CN1097482C - Process for preparing O(P)-methylbenzonitrile catalyst - Google Patents

Process for preparing O(P)-methylbenzonitrile catalyst Download PDF

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Publication number
CN1097482C
CN1097482C CN00136213A CN00136213A CN1097482C CN 1097482 C CN1097482 C CN 1097482C CN 00136213 A CN00136213 A CN 00136213A CN 00136213 A CN00136213 A CN 00136213A CN 1097482 C CN1097482 C CN 1097482C
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catalyst
preparation
nitrate
addition
ammonium molybdate
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CN1304796A (en
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于海斌
蒋建明
姜雪丹
张永刚
常俊石
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Tianjin Chemical Research & Design Inst Ministry Of Chemical Industry
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Tianjin Chemical Research & Design Inst Ministry Of Chemical Industry
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Abstract

The present invention relates to a technical field of catalyst manufacture, particularly to a preparation method of a catalyst used for an adjacent (opposite) methylbenzonitrile production device by using adjacent (opposite) xylene as a raw material in an ammonia catalyzed oxidation method. An ammonium molybdate solution is used to neutralize a bismuth nitrate, nickel nitrate, ferric nitrate, cabaltous nitrateand dilutenitric acid mixing solution to form precipitates; meanwhile, a carrier of silicon dioxide is added in, the precipitates are heated, dehydrated, baked, calcined, formed, baked again and calcined again to be manufactured into the adjacent (opposite) methylbenzonitrile catalyst. The technology has the advantages of unique technological routes, good product intensity and long service life, and the catalyst is superior to the existing catalysts no matter on selectivity and conversion rate aspects.

Description

A kind of neighbour (to) preparation method of methylbenzene nitrile catalyst
The present invention relates to catalyst manufacturing technology field, exactly for adjacent (to) dimethylbenzene is raw material, that the ammonia catalytic method is produced is adjacent (to) methylbenzene nitrile process units Preparation of catalysts method.
The present invention's technology in the past is as CA80:3281e; Ger2314151 is based on the lab scale test, its defective is the intensity extreme difference, evaluation is i.e. all efflorescence about 10 hours, its accessory substance terephthalonitrile productive rate is more than 11%, therefore, catalyst was difficult to carry out in industrialized application in the past, simultaneously, for adjusting the oxidation characteristic of catalyst, its catalyst component and co-catalyst component remain to be obtained more rational improvement.
The present invention is directed to the defective of catalyst existence in the past, purpose be to provide a kind of produce adjacent (to) preparation method of methylbenzene nitrile catalyst, fabricating technology route uniqueness of the present invention, the product strength of preparation is good, long service life, and the finished catalyst that makes all is being better than existing catalyst aspect selectivity, the conversion ratio.
The present invention realizes in the following manner:
With the ammonium molybdate ammonia solvent, be prepared into solution A.Bismuth nitrate, nickel nitrate, ferric nitrate, cobalt nitrate dilute nitric acid dissolution add phosphoric acid, are prepared into solution B, A is slowly added carry out co-precipitation among the B, add carrier silica simultaneously, get sediment C.With the C thermal dehydration, oven dry, calcining must be lumpd but looser material D, and D is crushed to about 200 orders, promptly gets grained catalyst of the present invention.Add adhesive and mediate, moulding, oven dry, calcine shape catalyst finished product of the present invention.The technical process of preparation is:
(1), obtains the ammonium molybdate solution A of 15%-70% concentration with ammoniacal liquor or water-solublely separate a certain amount of ammonium molybdate.
(2) with the bismuth nitrate of the dilute nitric acid dissolution amount of calculation of 0.5-10%, cobalt nitrate, ferric nitrate with
And nickel nitrate, the phosphoric acid of adding amount of calculation gets solution B.
(3) in B, add silica, A solution while stirring, get pulpous state sediment C.
(4) heating is concentrated down at 100 ℃-180 ℃ with C, and oven dry is 300-550 ℃ of calcining down
1.5-16 hour, get a caking but looser material D.
(5) D is crushed to below 200 orders with pulverizer, promptly gets grained catalyst.
(6) in interior grained catalyst, add adhesive, mediate, can be extruded into the wet stock of different shapes such as strip, clover shape, this material is dried down at 100 ℃-200 ℃ with banded extruder, calcine more than 16 hours down at 350 ℃-600 ℃, promptly get finished form catalyst of the present invention.
Above-mentioned (1) middle ammonium molybdate is the available water heating for dissolving also.
The time that phosphoric acid and carrier silica add in above-mentioned (2), (3) also can add in kneading, and wherein the adding of carrier silica is in order to reduce cost, also can not add.
The concentration of diluted acid is preferably in 2.5-3.5% in above-mentioned (2).
Above-mentioned (4) middle heating concentrates, bake out temperature is preferably in 120-140 ℃, and calcining heat is preferably in 350-600 ℃, and calcination time was preferably in more than 16 hours.
The material of the pulverizer in above-mentioned (5) is unrestricted, and the fineness of pulverizing preferably is controlled at below 200 orders.
In above-mentioned (6) grained catalyst can be on banded extruder extruded moulding, its shape is determined by orifice plate, be can be bar shaped, annular, cloverleaf pattern etc., its appearance and size is diameter phi 2.5-5 * 15mm preferably, perhaps punch forming is made lubricant with graphite, and shape is determined by template.
The catalyst that the present invention is prepared into has following performance:
Side pressure strength: 〉=80N/cm; Specific area: 30m 2/ g;
Bulk specific weight: 0.9-1.2g/ml
To methylbenzene nitrile conversion ratio: 〉=45%; Selection rate: 〉=98%;
O-methyl-benzene nitrile conversion ratio: 〉=40%; Selection rate: 〉=98%.
Characteristic of the present invention is: with certain density ammonia solvent ammonium molybdate, make the ammonium molybdate stabilizing solution of 15-70% 1..2. with in the ammonium molybdate solution and the mixed solution of bismuth nitrate, nickel nitrate, ferric nitrate, cobalt nitrate, sediment is pulverized through calcining and is formed grained catalyst, add adhesive again and mediate, extruded moulding, the shape catalyst.3. the catalyst of the inventive method preparation, be used for the neighbour (to) preparation of xylidine catalytic oxidation adjacent (to) have higher conversion ratio, selection rate and yield during the dimethyl benzene nitrile.4. the catalyst of the present invention preparation, be specially adapted to by adjacent (to) the dimethylbenzene preparation adjacent (to) the dimethyl benzene nitrile.
Through experimental evaluation, its intensity of catalyst of the present invention is greater than 80N/cm, apparently higher than the commercial Application requirement.Selectivity and conversion ratio increase (seeing the embodiment evaluation result), have reached the necessary condition of industrializing implementation.
Embodiment 1
The first step: take by weighing 40 kilograms of ammonium molybdates,, get ammonium molybdate solution with the ammonia solvent of 120 kg 18%.
Second step: 175 liters of dissolvings of the rare nitric acid with 3% bismuth nitrate (Bi (NO 3) 35H 2O) 9.1 kilograms, add nickel nitrate (Ni (NO 3) 26H 2O) 13.7 kilograms, ferric nitrate (Fe (NO 3) 9H 2O) 22.7 kilograms, cobalt nitrate (Co (NO 3) 26H 2O) 24.6 kilograms, stirring and dissolving adds phosphatase 11 .1 kilogram, slowly adds the ammonium molybdate solution of first step dissolving, stirs, and forms precipitation gradually, adds SiO while stirring 29.3 kilogram, being pulpous state, thermal dehydration 120-150 ℃ of oven dry down, was calcined 4 hours down at 420 ℃, got grained catalyst.
The 3rd step: grained catalyst is crushed to 200 orders, mediates, extrusion becomes φ 3mm cylindrical, 120 ℃ of oven dry 4 hours, gets finished catalyst in 12 hours 550 ℃ of calcinings.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 67%, yield 99%, selection rate 98%.
This catalyst is when making the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene, conversion ratio can reach 66%, yield 99%, selection rate 97%.
Embodiment 2
The first step is used 200 premium on currency instead, is heated to 80-90 ℃ of dissolving ammonium molybdate, and other is with embodiment 1.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 68%, yield 99%, selection rate 97%.
This catalyst is when making the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene, conversion ratio can reach 69%, yield 99%, selection rate 97%.
Embodiment 3
Remove phosphoric acid and change into adding when mediating in the 3rd step, other is with embodiment 1.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 72%, yield 99%, selection rate 98%.
This catalyst is when making the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene, conversion ratio can reach 73%, yield 99%, selection rate 97%.
Embodiment 4
Adding when changing into kneading except that carrier silica, other is with embodiment 1.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 70%, yield 99%, selection rate 97%.
This catalyst is when making the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene, conversion ratio can reach 73%, yield 99%, selection rate 98%.
Embodiment 5
Except that no carrier added silica, other is with embodiment 1.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 75%, yield 99%, selection rate 98.7%.
This catalyst is when making the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene, conversion ratio can reach 76%, yield 98.5%, selection rate 98.5%.
Embodiment 6
The amount of ferric nitrate changes 30 kilograms into, and other is with embodiment 1.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 74%, yield 99%, selection rate 98.8%.
This catalyst is when making the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene, conversion ratio can reach 76%, yield 99%, selection rate 98.1%.
Embodiment 7
The amount of phosphoric acid changes 1.4 kilograms into, and other is with embodiment 1.
This catalyst is when making the raw material ammonia catalytic oxidation and prepare adjacent dimethyl benzene nitrile of ortho-xylene, conversion ratio can reach 52%, yield 99% selection rate 99%.
This catalyst is being made the preparation of raw material ammonia catalytic oxidation to the dimethyl benzene nitrile of paraxylene
The time, conversion ratio can reach 53%, yield 99%, selection rate 98.9%.

Claims (11)

  1. A neighbour (to) preparation method of methylbenzene nitrile catalyst, with in the ammonium molybdate solution and the mixed solution of the bismuth nitrate of nitric acid dissolve, nickel nitrate, ferric nitrate, cobalt nitrate, sediment makes grained catalyst through calcining, adding adhesive again mediates, extruded moulding, calcining make the shape finished catalyst, shape is determined by template, it is characterized in that:
    (1) with ammoniacal liquor or the water-soluble ammonium molybdate of separating, the weight concentration of ammonium molybdate solution is controlled to be 15%-70%;
    (2) with the dilute nitric acid dissolution bismuth nitrate of weight concentration 0.5-10%, add nickel nitrate, ferric nitrate, cobalt nitrate afterwards, stirring and dissolving adds phosphoric acid, continues to stir;
    (3) add the ammonium molybdate solution that dissolves, stir, form precipitation gradually, be pulpous state;
    (4) thermal dehydration, oven dry was calcined 12 hours, got grained catalyst;
    (5) grained catalyst is crushed to 200 orders, mediates, extrusion is cylindrical, and oven dry is forged
    Burn and got finished catalyst in 12 hours.
  2. 2. according to the preparation method of claim 1, it is characterized in that: ammonium molybdate water or ammonia solvent, the both can heat, but temperature should not be above 100 ℃.
  3. 3. according to the preparation method of claim 1, it is characterized in that: when dissolving nitrate, add carrier silica, or when mediating, add carrier silica.
  4. 4. according to the preparation method of claim 3, it is characterized in that: the carrier silica of adding uses macro porous silica gel, or other low sodium silica.
  5. 5. according to the preparation method of claim 1, it is characterized in that: phosphoric acid adds when dissolving nitrate, or adds when mediating.
  6. 6. according to the preparation method of claim 1, it is characterized in that: the temperature that heating concentrates is at 90 ℃-200 ℃, and the temperature of oven dry is at 100 ℃-200 ℃, and the temperature of calcining is at 340 ℃-600 ℃.
  7. 7. according to the preparation method of claim 1, it is characterized in that: the time of oven dry is 2-10 hour, and the time of calcining is 2-16 hour.
  8. 8. according to the preparation method of claim 1, it is characterized in that: ammonium molybdate is (NH 4) 6Mo 7O 244H 2O form, its addition are 5-15%; Ferric nitrate is Fe (NO 3) 39H 2O form, its addition are 15-50%; Cobalt nitrate is Co (NO 3) 26H 2O form, its addition are 20-40%: nickel nitrate is Ni (NO 3) 26H 2O form, its addition are 8-30%; The addition of phosphoric acid is 0.5-3%; The addition of nitric acid is 1.5-10%; Bismuth nitrate is Bi (NO 3) 35H 2O form, its addition are 5-25%.
  9. 9. according to claim 3,4 preparation method, it is characterized in that: the addition of silica is 0-25%.
  10. 10. according to the preparation method of claim 1, it is characterized in that: extruded moulding on banded extruder, its shape are determined by orifice plate, can be bar shaped, annular or cloverleaf pattern.
  11. 11. the preparation method according to claim 1 is characterized in that: grained catalyst can adopt punch forming, can adopt graphite to do lubricant, and the shape of catalyst is determined by template.
CN00136213A 2000-12-25 2000-12-25 Process for preparing O(P)-methylbenzonitrile catalyst Expired - Fee Related CN1097482C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100335174C (en) * 2004-12-17 2007-09-05 武汉大学 Method of preparing catalyst camied by composite oxides and application
CN102340265A (en) * 2010-07-27 2012-02-01 宇威光电股份有限公司 Solar cell system
CN112439442B (en) * 2019-09-05 2023-08-11 中石油吉林化工工程有限公司 Preparation method of catalyst for preparing acrolein by propylene oxidation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124631A (en) * 1977-01-14 1978-11-07 Nippon Kayaku Kabushiki Kaisha Process for the production of aromatic nitriles
US4209457A (en) * 1978-01-28 1980-06-24 I.S. C. Chemicals Limited Production of halogenated benzonitriles
CN1268399A (en) * 1999-03-30 2000-10-04 中国石油化工集团公司 Fluidized-bed catalyst for preparing isophthalonitrile

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124631A (en) * 1977-01-14 1978-11-07 Nippon Kayaku Kabushiki Kaisha Process for the production of aromatic nitriles
US4209457A (en) * 1978-01-28 1980-06-24 I.S. C. Chemicals Limited Production of halogenated benzonitriles
CN1268399A (en) * 1999-03-30 2000-10-04 中国石油化工集团公司 Fluidized-bed catalyst for preparing isophthalonitrile

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