CN1351989A - Fluidized bed catalyst for preparing benzonitrile - Google Patents
Fluidized bed catalyst for preparing benzonitrile Download PDFInfo
- Publication number
- CN1351989A CN1351989A CN 00127436 CN00127436A CN1351989A CN 1351989 A CN1351989 A CN 1351989A CN 00127436 CN00127436 CN 00127436 CN 00127436 A CN00127436 A CN 00127436A CN 1351989 A CN1351989 A CN 1351989A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- cyanobenzene
- catalyst
- span
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention relates to a fluidized bed catalyst for preparation benzonitrile. The technological scheme is as follows: The catalyst contains silica carrier and composite with the chemical expression V1.0AaBbCcDdOx, where A is at least one selected from P, B and As; B is at least one selected from alkali metal and alkali earth metal; and C is at least one selected from Mn, Mg, Sn, Pb, Fe, Sb, Mo, W and RE. The catalyst is suitable for use in fluidized bed and has the feature of high benzonitrile yield. It may be used in industrial production.
Description
The present invention relates to be used to prepare the fluid catalyst of cyanobenzene.
Cyanobenzene is the important organic raw material of organic synthesis, be mainly used in the raw material of the benzoguanamine that serves many purposes, the high boiling solvent that also can be used as paint, printing-ink and resin etc. also can be used as intermediates such as oxidation inhibitor, dyeing carrier, fuel dope, agricultural chemicals, veterinary drug.
Simple, the most most economical manufacture method of cyanobenzene is that toluene gas phase oxidative ammonolysis under catalyst action obtains, and its core technology is a catalyzer.
The ammoxidation of aromatic hydrocarbon technology starts from the clear and electrician of the fifties Japan, be to adopt the synthetic Isophthalodinitrile production technology of ammoxidation of m-xylene fixed bed, the seventies Mitsubishi gas and U.S. Badger company cooperate and have developed fine particle fluidisation bed Isophthalodinitrile full scale plant afterwards, be mainly used in the production m-benzene diisocyanate, cause the ammoxidation of aromatic hydrocarbon state of the art to obtain large development.
In ammoxidation of aromatic hydrocarbon catalyzed reaction technology, the V series catalysts is the most general and effective a kind of catalyst system.General simple vanadium component or the vanadium of using of early stage catalyzer is furnished with other a small amount of composition, and its overall activity is too high, and selectivity is relatively poor, and yield is lower.Form development from recent catalyzer, mainly contain V-Sb, V-Cr, three kinds of compositions of Sb-Fe.Sb good catalyst activity, but because the Sb Preparation of Catalyst is complicated and reactor had factor such as particular requirement makes this catalyzer especially unreasonable to the economy of the industrial technology of many kinds of short run ammoxidation of aromatic hydrocarbon product.Opposite V-Cr Preparation of Catalyst is simple relatively, and good reproducibility has high reaction activity and high to ammoxidation of aromatic hydrocarbon, but the catalyst activity of two components is too high, easily causes deep oxidation, and ammonia is had stronger capacity of decomposition, causes generating a large amount of CO
2, CO, H
2O, HCN make reaction needed excessive N H greatly
3, can increase the three wastes and handle burden.
Existing cyanobenzene production technology mainly is the coarse particles fluid catalyst with immersion process for preparing that adopts V-Cr to form, aggregate level is lower, its deficiency on original catalysis is formed, also because the distribution of particle sizes and the reactor of catalyzer have influenced oxidative ammonolysis fluidization quality, cause at present existing coarse particles baffle plate reactor diameter in 600 millimeters of φ, can have serious engineering scale effect if reactor continues amplification.
Make a general survey of V-Cr catalyzer basis and form development, roughly divide ternary, quaternary, five-tuple to become:
Ternary is formed: V-Cr-B (US 4963387); V-Cr-Ba (JP61-4388).
V-Cr-B three components are with Al
2O
3Make carrier, under 398 ℃ of temperature, the fixed bed examination, cyanobenzene yield 83.9%, this catalyzer is along with the growth in reaction times, and catalytic activity has downtrending, is difficult to industrialization; V-Cr-Ba makes carrier with SiC, under 370 ℃ of temperature, and fixed bed examination, cyanobenzene yield 82.3%.
Quaternary is formed: V-Cr-B-Mo/SiO
2(JP01-275551), V-Cr-B-P/SiO
2(JP76-15028), V-Cr-Sn-P/SiO
2(the clear 45-19285 of JP) catalyzer is respectively by Mitsubishi gas and the disclosed patent of Japanese chemical gas companies, be respectively under 410 ℃, 412 ℃, the 435 ℃ conditions in temperature, fixed bed is estimated the best yield 83.3% of cyanobenzene lab scale and 85.2%, 83.2%, the subject matter of its catalyzer: one, reactive behavior, stable not ideal enough; Though two, catalytic perfomance increases on the basis of former three components, the reaction by-product is CO, CO especially
2, HCN amount is still higher.The nineties Mitsubishi gas has been announced V-Cr-B-P-Mo/SiO
2(JP05-170724) five catalyzer of forming, but this composition catalyzer is pointed out necessary expensive phospho-molybdic acid or the ammonium phosphomolybdate raw material of using, and just can obtain the ideal reaction result.
It may be noted that simultaneously above-mentioned conclusion all is the fixed bed evaluation result.Show according to research and commerical test experience, same catalyzer is checked and rated in the different reactor of fixed bed and fluidized-bed, its result has certain difference, general fixed bed is investigated the result, its cyanobenzene yield is than the fluidisation height of bed 3～5%, so the real standard of the difficult true reflection fluid catalyst of above-mentioned catalyzer.
The objective of the invention is in order to overcome in the conventional art, the cyanobenzene catalyzer only is suitable for fixed bed and investigates, and investigates the not high enough shortcoming of cyanobenzene yield as a result on fluidized-bed.A kind of new fluid catalyst that is used to prepare cyanobenzene is provided.This catalyzer has can be suitable for fluidized bed process, and keeps the characteristics of high cyanobenzene yield.
The objective of the invention is to realize by following technical scheme: a kind of fluid catalyst that is used to prepare cyanobenzene, form by silica supports with the following composition of atomic ratio measuring chemical formula:
V
1.0Cr
aA
bB
cC
dO
x
In the formula: A is selected from least a among P, B or the As;
B is selected from least a in basic metal or the alkaline-earth metal;
C is selected from least a in Mn, Mg, Sn, Pb, Fe, Sb, Mo, W or the rare earth element;
The span of a is 0.3～3.0;
The span of b is 0.02～3.0;
The span of c is 0.01～2.5;
The span of d is 0.01～2.0;
X satisfies the required oxygen atomicity of each element valence in the catalyzer;
The carrier dioxide-containing silica is 30～80% by weight percentage in the catalyzer.
The value preferable range of a is 0.5～2.5 in the technique scheme, and the value preferable range of b is 0.02～1.0, and the value preferable range of c is 0.01～0.9, and the value preferable range of d is 0.02～1.5; The basic metal preferred version is for being selected from Li, Na, K or Cs; The alkaline-earth metal preferred version is selected from Ca or Ba.
Preparation of Catalyst of the present invention is the fluid catalyst technology that adopts spraying to be shaped, and this catalyzer has overcome catalyticreactor engineering scale effect effectively and moved problem such as heat.The present invention has reduced by-product CO by add physics, the chemical property that suitable acidic oxide, basic metal and/or alkaline earth metal oxide and the above metal oxide of divalence have changed catalyzer on the basis of V, Cr catalyst component
2, CO, HCN growing amount, reached the purpose that improves the cyanobenzene reaction yield, make the catalyzer that makes, in fluidized-bed, check and rate, the cyanobenzene yield has been up to 85.4%, obtained effect preferably, the wherein application of acidic oxide element in the A component has improved catalyst activity and use properties; The basic metal and the alkali earth metal component that add the B component have strengthened catalyst abrasion intensity, have improved reaction preference; When catalyzer simultaneously of the present invention uses industrial raw material cheap and easy to get to prepare, can obtain good reaction activity equally.
Catalyzer deconditioning of the present invention also is adapted to the operation of fixed bed and moving-burden bed reactor, and all has good catalytic activity beyond the fluidized-bed reactor operation.
V
2O
5, Cr
2O
3And the corresponding oxide compound of each element of general formula A, B, C is the starting raw material of catalyzer of the present invention, also can select other compound of making through proper method raw material for catalyst component of the present invention.Example:
Vanadium raw materials: ammonium meta-vanadate, Vanadosulfuric acid, organic acid vanadium such as vanadium oxalate, tartrate vanadium;
Cr materials: chromic acid, chromic salt (ammonium), chromic anhydride, chromium nitrate, chromium+oxalic acid, chromic tartrate;
A raw material: pairing acid of the oxide compound of selected element or sour ammonium;
B raw material: the nitrate of selected element or the oxide compound of its element;
C raw material: the oxide compound of selected element nitrate or its element or the compound of solubility;
Silicon raw material: can use silicon sol, silicon gel or silicon-dioxide carrier as catalyzer.
Preparation of catalysts method of the present invention: A, B, the C solution of solubility are added to V
2O
5, Cr
2O
3Oxalic acid solution in, add three solution must suspend material mixture the time, but add then spent glycol etc. of solvent as needs, evaporation then, slurry be through spraying be shaped dry, roasting, finished catalyst.The fixed bed catalyst slurry is through evaporation after drying, roasting.
The roasting of catalyzer of the present invention under air conditions, but each element decomposition of salts and two stages of high-temperature roasting in the divided catalyst.The preroasting of catalyzer is influential to reactive behavior, generally 200～400 ℃ of following preroastings; 450～800 ℃ of maturing temperatures are suitable for 450～650 ℃, and the time is 2～15 hours; Decomposition and roasting can be carried out in two stoving ovens, also can carry out in a stoving oven, or will decompose in the continous way rotary roasting furnace with roasting and carry out simultaneously.
Oxide content is with V in the catalyzer of the present invention
2O
5, Cr
2O
3Weight percent meter with the element maxivalence oxide compound of acidic oxide, basic oxide and the above metal of divalence etc.
The ammonia oxidation aroamtic hydrocarbon raw material that catalyzer of the present invention is suitable for is alkylbenzene or substituting group alkylbenzene.Wherein alkyl can be methyl, ethyl, n-propyl, sec.-propyl etc.; Substituting group can be alkyl, non-substituting group, can be a substituting group, disubstituted and three substituting groups simultaneously; Main as toluene, o-Xylol, m-xylene, p-Xylol, sym-trimethylbenzene etc.; The embodiment of the invention is a toluene.
When catalyzer of the present invention was oxygen source with the air, the concentration of substituting group alkylbenzene in mixture was 0.1～10.0% (volume), preferable range 0.2～5.0% (volume).
The ammonia usage quantity of catalyzer of the present invention is theoretical amount at least, and excess of ammonia is favourable to reaction slightly, but has NH
3Recovery and pollute problem such as aftertreatment.This technology NH
3Amount is 2～13 times of theoretical amount, and preferable range is 3～10 times.
Catalyzer O of the present invention
2At least be theoretical amount, more suitable scope is 2～10 times.Usually make oxygen source with air, N
2, CO
2, water vapor also can be used as the thinner of reaction process rare gas element.
Catalyst process temperature of the present invention is 300～500 ℃, and preferable range is 330～450 ℃; Temperature is lower than 300 ℃, and reaction conversion ratio is low, and it is serious to be higher than 500 ℃ of deep oxidation reactions, CO
2, CO, HCN content obviously increase, fragrant nitrile yield descends.The optimum temps of this reaction depends on the various conditions and the factor such as roasting condition, reaction contact time, load of elementary composition, catalyzer of concentration, the catalyzer of the alkyl of aromatic hydrocarbons and substituent number, position, initiator, thereby a suitable reaction temperature is to change with above-mentioned condition.
The bigger scope of application is arranged the duration of contact of catalyzer of the present invention, and generally at 0.2～20 second, more suitable scope is 0.5～15 second.
Catalyzer of the present invention reacts under normal pressure usually, also can depress reaction adding.
Catalyzer of the present invention and technology both can be used for fluidized-bed, can be used for moving-bed and fixed bed again.
Catalyzer of the present invention transformation efficiency, cyanobenzene selectivity and the cyanobenzene once through yield of toluene in an embodiment is defined as follows:
It is to carry out in 38 millimeters * 1800 millimeters stainless steel fluidized-bed reactors of φ that catalyzer embodiment of the present invention investigates, add-on 550 grams of catalyzer, and reacting system pressure is 0.01MPa.
The invention will be further elaborated below by embodiment.[embodiment 1]
Preparation of Catalyst:
224 gram V
2O
5Be added to the temperature of forming by 490 ml waters 468 gram oxalic acid and be in 80～90 ℃ the solution, fully stirring, react vanadium oxalate solution.
With concentration expressed in percentage by weight is 40%SiO
2Silicon sol 1250 grams under agitation slowly are added in the above-mentioned solution, add respectively then by 838.4 gram Cr (NO
3)
39H
2The solution that O and 300 ml waters are formed, 91.4 gram H
3BO
3The solution of forming with 560 ml waters and 43.5 restrains (NH
4)
6Mo
7O
244H
2The solution that O and 50 ml waters are formed adds 12.4 gram KNO at last
3, stirring, heating evaporation gets viscous paste to solid content 42% (weight).
Above-mentioned slurry spraying is shaped, and the catalyzer after the shaping, gets catalyzer and forms with atomic ratio then 650 ℃ of roastings 4.5 hours in 300 ℃ of preroastings 2 hours:
V
1.00Cr
0.85B
0.60P
0.10Mo
0.10K
0.05/ SiO
2, catalyzer master weight-carrying capacity is than 50/50, and the median size of catalyzer is 200 orders.
The performance evaluation of catalyzer:
Technology: toluene: ammonia: air=1: 4: 20 (mole)
Load 50 gram/grams hour
425 ℃ of temperature of reaction
Result: toluene conversion 98.6%
Cyanobenzene selectivity 86.3%
Cyanobenzene yield 85.4%[embodiment 2～12]
Method for preparing catalyst changes the proportioning or the composition of catalyzer with embodiment 1, must form by table 1 catalyzer, presses the evaluation of embodiment 1 evaluating catalyst method simultaneously.Its results list 1.
Table 1
[comparative example 1～3]
| Embodiment | Catalyzer | Toluene conversion % | Cyanobenzene selectivity % | Cyanobenzene yield % |
| ???2 | ?V 1.00Cr 0.85B 0.60P 0.10Na 0.05 | ????99.5 | ????81.8 | ????81.4 |
| ???3 | ?V 1.00Cr 0.85B 0.60P 0.10Ba 0.04 | ????99.6 | ????83.4 | ????83.1 |
| ???4 | ?V 1.00Cr 0.85B 0.50P 0.40K 0.03Ba 0.03 | ????95.5 | ????86.5 | ????82.6 |
| ???5 | ?V 1.0Cr 0.90B 0.50P 0.50W 0.10Fe 0.10Na 0.05 | ????97.0 | ????80.0 | ????77.6 |
| ???6 | ?V 1.00Cr 1.0B 0.50Mo 0.01Na 0.05 | ????97.0 | ????85.3 | ????83.5 |
| ???7 | ?V 1.00Cr 0.92B 0.40P 0.20Mo 0.05W 0.05Na 0.05 | ????97.6 | ????85.4 | ????82.7 |
| ???8 | ?V 1.00Cr 0.92B 0.10P 0.10K 0.05 | ????96.0 | ????81.6 | ????78.4 |
| ???9 | ?V 1.00Cr 0.85Fe 0.10Sb 0.30 | ????94.0 | ????82.3 | ????77.4 |
| ???10 | ?V 1.00Cr 0.80B 0.50P 0.30W 0.10Na 0.03 | ????96.0 | ????80.6 | ????77.3 |
| ???11 | ?V 1.00Cr 0.70B 0.60P 0.40Fe 0.10Na 0.02 | ????99.6 | ????77.4 | ????77.1 |
| ???12 | ?V 1.00Cr 0.90B 0.20Mo 0.10Ba 0.04 | ????98.4 | ????82.4 | ????81.1 |
Method for preparing catalyst is with embodiment 1, and the proportioning of catalyzer or composition and embodiment 1～12 catalyzer contrast, and must form by table 2 catalyzer, presses the evaluation of embodiment 1 evaluating catalyst method simultaneously.Its results list 2.
Table 2
[embodiment 13]
| Embodiment | Catalyzer | Toluene conversion % | Cyanobenzene selectivity % | Cyanobenzene yield % |
| ????1 | ?V 1.00Cr 0.85B 0.60P 0.10Mo 0.10 | ????99.6 | ????81.6 | ????81.3 |
| ????2 | ?V 1.00Cr 1.00B 0.20Mo 0.20 | ????98.8 | ????80.3 | ????79.4 |
| ????3 | ?V 1.00Cr 0.85B 0.60P 0.10 | ????99.0 | ????80.9 | ????80.1 |
Press embodiment 1 method for preparing catalyst and composition, produce 2.0 tons of industrial catalysts, one-time pad is in 500 tons of/year cyanobenzene fluidized-bed reactors, and carry out industrial production by example 1 technology assessment condition, catalyzer shows that through industry operation demarcation half a year catalyzer has good activity and stable.Its result is as follows:
Toluene conversion 99.5%
Cyanobenzene selectivity 85.1%
Cyanobenzene yield 84.7%[embodiment 14]
Carry out fixed bed by embodiment 1 catalyzer composition and processing condition and investigate evaluation, its appraisal result is as follows:
Toluene conversion 99.0%
Cyanobenzene selectivity 89.8%
Cyanobenzene yield 88.9%
Claims (7)
1, a kind of fluid catalyst that is used to prepare cyanobenzene, form by silica supports with the following composition of atomic ratio measuring chemical formula:
V
1.0Cr
aA
bB
cC
dO
x
In the formula: A is selected from least a among P, B or the As;
B is selected from least a in basic metal or the alkaline-earth metal;
C is selected from least a in Mn, Mg, Sn, Pb, Fe, Sb, Mo, W or the rare earth element;
The span of a is 0.3～3.0;
The span of b is 0.02～3.0;
The span of c is 0.01～2.5;
The span of d is 0.01～2.0;
X satisfies the required oxygen atomicity of each element valence in the catalyzer;
The carrier dioxide-containing silica is 30～80% by weight percentage in the catalyzer.
2,, it is characterized in that basic metal is selected from Li, Na, K or Cs according to the described fluid catalyst that is used to prepare cyanobenzene of claim 1.
3,, it is characterized in that alkaline-earth metal is selected from Ca or Ba according to the described fluid catalyst that is used to prepare cyanobenzene of claim 1.
4, according to the described fluid catalyst that is used to prepare cyanobenzene of claim 1, the span that it is characterized in that a is 0.5～2.5.
5, according to the described fluid catalyst that is used to prepare cyanobenzene of claim 1, the span that it is characterized in that b is 0.02～1.0.
6, according to the described fluid catalyst that is used to prepare cyanobenzene of claim 1, the span that it is characterized in that c is 0.01～0.9.
7, according to the described fluid catalyst that is used to prepare cyanobenzene of claim 1, the span that it is characterized in that d is 0.02～1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00127436 CN1102577C (en) | 2000-11-15 | 2000-11-15 | Fluidized bed catalyst for preparing benzonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00127436 CN1102577C (en) | 2000-11-15 | 2000-11-15 | Fluidized bed catalyst for preparing benzonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351989A true CN1351989A (en) | 2002-06-05 |
| CN1102577C CN1102577C (en) | 2003-03-05 |
Family
ID=4592451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00127436 Expired - Lifetime CN1102577C (en) | 2000-11-15 | 2000-11-15 | Fluidized bed catalyst for preparing benzonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1102577C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721729A (en) * | 2013-12-17 | 2014-04-16 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compound |
| CN105085315A (en) * | 2014-05-04 | 2015-11-25 | 中国科学院大连化学物理研究所 | Method for preparing nitrile compounds by catalytic oxidation of amine |
-
2000
- 2000-11-15 CN CN 00127436 patent/CN1102577C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721729A (en) * | 2013-12-17 | 2014-04-16 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compound |
| CN105085315A (en) * | 2014-05-04 | 2015-11-25 | 中国科学院大连化学物理研究所 | Method for preparing nitrile compounds by catalytic oxidation of amine |
| CN105085315B (en) * | 2014-05-04 | 2017-02-22 | 中国科学院大连化学物理研究所 | Method for preparing nitrile compounds by catalytic oxidation of amine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1102577C (en) | 2003-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1255215C (en) | Improved catalyst for the manufacture of acrylonitrile | |
| CN102527419A (en) | Method for preparing m-phthalodinitrile catalyst through ammoxidation | |
| CN1102577C (en) | Fluidized bed catalyst for preparing benzonitrile | |
| CN1102576C (en) | Fluidized bed catalyst for ammoxidating propylene to prepare acrylonitrile | |
| CN1204114C (en) | Method for preparing m-phthalonitrile | |
| CN1136980C (en) | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile | |
| CN1223579C (en) | Method for preparing p-chloro cyanobenzene | |
| CN1123385C (en) | Fluidized-bed catalyst for preparing isophthalonitrile | |
| CN1187320C (en) | Fluidized bed catalyst for preparing o-chlorobenzonitrile | |
| CN1193009C (en) | Method for producing o-chlorobenzonitrile | |
| CN102219710A (en) | Method for preparing cyanobenzene | |
| CN103664696A (en) | Method for preparing cyanobenzene | |
| CN1204113C (en) | Preparation of tephthalyl intrile | |
| CN1207278C (en) | Prepn process of o-chlorobenzonitrile | |
| CN1212187C (en) | Fluidized bed catalyst for preparing acrylonitrile | |
| CN1101264C (en) | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation | |
| CN1810364A (en) | Fluid-bed catalyst for ammoxidation to prepare acrylonitrile | |
| CN1094073C (en) | Fluidized bed catalyst for production of acrylonitrile | |
| CN1810358A (en) | Acrylonitrile fluid bed catalyst | |
| CN1099316C (en) | Catalyst for acrylonitrile fluid bed | |
| CN1100612C (en) | Fluidized bed catalyst for oxidation of propene ammonia | |
| CN1107541C (en) | Fluid bed catalyst for acrylonitrile production | |
| CN1212185C (en) | Fluidized bed catalyst for preparing acrylonitrile by ammonia oxidation of propene | |
| CN102746192A (en) | Method for ammoxidation preparation of 2,4-dichlorobenzonitrile | |
| CN102040543B (en) | Method for producing unsaturated nitrile through ammoxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030305 |
|
| CX01 | Expiry of patent term |