CN1137778C - Method for preparing 2,4-dichlorophenylnitrile by using ammonia oxidation process and special-purpose catalyst - Google Patents
Method for preparing 2,4-dichlorophenylnitrile by using ammonia oxidation process and special-purpose catalyst Download PDFInfo
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- CN1137778C CN1137778C CNB001146408A CN00114640A CN1137778C CN 1137778 C CN1137778 C CN 1137778C CN B001146408 A CNB001146408 A CN B001146408A CN 00114640 A CN00114640 A CN 00114640A CN 1137778 C CN1137778 C CN 1137778C
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- catalyst
- dichlorobenzonitrile
- dichlorotoleune
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- ammonia oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 12
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 8
- 230000008569 process Effects 0.000 title claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 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
- 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
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 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
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 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
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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
- 239000011135 tin Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 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
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 description 1
- NJYBIFYEWYWYAN-UHFFFAOYSA-N 2,4-difluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1F NJYBIFYEWYWYAN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 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
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 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
- -1 nitrile compounds Chemical class 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
- 230000009467 reduction Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method and a special catalyst for preparing 2, 4-dichlorobenzonitrile by ammonia oxidation. The special catalyst in a chemical structure of Va Tib Pc Dd Ee Ox is a multicomponent catalyst comprising vanadium, titanium and phosphorus as main catalysts and ferrum, nickel, cobalt, bismuth, manganese, chromium, molybdenum, copper, zinc, tin, boron, potassium, litium, magnesium, etc. as cocatalysts. The catalyst for preparing 2, 4-dichlorobenzonitrile by ammonia oxidation has the advantages of high activity, high selectivity, high product yield, high product purity, simple manufacturing process, etc.
Description
The present invention relates to a kind of ammonia oxidation preparation 2, 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.
2,4-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, 2,4-dichlorobenzonitrile and its fluorinated derivatives are as 2,4-difluorobenzonilyile, 2,4-difluoro-benzoic acid, 2,4-difluoroaniline, 2,4-two chloro-5-fluobenzoic acids and 2,4, fine-chemical intermediates such as the stupid formic acid of 5-trifluoro can be widely used in industries such as agricultural chemicals, medicine, pigment, dyestuff.
2, the general preparation method of 4-dichlorobenzonitrile have with European patent EP 441004 be representative by α, α, α, 2,4-toluene pentachloride and NH
3Obtain Deng reaction; The flat 01-96163 of Japan Patent report with 2, the 4-dichlorobenzoyl chloride is the method for raw material or is got by corresponding aldoxime dehydration or carboxylic acid and urea reaction.But these methods exist shortcomings such as raw material sources difficulty, reaction scheme is long, pollution is big.By 2, the 4-dichlorotoleune makes 2 through ammoxidation reaction under catalyst action, and 4-dichloro formonitrile HCN is the method for preparing the best of many fragrant nitrile compounds at present, and its key is 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.Adopt ammonia oxidation preparation 2, the 4-dichlorobenzonitrile have technology simple and direct, can carry out continuously, advantage such as production capacity is strong, environmentally friendly and raw material is easy to get, other that alternative route is long, energy consumption is high, environmental pollution is serious produced the method for fragrant nitrile.At present, use ammonia oxidation preparation 2 in the world, the 4-dichlorobenzonitrile mainly contains: report such as (1) Martin adopts VOHPO
4H
2O] as catalyst precarsor, carry out 2, the ammoxidation of 4-dichlorotoleune, optimal conditions is: reaction temperature 708K, 2,4-dichlorotoleune: O
2: NH
3: H
2O=1: 5: 8: 25, space velocity (W/F) 10g
CatH/mol, 2,4-dichlorotoleune conversion ratio is about 85%, 2, the productive rate of 4-dichlorobenzonitrile be about 48% (Martin A, L ü cke B, Wolf G-U et al.Catalysis Letters, 1995,33:349).(2) U.S. Pat 4124631 (or German patent DE 2711332) report V
1P
1Co
0.3/ SiO
2Catalyst carries out 2, and 4-dichlorotoleune ammoxidation reaction, the conversion ratio of dichlorotoleune are 97.6%, and productive rate is 80.8%.
The purpose of this invention is to provide a kind of ammoxidation preparation 2, 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 2, the conversion ratio of 4-dichlorotoleune and 2, the productive rate of 4-dichlorobenzonitrile.
For realizing that the present invention adopts following measure:
A kind of ammoxidation preparation 2, the catalyst of 4-dichlorobenzonitrile, it is to be major catalyst with vanadium, titanium, phosphorus, iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, copper, zinc, tin, boron, potassium, lithium, magnesium etc. are the multicomponent catalyst of co-catalyst, it consists of:
V
aTi
bP
cD
dE
eO
x/ SiO
2Wherein D is iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, and E is copper, zinc, tin, boron, potassium, lithium or magnesium; A=1; B=0.3～2.5; C=0.5～1.7; D=0～1.2; E=0～0.9; X then decides according to the content of above 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, and still aging after fully flooding with carrier silica gel again, 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, titanium can be used TiCl
4, Ti
2(C
2O
4)
3Deng, phosphorus can be used H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, (NH
4) H
2PO
4Or P
2O
5Deng, 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, 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., cobalt can be used Co (OAc)
2, Co (NO
3)
26H
2O, Co
3O
4Or CoCl
2Deng, nickel can be used NiCl
26H
2O or Ni (NO
3)
26H
2O etc., 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., tin can be used SnCl
2Or SnCl
4Deng, boron can be used H
3BO
3, 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.
The optimum process condition scope of the open catalyst ammoxidation reaction of the present invention is as follows: reaction temperature 623～723K, air and 2, the mol ratio of 4-dichlorotoleune are 8～60, ammonia and 2, the mol ratio of 4-dichlorotoleune is 2～12, catalyst loading 30～100g/ (kgcath).Be on the quartz ampoule fixed bed reactors of 30mm and under the stable reaction condition at internal diameter, 2, the conversion ratio of 4-dichlorotoleune can be higher than 98%, 2, and the molar yield of 4-dichlorobenzonitrile can be up to 89.5%, and product purity is higher than 98.0%.
Adopting with vanadium, phosphorus among the present invention is major catalyst, titanium, iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, copper, zinc, tin, boron, potassium, lithium, magnesium etc. are five component catalysts of co-catalyst, can make 2, the 4-dichlorotoleune makes 2 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 2, the productive rate and the selectivity of 4-dichlorobenzonitrile all improve a lot.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 4.899 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, adds 1.493 grams, 85% SPA, 2.3559 gram V then respectively
2O
5TiCl with 11.60mL0.139mol/L
4Solution after the uniform solution to be formed, is poured solution in the 30 gram silica gel (φ 125～425 μ m) into.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
1Ti
1.3P
0.5/ 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 2,4-dichlorotoleune: NH
3: Air=1: 7: 15, reaction temperature was 673 ± 1K, and the load of catalyst is 50g/ (kgcath).React after 8 hours, 2, the conversion ratio 99.1%, 2 of 4-dichlorotoleune, the molar yield of 4-dichlorobenzonitrile is 82.1%, 2, and the selectivity of 4-dichlorobenzonitrile is 82.8%, and product purity is 98.9%.Embodiment 2～4: catalyst is formed different, and process conditions are with embodiment 1, result such as following table:
Embodiment 5
| Embodiment | Catalyst | Conversion ratio/% | Productive rate/% | Selectivity/% |
| 2 | V 1Ti 0.4P 1.4Bi 0.1/SiO 2 | 98.7 | 83.4 | 84.5 |
| 3 | V 1Ti 1.8P 0.4K 0.2/SiO 2 | 99.4 | 85.2 | 85.7 |
| 4 | V 1Ti 2.1P 0.8Cr 0.2/SiO 2 | 99.2 | 86.7 | 87.4 |
With 4.8497 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, adds 4.7293 grams, 85% SPA, 2.3322 gram V then respectively
2O
5, behind the dark blue solution to be formed, add 0.139mol/LdeTiCl
4Solution 2.65mL, 50%Mn (NO
3)
2Solution 2.2946mL and 0.1202 gram LiCl after the uniform solution to be formed, pour solution rapidly in the 30 gram silica gel (φ 125～425 μ m).Stir, placement is spent the night.In high temperature furnace, progressively be warmed up to 580 ℃, be incubated 12 hours.After treating the nature cooling, preserve stand-by.Consisting of of this catalyst: V
1Ti
0.3P
1.6Mn
0.25Li
0.2/ SiO
2, activity of such catalysts composition weight content is 10%.
The 15g catalyst is packed in the internal diameter 30mm quartz ampoule fixed bed reactors, and material mixed gas passes through catalyst bed reaction.Consisting of of material mixed gas: 2,4-dichlorotoleune: ammonia: air=1: 6: 20.Reaction temperature is 673K, and the load of catalyst is 50g/ (kgcath).React after 8 hours, 2,4-dichlorotoleune conversion ratio 98.1%, 2,4-dichlorobenzonitrile molar yield 89.5%, selectivity 91.3%, product purity 98.7%.Major impurity in the product is contained 3 in the raw material, the ammoxidation of 4-dichlorotoleune generate 3, the 4-dichlorobenzonitrile.Embodiment 6～7: catalyst is formed different, and process conditions are with embodiment 5, result such as following table:
| Embodiment | Catalyst | Conversion ratio/% | Productive rate/% | Selectivity/% |
| 6 | V 1Ti 2.2P 0.7Fe 0.2Mg 0.1/SiO 2 | 99.3 | 87.9 | 88.5 |
| 7 | V 1Ti 0.9P 0.5Cu 0.1B 0.15/SiO 2 | 98.7 | 88.7 | 89.9 |
Claims (3)
1. ammonia oxidation preparation 2, the special-purpose 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
aTi
bP
cD
dE
eO
x, wherein D is titanium, iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, E=copper, zinc, tin, boron, potassium, lithium or magnesium; A=1; B=0.3～2.5; C=0.5～1.7; D=0～1.2; E=0～0.9; X then decides according to the content and the valence state 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 2, the 4-dichlorobenzonitrile, its process conditions are: reaction temperature 623～723K, air and 2, the mol ratio of 4-dichlorotoleune is 8～60, ammonia and 2,4-dichlorotoleune mol ratio is 2～12, catalyst loading 30～100g/ (kgcath).
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| CNB001146408A CN1137778C (en) | 2000-06-20 | 2000-06-20 | Method for preparing 2,4-dichlorophenylnitrile by using ammonia oxidation process and special-purpose catalyst |
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| CNB001146408A CN1137778C (en) | 2000-06-20 | 2000-06-20 | Method for preparing 2,4-dichlorophenylnitrile by using ammonia oxidation process and special-purpose catalyst |
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| CN1137778C true CN1137778C (en) | 2004-02-11 |
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| CN106111172B (en) * | 2016-06-22 | 2018-06-15 | 徐州恒鼎生物科技有限公司 | Catalyst for preparing 3-cyanopyridine by catalytic ammoxidation and preparation method thereof |
| ES2922381T3 (en) * | 2018-03-30 | 2022-09-14 | Mitsubishi Gas Chemical Co | Method for producing aromatic nitrile by ammoxidation reaction |
| CN115646520B (en) * | 2022-11-15 | 2024-05-14 | 江苏新河农用化工有限公司 | Catalyst for synthesizing p-chlorobenzonitrile and preparation method and application thereof |
| CN116351434B (en) * | 2023-02-17 | 2024-05-03 | 中南民族大学 | Catalyst for preparing 2, 4-dichlorobenzonitrile, preparation method and application |
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