CN1137779C - Method for preparing 3,4-dichlorophenylnitrile by using ammonia oxidation process and its special-purpose catalyst - Google Patents
Method for preparing 3,4-dichlorophenylnitrile by using ammonia oxidation process and its special-purpose catalyst Download PDFInfo
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- CN1137779C CN1137779C CNB001146416A CN00114641A CN1137779C CN 1137779 C CN1137779 C CN 1137779C CN B001146416 A CNB001146416 A CN B001146416A CN 00114641 A CN00114641 A CN 00114641A CN 1137779 C CN1137779 C CN 1137779C
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- Prior art keywords
- catalyst
- dichlorobenzonitrile
- preparation
- ammonia oxidation
- dichlorotoleune
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [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 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- KUWBYWUSERRVQP-UHFFFAOYSA-N 3,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1Cl KUWBYWUSERRVQP-UHFFFAOYSA-N 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 150000002825 nitriles Chemical class 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ROBIUDOANJUDHD-ONNFQVAWSA-N (ne)-n-[(3,4-dichlorophenyl)methylidene]hydroxylamine Chemical compound O\N=C\C1=CC=C(Cl)C(Cl)=C1 ROBIUDOANJUDHD-ONNFQVAWSA-N 0.000 description 1
- FPENCTDAQQQKNY-UHFFFAOYSA-N 3,4-difluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C(F)=C1 FPENCTDAQQQKNY-UHFFFAOYSA-N 0.000 description 1
- PKTSBFXIHLYGEY-UHFFFAOYSA-N 3-chloro-4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C(Cl)=C1 PKTSBFXIHLYGEY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention discloses a method and a special catalyst for preparing 3, 4-dichlorobenzonitrile by ammonia oxidation. The special catalyst is a multicomponent catalyst using vanadium and phosphorus as main catalysts and using titanium, manganese, chromium, molybdenum, boron, ferrum, nickel, cobalt, copper, zinc, potassium, litium, magnesium, tin, etc. as cocatalysts; the chemical structure of the catalyst is Va Pb Cc Dd Ee Ox/SiO2. The catalyst for preparing 3, 4-dichlorobenzonitrile by ammonia oxidation has the advantages of high activity, high selectivity, high product yield, high purity, long service life, simple manufacturing process, etc.
Description
The present invention relates to a kind of ammonia oxidation preparation 3, the method for 4-dichlorobenzonitrile and special-purpose catalyst, it belongs to technical field of organic chemistry, also belongs to organic fine chemicals technical field.
3,4-dichlorobenzonitrile, molecular formula C
7H
3Cl
2N, white needle-like crystals.Because the fluoro virtue nitrile that chloro virtue nitrile makes through the high temperature fluoro by other reaction such as hydrolysis, degraded, reduction, is one of best method of preparation fluoro aromatic intermediate.And fluorine-containing novel pesticide and medical kind constantly occurs at present, to the demand sharp increase of fluoro aromatic.Therefore, 3,4-dichlorobenzonitrile and its fluorinated derivatives, as 3,4-difluorobenzonilyile, 4-fluoro-3-6-chlorophenyl nitrile, 3,4-difluoro-benzoic acid, 4-fluoro-3-chlorobenzoic acid can be widely used in industries such as agricultural chemicals, medicine, pigment, dyestuff.
3, the synthetic method of 4-dichlorobenzonitrile mainly contain report such as European patent EP 441004 and the flat 08-119925 of Japan Patent by α, α, α, 3,4-toluene pentachloride and NH
4Reaction such as Cl is synthetic; By 3, the 4-dichloro-benzamide is at H
2SO
4In be dehydrated into nitrile; By 3,4-dichloro benzaldoxime dehydration preparation.But this several method exists raw material costliness, shortcoming such as seriously polluted, is difficult to realize industrialization.By 3, the 4-dichlorotoleune is preparation 3 at present through ammoxidation reaction under catalyst action, and the method for the best of 4-dichloro formonitrile HCN, its key are to find the catalyst of high activity, high selectivity.Ammoxidation is meant under catalyst action, labile methyl group in the organic molecule and cheap ammonia and oxygen (air) reaction, and a step is converted into the catalytic reaction of cyano group.After the ammoxidating propylene to produce acrylonitrile industrialization, developed country falls over each other to carry out the research that the ammoxidation of aromatic hydrocarbon legal system is equipped with fragrant nitrile, and is long with alternative route, energy consumption is high, environmental pollution is serious, and other produces the method for fragrant nitrile.Up to the present, Martin etc. is only arranged with the VOHPO of load not
40.5H
2O prepares 3 as catalyst precarsor, the report of 4-dichlorobenzonitrile.Its optimum reaction condition is: reaction temperature 713K, 3,4-dichlorotoleune: O
2: NH
3: H
2O=1: 5: 8: 25, (W/F)=10.2g
CatH/mol.With this understanding, 3,4-dichlorotoleune conversion ratio is about 88%, 3, and the productive rate of 4-dichlorobenzonitrile only is 50%, and this catalyst mechanical strength is not high, is difficult to satisfy industrial production requirement.
The purpose of this invention is to provide a kind of ammoxidation preparation 3, the method for 4-dichlorobenzonitrile and special-purpose catalyst, this catalyst answer that cost is low, heat endurance and mechanical strength are good, tool is than high selectivity and activity, can improve 3, the conversion ratio of 4-dichlorotoleune and 3, the productive rate of 4-dichlorobenzonitrile.
For realizing that the present invention adopts following measure:
A kind of ammoxidation preparation 3, the catalyst of 4-dichlorobenzonitrile, it is to be major catalyst with vanadium, phosphorus, titanium, manganese, chromium, molybdenum, boron, iron, nickel, cobalt, copper, zinc, potassium, lithium, magnesium, tin etc. are the multicomponent catalyst of co-catalyst, its active ingredient consists of:
V
aP
bC
cD
dE
eO
xC wherein is titanium, manganese, chromium, molybdenum or boron, D=iron, nickel, cobalt or copper, E=zinc, potassium, lithium, magnesium or tin; A=1; B=0.5～2.5; C=0～1.3; D=0～1.2; E=0～0.4; X then decides according to the content of above-mentioned each element.Active component element wt content is 3～40%, and preferably scope is 5～30%.Carrier is a microsphere silica gel, and the microsphere diameter scope is 125～450 μ m.
Preparation of catalysts adopts infusion process: the active ingredient of catalyst dissolved respectively, mixed, pour into again in the carrier silica gel, and still aging after fully stirring, under suitable temperature, activate the regular hour then.Generally between 673～923K, preferably temperature range is 723～873K to activation temperature.Soak time was generally 2～20 hours, and the optimum activating time scope is 3～15 hours.
Preparation is during catalyst, and each component can be with oxide, salt or the alkali etc. of this element.For example vanadium can be used V
2O
5Or NH
4VO
3Deng, phosphorus can be used H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, (NH
4) H
2PO
4Or P
2O
5Deng, titanium can be used TiCl
4, Ti
2(C
2O
4)
3Deng, manganese can be used MnO
2, MnCl
2, Mn (NO
3)
2Deng, chromium can be used CrCl
3, Cr (NO
3)
39H
2O, Cr
2O
3, CrO
3Or (NH
4)
2Cr
2O
7Deng, molybdenum can be used MoO
3, (NH
4)
6Mo
7O
24Deng, tungsten can be used (NH
4)
2WO
4, boron can be used H
3BO
3, iron can be used FeCl
3, Fe
2O
3, Fe
3O
4, Fe (NO
3)
39H
2O, Fe (OAc)
2, Fe (C
2O
4) 2H
2O or Fe
2(C
2O
4)
36H
2O etc., nickel can be used NiCl
26H
2O or Ni (NO
3)
26H
2O etc., cobalt can be used Co (OAc)
2, Co (NO
3)
26H
2O, Co
3O
4Or CoCl
2Deng, copper can be used CuCl
2Or Cu (NO
3)
2Deng, zinc can be used ZnO, ZnCl
2, Zn (NO
3)
2Or Zn (OAc)
22H
2O etc., potassium can be used KOH, KCl, KNO
3, K
2CO
3Or K
2C
2O
4Deng, lithium can be used Li
2O, LiCl, LiNO
3Or Li
2CO
3Deng, magnesium can be used MgO, MgCl
2Or Mg (NO
3)
26H
2O etc., tin can be used SnCl
2Or SnCl
4Deng.
The optimum process condition scope of the open catalyst ammoxidation reaction of the present invention is as follows: reaction temperature 623～723K, air and 3,4-dichlorotoleune mol ratio is 8～60, ammonia and 3, the mol ratio of 4-dichlorotoleune is 2～12, catalyst loading 30～100g/ (kgcath).Under stable reaction condition, 3, the conversion ratio of 4-dichlorotoleune is higher than 97%, 3, and the molar yield of 4-dichlorobenzonitrile is higher than 83%, and product purity is higher than 98%.
Adopting with vanadium, phosphorus among the present invention is major catalyst, titanium, manganese, chromium, molybdenum, boron, iron, nickel, cobalt, copper, zinc, potassium, lithium, magnesium, tin etc. are the multicomponent catalyst of co-catalyst, can make 3, the 4-dichlorotoleune makes 3 through ammoxidation reaction one step, and the 4-dichlorobenzonitrile is can alternative route long, energy consumption is high, environmental pollution is serious, and other produces the method for fragrant nitrile.Simultaneously, this catalyst tool is than high selectivity and activity, and 3, the productive rate and the selectivity of 4-dichlorobenzonitrile all increase substantially.And catalyst uses silica gel to make carrier, and carrier silica gel can provide the effective ratio area and the pore structure of catalytic reaction, the heat endurance and the mechanical strength of catalyst have been improved greatly, reduced the use amount of catalyst activity component, the Preparation of catalysts cost is reduced, on fixed bed and fluidized-bed reactor, all can use.
Below in conjunction with embodiment, the technology of the present invention is described in further detail.
Embodiment 1
With 7.693 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, adds 4.706 grams, 85% SPA, 3.701 gram V then respectively
2O
5, after the uniform solution to be formed, solution is poured into rapidly in the 30 gram silica gel (φ 125～450 μ m).Stir, after the drying, in muffle furnace, progressively be warmed up to 580 ℃, be incubated 12 hours.Naturally after the cooling, stand-by.Consisting of of catalyst: V
1P
1O
4.8/ SiO
2, activity of such catalysts composition weight content is 10%.
At internal diameter is the above-mentioned solid catalyst of filling 15g in the quartz ampoule fixed bed reactors of 30mm, and the mole proportioning of reaction raw materials is 3,4-dichlorotoleune: NH
3: Air=1: 7: 30, reaction temperature was 673 ± 1K, and the load of catalyst is 50g/ (kgcath).React after 8 hours, 3, the conversion ratio 97.8%, 3 of 4-dichlorotoleune, the molar yield of 4-dichlorobenzonitrile is 67.3%, 3, the selectivity of 4-dichlorobenzonitrile is 68.9%.Product purity is 98.3%.Embodiment 2 catalyst consist of V
1P
2O
9.5/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio 96.9%, productive rate are 71.4%, and selectivity is 73.7%.Embodiment 3 catalyst consist of V
1P
1.2Ti
0.8O
6.5/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 98.1%, and productive rate is 73.6%, selectivity is 75.0%.Embodiment 4 catalyst consist of V
1P
2.4Fe
0.7O
9.4/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 98.6%, and productive rate is 75.2%, selectivity is 76.3%.Embodiment 5 catalyst consist of V
1P
0.7Zn
0.8O
4.95/ SiO2, its preparation method are with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 97.3%, and productive rate is 74.9%, and selectivity is 77%.Embodiment 6 catalyst consist of V
1P
1.7Mn
1.0Ni
0.3O
8.8/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 98.8%, and productive rate is 81.2%, selectivity is 82.2%.Embodiment 7 catalyst consist of V
1P
1.9W
0.4K
0.1O
8.4/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 97.6%, and productive rate is 80.5%, selectivity is 82.5%.Embodiment 8 catalyst consist of V
1P
0.8Co
0.5Mg
0.2O
5.1/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 99.2%, and productive rate is 78.8%, selectivity is 79.4%.Embodiment 9 catalyst consist of V
1P
1.1Cr
0.4Co
0.4K
0.02O
6.17/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 98.5%, and productive rate is 85.5%, selectivity is 86.8%.Embodiment 10 catalyst consist of V
1P
2.5Mo
0.1Cu
0.1Li
0.2O
9.0/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio is 98.4%, and productive rate is 84.7%, selectivity is 96.1%.Embodiment 11 catalyst consist of V
1P
0.5B
0.1Fe
0.8Sn
0.1O
5.05/ SiO
2, its preparation method is with embodiment 1, and with this Preparation of Catalyst 3, the condition of 4-dichlorobenzonitrile is with embodiment 1, and conversion ratio 99.5%, productive rate are 85.3%, and selectivity is 85.7%.
Claims (4)
1. ammonia oxidation preparation 3, the catalyst of 4-dichlorobenzonitrile, and it is to be carrier with silica gel, it is characterized in that: this catalyst activity composition consists of: V
aPXC
cD
dE
eO
x, wherein C is titanium, manganese, chromium, molybdenum or boron, D=iron, nickel, cobalt or copper, E=zinc, potassium, lithium, magnesium or tin; A=1; B=0.5～2.5; C=0～1.3; D=0～1.2; E=0～0.4; X then decides according to the content of above each element, and its active component element wt content is 3～40%.
2. the described catalyst of claim 1, it is characterized in that: described active component element wt content is 5～30%.
3. claim 1 or 2 described Preparation of catalysts methods, it is characterized in that: oxide, salt or the alkali of each element of this catalyst active principle are dissolved mixing respectively, with carrier silica gel dipping, fully stirring, still aging again, between 673～923K, activate 2～20 hours then.
4. claim 1 or 2 described catalyst are used for ammoxidation preparation 3, the 4-dichlorobenzonitrile, its process conditions are: reaction temperature 623～723K, reaction pressure is a normal pressure, air and 3,4-dichlorotoleune mol ratio is 8～60, ammonia and 3,4-dichlorotoleune mol ratio is 2～12, catalyst loading 30～100g/ (kgcath).
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| CNB001146416A CN1137779C (en) | 2000-06-20 | 2000-06-20 | Method for preparing 3,4-dichlorophenylnitrile by using ammonia oxidation process and its special-purpose catalyst |
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| CNB001146416A CN1137779C (en) | 2000-06-20 | 2000-06-20 | Method for preparing 3,4-dichlorophenylnitrile by using ammonia oxidation process and its special-purpose catalyst |
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| CN1137779C true CN1137779C (en) | 2004-02-11 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803285B (en) * | 2005-12-27 | 2010-05-05 | 张荣成 | Selective ammoxidation catalyst for multiple methyl arene, its preparation method and uses |
| CN101759596B (en) * | 2010-01-25 | 2013-02-13 | 南通泰禾化工有限公司 | Method for preparing 3,4-dichloro-cyanobenzene |
| CN102295581A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing 3,4-dichlorobenzonitrile by ammonia oxidation |
| CN102746192A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for ammoxidation preparation of 2,4-dichlorobenzonitrile |
| CN102744090B (en) * | 2011-04-20 | 2014-12-10 | 中国石油化工股份有限公司 | Catalyst for ammoxidation preparation of 2,4-dichlorobenzonitrile |
| CN102603569A (en) * | 2012-02-21 | 2012-07-25 | 南通市东昌化工有限公司 | Production method of 3,4-dichlorobenzonitrile |
| CN103539701B (en) * | 2012-07-12 | 2015-12-16 | 中国石油化工股份有限公司 | For the method for prepared by ammoxidation for o-Cyanochlorobenzene |
| CN102924329A (en) * | 2012-11-14 | 2013-02-13 | 连云港阳方催化科技有限公司 | Method of ammoxidation synthesis of 3, 4- dichlorobenzonitrile |
| CN103041838A (en) * | 2012-12-28 | 2013-04-17 | 武汉今福科技有限公司 | Catalyst for preparing 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene by means of ammoxidation |
| CN103769184A (en) * | 2014-01-24 | 2014-05-07 | 先尼科化工（上海）有限公司 | Catalyst for producing aromatic nitrile through aromatic ammoxidation, and applications of catalyst |
| CN104496849A (en) * | 2014-11-24 | 2015-04-08 | 苏州乔纳森新材料科技有限公司 | Method used for synthesizing 3,4-dichlorobenzonitrile via ammoxidation |
| CN109912453B (en) * | 2017-12-13 | 2021-09-24 | 中南民族大学 | Method for preparing 2, 5-dichlorobenzonitrile, special catalyst and preparation method thereof |
| CN109847772B (en) * | 2018-12-17 | 2022-02-18 | 中南民族大学 | Special catalyst for preparing parachlorobenzonitrile by ammoxidation method, preparation method and application |
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