%, CO1.2%, methacrylaldehyde 0.3%.
Above result shows that catalyst containing sodium of the present invention has high activity and selectivity.
Claims (7)
1, a kind of fluid catalyst that is used for propylene, ammonia and molecular oxygen reaction production acrylonitrile, form by silica supports and the following composition of chemical formula:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hMo
12O
x
In the formula: A is alkali metal (K, Rb, Cs) or their mixture; B is divalent metal element (Mn, Mg, Ca, Sr, Ba) or their mixture; C is acid element (P, As, B, Sb, Cr) or their mixture.
A is 0.01-1, and b is 0.1-3, and c is 0.01-2, and d is 0.01-8, and e is 0.01-12, and f is 0.2-0.7, and g is 0.01-8, and h is 0.01-6, and x is the summation that satisfies other element valence requisite oxygen atomicity in the catalyst.
When wherein preparing catalyst, component sodium can be added in ammonium molybdate solution, the nitrate solution with the form of the compound of sodium nitrate, NaOH, sodium metasilicate or any decomposable sodium, or be added in advance in the support material ammonia stable silicon solution, but the necessary SiO that keeps this ammonia stabilized colloidal silica
2/ Na
2The O weight ratio should be 150-550.
2, catalyst according to claim 1, wherein a is 0.03-0.3, and b is 0.5-2, and c is 0.1-1.5, d is 0.5-5, and e is 0.5-8, and f is 0.3-0.5, g is 0.1-4, and h is 0.1-4, and x is the summation that satisfies other element valence requisite oxygen atomicity in the catalyst.
3, catalyst according to claim 1, the wherein SiO of ammonia stabilized colloidal silica
2/ Na
2The O weight ratio is 200-400.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103455.7A CN1005248B (en) | 1987-05-14 | 1987-05-14 | Acrylonitrile fluidized bed sodium-containing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103455.7A CN1005248B (en) | 1987-05-14 | 1987-05-14 | Acrylonitrile fluidized bed sodium-containing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033014A CN1033014A (en) | 1989-05-24 |
| CN1005248B true CN1005248B (en) | 1989-09-27 |
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ID=4814439
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87103455.7A Expired CN1005248B (en) | 1987-05-14 | 1987-05-14 | Acrylonitrile fluidized bed sodium-containing catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279265B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
| CN1086152C (en) * | 1997-09-03 | 2002-06-12 | 中国石油化工总公司 | Production of propylene by ammoxidation of olefins |
| CN1081488C (en) * | 1998-03-30 | 2002-03-27 | 中国石油化工总公司 | Catalyst for ammonoxidating propylene to produce acrylonitrile |
| JP5011167B2 (en) * | 2008-03-03 | 2012-08-29 | ダイヤニトリックス株式会社 | Catalyst for producing acrylonitrile and method for producing acrylonitrile |
| CN105664962A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile from propylene by ammoxidation |
-
1987
- 1987-05-14 CN CN87103455.7A patent/CN1005248B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279265B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile |
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|---|---|
| CN1033014A (en) | 1989-05-24 |
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