CN106268890B - Ammoxidation of aromatic hydrocarbon fluid catalyst, preparation method and purposes - Google Patents
Ammoxidation of aromatic hydrocarbon fluid catalyst, preparation method and purposes Download PDFInfo
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- CN106268890B CN106268890B CN201610634733.XA CN201610634733A CN106268890B CN 106268890 B CN106268890 B CN 106268890B CN 201610634733 A CN201610634733 A CN 201610634733A CN 106268890 B CN106268890 B CN 106268890B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/30—Tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
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Abstract
The present invention relates to ammoxidation of aromatic hydrocarbon fluid catalysts of a kind of high abrasion and preparation method thereof.It is poor mainly to solve existing ammoxidation of aromatic hydrocarbon fluid catalyst wear-resisting property, the technical issues of rate of catalyst loss is high, high production cost.By preparing by carrier and forming V with the following composition of atomic ratio measuring chemical formula1.0CraAbBcCdMeOxMixed catalyst, wherein A is selected from least one of P, B, Bi, Sb, As element；B is selected from least one of Mn, Ni, Co, Ti, Sn, Mo or rare earth element；C is selected from least one of alkali or alkaline earth metal；M is selected from least one of Zr, W；And the technical solution of the preparation method by strict control each component order of addition, the wearability of catalyst is effectively improved, gained catalyst can be used in the industrialized production of ammoxidation of aromatic hydrocarbon.
Description
Technical field
The present invention relates to a kind of ammoxidation of aromatic hydrocarbon fluid catalyst, preparation method and purposes；More particularly to a kind of high
Wear-resisting ammoxidation of aromatic hydrocarbon fluid catalyst, preparation method and purposes.
Background technique
Fragrant nitrile is a kind of important fine chemicals, can be used for producing medicine, pesticide, dyestuff and special material etc., purposes
It is very extensive.The important intermediate 2- cyanogen that multipurpose azo dispersion dyes can be made through nitrifying ammonolysis reaction such as o-chlorobenzonitrile
Base -4- nitre aniline；Biphenol compound is synthesized with halogeno-benzene and is used to prepare non-peptide type antiangiotensin, can also prepare a variety of anti-inflammatory
Germ killing drugs；High-efficiency low-toxicity fungicide termil, hydrogenated reaction system can be made through chlorination reaction in isophthalodinitrile
The m-xylene diamine obtained can be used for producing heatproof epoxy curing agent and synthesize extraordinary nylon and polyurethane；Benzonitrile can with it is double
The benzoguanamine that cyanamide reaction generates, for producing metallic paint, decorative panel, colorant and printing ink, additionally
It is the high boiling point polar organic solvent of function admirable.
The production of fragrant nitrile has the methods of chemical synthesis, gas phase ammonoxidation, wherein by aromatic hydrocarbons, ammonia and air through gas phase ammonoxidation
One-step synthesis fragrant nitrile is reacted, process is short, and pollution is few, is the main method of current fragrant nitrile production.The characteristics of reaction is that major-minor is anti-
It should all be strong exothermal reaction process.Thus, the selection of catalyst activity component and form and the selection of respective reaction device just seem
It is most important.
The gas phase ammonoxidation technique of aromatic hydrocarbons mainly includes fixed bed and fluidized-bed process, and fluid is in approximate flat-pushing in fixed bed
Stream movement, catalyst has greater catalytic efficiency, but its heat transfer property is poor, and enlarge-effect is obvious, and device enlargement is difficult；Stream
Changing bed accessory has the advantages that heat and mass is high-efficient, is easy to enlargement, but to fluidised form in catalyst physical chemical property and reactor
Change quality control to have higher requirements.
In the fluid catalyst of ammoxidation of aromatic hydrocarbon fragrant nitrile, V series catalysts are maximally efficient catalyst system, such as V-
P, the catalyst systems such as V-Cr are prepared into varigrained spheric granules and exist usually using aluminium oxide, silicon carbide, silica as carrier
It is applied in fluidized-bed reactor.The catalyst of early stage usually using compound systems such as V-P, V-Cr for simply forming as catalyst,
The selectively lower problem of generally existing fragrant nitrile.In recent years production fragrant nitrile fluid catalyst, mostly uses greatly multi-component V system to urge
Agent improves the selectivity of fragrant nitrile to a certain extent.
CN99113575.X is related to a kind of ammoxidation of m-xylene isophthalodinitrile fine grained fluid catalyst.This is urged
Agent contains silica supports and the following composition of chemical formula:V1.0CraAbBcCdOx, wherein A is selected from the oxide of P, B or As；
B is selected from least one of Li, Na, K or Cs oxide；C is selected from Mn, Mg, Sb, Pb, Fe, Mo, W or rare earth element.Originally it urges
Agent has that raw material is inexpensive, is easy to get, and has the characteristics that the active and higher isophthalodinitrile yield of sound response, mainly solves to show
Have the shortcomings that catalyst is difficult to adapt to fluidized bed requirement or poor using price more expensive raw material or reaction selectivity in technology.
CN02137455.4 is related to a kind of method for preparing para-Phthalonitrile, by using with paraxylene, ammonia and oxygen
For raw material, it is expressed as follows using activity composition chemical general formula in catalyst:V1.0CraTibAcBdCeOx, wherein A be selected from P,
B, at least one of Bi, Sb or As；B is selected from least one of alkali metal or/and alkaline-earth metal；C be selected from Mn, Ni, Co,
The technical solution of at least one of Pb, Fe, Mo, W or rare earth element solves conventional art and is often suitable for fixing there are catalyst
Bed examination, and check and rate in a fluidized bed, often yield is low for purpose product, and reactor has engineering enlarge-effect.
CN201010147809.9 is related to a kind of ammoxidation catalyst containing antimony, by using catalyst activity component
VSbaAbBcCdOx, wherein A is selected from least one of alkali metal；B be selected from Mg, Ca, Ba, Cr, W, Mo, Mn, Fe, Co,
At least one of Ni or Sn；C is the technical solution selected from least one of B or P, and resulting catalyst can be used for isophthalic two
The industrial production of formonitrile HCN.
CN201210240053.1 is related to a kind of method for preparing o-chlorobenzonitrile, by using a kind of fluidized bed catalytic
Agent, for the catalyst with silica supported, active component is VPaXbYcZdOm with atomic ratio measuring general formula, wherein X be selected from B or
At least one of oxide of As；Y is selected from least one of alkali or alkaline earth metal oxide；Z be selected from Ni, Co, Pb,
It is negative to solve prior art o-chlorobenzonitrile yield low reaction for the technical solution of at least one of the metal oxide of Fe, Mo or W
The small problem of lotus.
Although foregoing invention has many researchs to ammoxidation of aromatic hydrocarbon fluid catalyst, for the wearability of catalyst
Can but rarely have and refer to.In ammoxidation of aromatic hydrocarbon production, the characteristic of fluidized-bed reactor determines it for the wearability of catalyst
There is high requirement, catalyst wears no resistance, and will cause fluidization quality in reactor and declines, and catalyst loss amount is big,
The problems such as stability declines, frequent catalyst, which is added and replaced, can greatly promote cost, seriously affect ammoxidation of aromatic hydrocarbon
Industrial production.A kind of ammoxidation of aromatic hydrocarbon catalyst is disclosed in US 6429330, with V-Cr-Sb-Fe-B-Mo etc. for main group
Point, the catalyst for being added to the elements such as Fe, Sb has optimal wear resistance, rate of wear about 2.1%-2.6%.CN103896807 is public
A kind of fine grained fluid catalyst for preparing para-Phthalonitrile has been opened, has been used as main group using V-Cr-P-B-Mo-Co-K etc.
Point, best rate of wear can reach 1.5%-1.6%.
The side such as auxiliary agents such as Fe, Sb, P is added by using the carrier of wearability in above-mentioned these catalyst reported in the literature
Method improves the wearability of catalyst, but satisfactory level cannot be still fully achieved in its rate of wear.For expensive aromatic hydrocarbons ammonia
For aoxidizing fluid catalyst, its wearability how is further increased, and guarantee the activity yield of catalyst simultaneously, to promotion
The economic and technical level of ammoxidation of aromatic hydrocarbon catalyst is of great significance.
Summary of the invention
The present invention provides a kind of high abrasion ammoxidation of aromatic hydrocarbon fluid catalyst and preparation method thereof, to solve existing catalysis
The problem of agent wear-resisting property is poor, loss amount is higher, poor catalyst activity.The height prepared by preparation method is resistance to through the invention
Catalyst is ground, there is splendid wear-resisting property, maintain preferable catalytic activity, can effectively reduce in production process
Catalyst consumption keeps stablizing for ammoxidation of aromatic hydrocarbon production to carry out.
In order to solve the above technical problems, technical scheme is as follows：
A kind of ammoxidation of aromatic hydrocarbon fluid catalyst, including carrier and the composition following with atomic ratio measuring chemical formula：
V1.0CraAbBcCdMeOx
In formula：A is selected from least one of P, B, Bi, Sb, As element；
B is selected from least one of Mn, Ni, Co, Ti, Sn, Mo or rare earth element；
C is selected from least one of alkali or alkaline earth metal；
M is selected from least one of Zr, W.
Wherein
The value range of a is 0.4~2.0；
The value range of b is 0.2~2.0；
The value range of c is 0~1.0；
The value range of d is 0~0.2；
The value range of e is 0.01~0.3；
X is to meet oxygen atomicity needed for each element chemical valence in catalyst.
V2O5、Cr2O3And general formula A, B, C, M each element corresponds to the starting material that oxide is catalyst of the present invention, it can also be with
It selects through other compounds made from proper method to be the raw material of catalyst component of the present invention.
In above-mentioned technical proposal, it is preferred that carrier be selected from silica, aluminium oxide, silica solution, waterglass, Aluminum sol, intend it is thin
At least one of diaspore, titanium oxide, zirconium oxide, magnesia, molecular sieve.
In above-mentioned technical proposal, molecular sieve is preferably Si-Al molecular sieve or pure silicon molecular sieve.
In above-mentioned technical proposal, it is furthermore preferred that carrier is selected from silica, aluminium oxide, titanium oxide, zirconium oxide, magnesia, divides
One of son sieve.
Carrier described in above-mentioned catalyst, it is characterised in that the carrier is silica or aluminium oxide.Silica herein
Or aluminium oxide refers to the catalyst substance that carrier is presented wherein after final roasting.Not equivalent to prepared by catalyst
Added substance in the process.
Carrier described in above-mentioned catalyst, it is characterised in that in terms of catalyst weight percent, vector contg be 30%~
70%；More preferably 40~60%；In this weight range, made catalyst is able to maintain that preferable catalytic performance, compares table
Area and intensity.
The more preferably value range of a is 0.5~1.5 in above-mentioned catalyst activity component；More preferably 0.7~1.2.
The more preferably value range of b is 0.5~1.8 in above-mentioned catalyst activity component；More preferably 0.7~1.5.
In above-mentioned technical proposal, it is preferred that the value range of c is to be less than or equal to 1.0 greater than 0；It is furthermore preferred that the value of c
Range is 0.1~0.8；Most preferably the value range of c is 0.2~0.6.
In above-mentioned technical proposal, it is preferred that the value range of d is to be less than or equal to 0.3 greater than 0；It is furthermore preferred that the value of d
Range is 0.05~0.2；Most preferably the value range of d is 0.08~0.15.
In above-mentioned technical proposal, it is preferred that the value range of e is 0.02~0.25；Preferably, the value range of e is
0.05~0.2；Most preferably the value range of e is 0.08~0.15.
In above-mentioned technical proposal, it is preferred that A is selected from least one of P, Bi, Sb, As element；It is furthermore preferred that A is selected from
P, one of Bi, Sb, As element；It is furthermore preferred that A is selected from one of Bi, Sb, As element.
In above-mentioned technical proposal, it is preferred that A is selected from least one of P, B, Bi, As element.
In above-mentioned technical proposal, it is preferred that A is selected from B.
In above-mentioned technical proposal, it is preferred that A is selected from P and B.
In above-mentioned technical proposal, it is preferred that B is selected from least one of Mn, Ni, Co, Ti；It is furthermore preferred that B be selected from Mn,
One of Ni, Co, Ti；Preferably, B is selected from Mo and Co.
In above-mentioned technical proposal, it is preferred that B is selected from Mo；Preferably, B is selected from Sn.
In above-mentioned technical proposal, it is preferred that B is selected from least one of rare earth element.
In above-mentioned technical proposal, it is preferred that C is selected from one of alkali or alkaline earth metal.
In above-mentioned technical proposal, it is preferred that C is selected from alkali metal.
In above-mentioned technical proposal, it is preferred that when containing alkali metal in catalyst, alkali metal is preferably in K, Cs or Rb
It is at least one；It is furthermore preferred that alkali metal is preferably one of K, Cs or Rb.
In above-mentioned technical proposal, it is preferred that C is selected from alkaline-earth metal；It is furthermore preferred that C is selected from least one of Mg and Sr；
It is furthermore preferred that the molar ratio of Mg and Sr is (1:4)~(4:1).
In above-mentioned technical proposal, it is preferred that M is selected from Zr and/or W；Preferably, the molar ratio of Zr and W is 0~10 in M；It is excellent
Choosing, the molar ratio of Zr and W is 0.01~10 in M；It is furthermore preferred that the molar ratio of Zr and W is 0.01~5 in M；It is furthermore preferred that M
The molar ratio of middle Zr and W is 0.1~5；It is furthermore preferred that the molar ratio of Zr and W is 0.2~5 in M；Most preferably, Zr and W in M
Molar ratio is 0.2~0.5.
In above-mentioned technical proposal, it is preferred that carrier is preferably Silicate-1 and SiO2；It is furthermore preferred that Silicate-1
And SiO2Molar ratio be (1:5)：(5:1).
Above-mentioned catalyst wear-resisting property with higher, it is characterised in that the attrition of catalyst rate can be achieved to be lower than
1.5%.The rate of wear is measured using high-speed air gunite.
In above-mentioned technical proposal, the test of rate of wear, which uses, meets the ASTM D5757-00 (method consumed with air jet mill
To judge the relative wear characteristic of fine catalyst) test method of standard carries out.
It is weight wt%/hour that finished catalyst, which measures rate of wear unit,.
Above-mentioned high abrasion ammoxidation of aromatic hydrocarbon fluid catalyst, it is characterised in that the average grain diameter of catalyst is 10-100 μ
m.Particularly preferably 30-80 μm.
In above-mentioned technical proposal, the preparation method of ammoxidation of aromatic hydrocarbon fluid catalyst is comprised the steps of：
1) it will be added in solvent containing the compound of V, Cr, A, B, C element and be persistently stirred to form mixed solution I；
2) mixed solution I is added in carrier or compound containing carrier and forms mixed solution II after continuing stirring；
3) mixed solution II is added in the compound containing M element and heating is concentrated solution；
4) solution after concentration is spray-dried to obtain presoma；
5) finished catalyst is obtained after roasting presoma.
Solvent described in above-mentioned preparation method by water, alcohol, polyalcohol or other to the V, Cr, A, B, C element being added
Compound have deliquescent substance.Use of water is preferred, and cost is relatively low and preparation is convenient.
Carrier compound described in above-mentioned preparation method can be silica, aluminum oxide, silica solution, waterglass,
Or mixtures thereof Aluminum sol, boehmite.Wherein it is preferable to use silica solution and waterglass.
M element compound described in above-mentioned preparation method can be organic gold of zirconium oxide, zirconium hydroxide, zirconium nitrate, zirconium
Belong to salt, tungstates, phosphotungstic acid, tungsten carbide.The addition of M element compound advantageously improves catalyst wear-resisting property, but it is added
Time has great influence to the promotion of wear-resisting property, is preferably added in the final stage of preparation.
Above-mentioned preparation method, it is characterised in that solid content is 20wt%-60wt% after the mixed solution concentration.Favorably
The fluid catalyst particle of the partial size needed for spray drying is formed.
In above-mentioned technical proposal, the purposes of catalyst is as follows：
A method of isophthalodinitrile being prepared, using meta-xylene, ammonia, air or oxygen as reaction raw materials, above-mentioned
It is 300~500 DEG C in reaction temperature, reaction pressure is calculated as normal pressure~0.30MPa, catalyst with gauge pressure in the presence of catalyst
Load is 0.02~0.20 hour-1WWH, meta-xylene: ammonia: the molar ratio of air and/or oxygen is 1: (1~13): (20~
60) reaction generates isophthalodinitrile under conditions of.
In above-mentioned technical proposal, it is preferred that reaction temperature is 380-450 DEG C；
In above-mentioned technical proposal, it is preferred that reaction pressure is calculated as 0.01~0.1MPa with gauge pressure；
In above-mentioned technical proposal, it is preferred that catalyst loading is 0.03-0.1 hours-1WWH。
A method of o-chlorobenzonitrile being prepared, using ortho-chlorotolu'ene, ammonia, air or oxygen as reaction raw materials, above-mentioned
In the presence of catalyst, reaction temperature is 300~500 DEG C, and reaction pressure is for normal pressure to 0.30MPa, catalyst loading WWH
0.02~0.20h-1, reaction raw materials molar ratio is ortho-chlorotolu'ene: ammonia: air=1: (1~13): being reacted under conditions of (20~60)
Generate o-chlorobenzonitrile.
A method of it being used to prepare benzonitrile, using toluene, ammonia, air or oxygen as raw material, is matched in feed molar：
Toluene:Ammonia:Air=1:(2~10):(10~50), reaction temperature be 300~500 DEG C, reaction pressure be 0.01~
0.1Mpa, catalyst weight load (WWH) are 0.03~0.1 hour-1Under conditions of, raw material and above-mentioned catalyst haptoreaction are raw
At benzonitrile.
A method of it being used to prepare fragrant nitrile, using aromatic hydrocarbons, ammonia, air or oxygen as raw material, in depositing for above-mentioned catalyst
Under, matched in feed molar：Aromatic hydrocarbons:Ammonia:Air=1:(2~10):(10~50), reaction temperature are 300~500 DEG C,
Reaction pressure is 0.01~0.1Mpa, and catalyst weight load (WWH) is 0.03~0.1 hour-1Under conditions of, raw material and catalysis
Agent haptoreaction generates fragrant nitrile.
In above-mentioned technical proposal, it is preferred that crude oil is that the carbon atom being connected with aromatic ring has hydrogen atom coupled.
Such as toluene, ethylbenzene, benzyl halide, dimethylbenzene, dihalotoluene.
The conversion ratio of middle aromatic hydrocarbons, fragrant nitrile selectivity and fragrant nitrile yield are defined as follows in technical solution of the present invention：
Catalyst of the invention can be applied in the fluidized-bed reactor of conventional design, as long as usually guaranteeing the fluidised form of air-flow
Change quality, reduce the generation of improper fluidisation phenomenon in fluid mapper process " bubble ", " channel " and " slugging " etc., while reducing as far as possible
The degree of air-flow back-mixing, to improve the selectivity of reaction.
The roasting of catalyst of the present invention can be divided into two stages of decomposition and high-temperature roasting of each element salt in catalyst.Point
Solution and high-temperature roasting can carry out in two roasters, can also carry out in a roaster, or in continous way rotary calcination
Decomposition and high-temperature roasting are carried out in furnace simultaneously.
Using technical solution of the present invention, W and Zr is introduced in catalyst composition by the way that step is particularly added, is significantly mentioned
The high wearability of catalyst, technical solution of the present invention there is no particular requirement that the average grain diameter or partial size of catalyst,
Different particle diameter distributions can obtain good activity and wear hardness；
In the art, since the research for ammoxidation of aromatic hydrocarbon attrition of catalyst rate is relatively mature, therefore identical
Under the conditions of the promotion of rate of wear 0.01wt%/h be also highly difficult, it is also desirable to pay creative labor.
Compared with conventional catalyst, about 25% can be reduced using attrition of catalyst rate prepared by technical solution of the present invention, together
When catalyst still there is good catalytic effect, achieve good technical effect.
The present invention will be further described below by way of examples, but range not thereby limiting the invention.
Specific embodiment
【Embodiment 1】
Catalyst preparation：
By 224 grams of V2O5With 187 grams of Cr2O3Being added by the temperature that 980 milliliters of water and 912 grams of oxalic acid form is 80~90 DEG C
Solution in, 2h is sufficiently stirred, obtains mixed solution.
By 85% phosphoric acid, 283.6 grams, 12.4 grams KNO3, 71.6 grams of Co (NO3)·6H2The solution of O and 500 milliliter of water composition,
76.4 gram H3BO3With the solution and 43.5 grams of (NH of 500 milliliters of water composition4)6Mo7O24·4H2The solution of O and 100 milliliter of water composition,
Concentration expressed in percentage by weight is 40%SiO21250 grams of silica solution is successively slowly added to the above-mentioned mixed solution containing vanadium and chromium under stiring
In, 2h is mixed, by 59g phosphotungstic acid, 21gZr (NO3)4·5H2O and 150 milliliter of water is added mixed solution and continues to stir
1h, heating evaporation obtain viscous paste to solution solid content 40% (weight).
Above-mentioned slurry is spray-dried to forming in spray dryer, the catalyst precarsor after forming is in 300 DEG C of preroasts 2
Hour, it is then roasted 4.5 hours at 650 DEG C, obtains catalyst and formed with atomic molar ratio：
V1Cr1P1B0.5Mo0.1Co0.1K0.05W0.1Zr0.02/ 50wt%SiO2, attrition of catalyst rate：1.18%.
The evaluation of catalyst carries out in 38 millimeters × 1800 millimeters stainless steel fluidized-bed reactors of φ, the addition of catalyst
550 grams of amount, raw material are meta-xylene, and reaction temperature is 420 DEG C, reaction pressure 0.05MPa, reaction velocity 0.05h-1
(WWH), material rate is 1 (meta-xylene)：10 (ammonias)：40 (air)；Evaluation result is shown in Table 2.
【Embodiment 2-20】
Catalyst is prepared using method same as Example 1, but adjusts each component additional amount, obtains urging for different content composition
Agent tests attrition of catalyst rate, as a result as shown in table 1 below respectively；Using the identical evaluation condition of embodiment 1, evaluation result
It is shown in Table 2.
【Embodiment 21】
Catalyst preparation：
By 224 grams of V2O5With 187 grams of Cr2O3Being added by the temperature that 980 milliliters of water and 912 grams of oxalic acid form is 80~90 DEG C
Solution in, 2h is sufficiently stirred, obtains mixed solution.
By 85% phosphoric acid, 283.6 grams, 12.4 grams KNO3, 71.6 grams of Co (NO3)·6H2O, 59g phosphotungstic acid, 21gZr
(NO3)4·5H2Solution, the 76.4 grams of H of O and 500 milliliter of water composition3BO3With the solution of 500 milliliters of water composition and 43.5 grams
(NH4)6Mo7O24·4H2Solution, the concentration expressed in percentage by weight 40%SiO of O and 100 milliliter of water composition21250 grams of silica solution are being stirred
Mix it is lower be successively slowly added in the above-mentioned mixed solution containing vanadium and chromium, 2h is mixed, then mixed solutions are added in 150 milliliters of water
And continue to stir 1h, heating evaporation obtains viscous paste to solution solid content 40% (weight).
Above-mentioned slurry is spray-dried to forming in spray dryer, the catalyst precarsor after forming is in 300 DEG C of preroasts 2
Hour, it is then roasted 4.5 hours at 650 DEG C, obtains catalyst and formed with atomic molar ratio：
V1.00Cr1.00P1.00B0.50Mo0.10Co0.10K0.05W0.10Zr0.02/ 50wt%SiO2,
Measuring attrition of catalyst rate is 1.47wt%/h.
【Comparative example 1-3】
Catalyst is prepared using method same as Example 1, but adjusts each component additional amount, obtains urging for different content composition
Agent tests attrition of catalyst rate, as a result as shown in table 1 below respectively；Using the identical evaluation condition of embodiment 1, evaluation result
It is shown in Table 2.
【Comparative example 4】
By the preparation method of patent CN201210576543.9 specification embodiment 1：
Catalyst preparation：
224 grams of V2O5With 187 grams of Cr2O3Being added to the temperature being made of 980 milliliters of water, 912 grams of oxalic acid is 80~90 DEG C molten
It in liquid, is sufficiently stirred, reacts to obtain oxalic acid vanadium solution.
It is 40%SiO by concentration expressed in percentage by weight21250 grams of silica solution are slowly added in above-mentioned solution under stiring, then divide
It Jia Ru not be by 85% phosphoric acid, 283.6 grams, 12.4 grams KNO3, 71.6 grams of Co (NO3)·6H2The solution of O and 500 milliliter of water composition,
76.4 gram H3BO3With the solution and 43.5 grams of (NH of 500 milliliters of water composition4)6Mo7O24·4H2The solution of O and 100 milliliter of water composition,
Stirring, heating evaporation obtain viscous paste to solid content 40% (weight).
Above-mentioned slurry is spray-dried to forming in spray dryer, the catalyst precarsor after forming is in 300 DEG C of preroasts 2
Hour, it is then roasted 4.5 hours at 650 DEG C, obtains catalyst and formed with atomic ratio：
V1.00Cr1.00P1.00B0.50Mo0.10Co0.1K0.05/SiO2, than 50/50, catalyst is averaged the main loading capacity of catalyst
Partial size is 40 microns.
The test of the rate of wear of above-mentioned catalyst is used and meets the ASTM D5757-00 (method consumed with air jet mill
To judge the relative wear characteristic of fine catalyst) test method of standard carries out.Test obtained rate of wear be 1.92wt%/
h。
Table 1
Table 2
【Embodiment 26-37】
Using catalyst prepared by embodiment 1, it is anti-that gas phase ammonoxidation is carried out under differential responses raw material and reaction condition
It answers, reaction is carried out in 38 millimeters × 1800 millimeters stainless steel fluidized-bed reactors of φ, 550 grams of the additional amount of catalyst.
Acquired results are as shown in table 3 below.
Table 3
Claims (21)
1. a kind of ammoxidation of aromatic hydrocarbon fluid catalyst, including carrier and the composition following with atomic ratio measuring chemical formula：
V1.0CraAbBcCdMeOx
In formula：A is selected from least one of P, B, Bi, Sb, As element；
B is selected from least one of Mn, Ni, Co, Ti, Sn, Mo or rare earth element；
C is selected from least one of alkali or alkaline earth metal；
The molar ratio that M is selected from Zr and W, Zr and W is 0.2~0.5；
Wherein the value range of a is 0.4~2.0；The value range of b is 0.2~2.0；The value range of c be greater than 0 be less than etc.
In 1.0；The value range of d is to be less than or equal to 0.3 greater than 0；The value range of e is 0.01~0.3；X is to meet in catalyst respectively
Oxygen atomicity needed for element valence；
The preparation method of the ammoxidation of aromatic hydrocarbon fluid catalyst, comprises the steps of：
1) it will be added in solvent containing the compound of V, Cr, A, B, C element and be persistently stirred to form mixed solution I；
2) mixed solution I is added in carrier or compound containing carrier and forms mixed solution II after continuing stirring；
3) mixed solution II is added in the compound containing M element and heating is concentrated solution；
4) solution after concentration is spray-dried to obtain presoma；
5) finished catalyst is obtained after roasting presoma.
2. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the carrier be selected from silica,
At least one of aluminium oxide, titanium oxide, zirconium oxide, magnesia, molecular sieve.
3. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that with catalyst weight percent
Meter, vector contg are 30%~70%.
4. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the attrition of catalyst rate is low
In 1.5%.
5. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 4, it is characterised in that the attrition of catalyst rate is low
In 1.3%.
6. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 5, it is characterised in that the attrition of catalyst rate is low
In 1.2%.
7. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the value range of a is
0.5~1.5.
8. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the value range of the b is
0.5~1.8.
9. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the average grain diameter of catalyst is
10-100μm。
10. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 9, it is characterised in that the average grain diameter of catalyst is
30-80μm。
11. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that V, Cr, A, B, C member
The compound of element is selected from oxide, salt, oxyacid or the organo-metallic compound of above-mentioned element.
12. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the solvent be water, alcohol or
Other pairs be added V, Cr, A, B, C element compound have deliquescent substance.
13. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the compound of carrier is selected from silicon
At least one of colloidal sol, waterglass, Aluminum sol, boehmite, silicon-aluminum sol.
14. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the M element compound
For at least one of zirconium oxide, zirconium hydroxide, zirconium nitrate, the organic metal salt of zirconium, tungstates, phosphotungstic acid and tungsten carbide.
15. ammoxidation of aromatic hydrocarbon fluid catalyst according to claim 1, it is characterised in that the mixed solution II is dense
Solid content is 20wt%-60wt% after contracting.
16. a kind of method for preparing isophthalodinitrile is wanted using meta-xylene, ammonia, air or oxygen as reaction raw materials in right
It is 300~500 DEG C in reaction temperature, reaction pressure is calculated as normal pressure with gauge pressure in the presence of seeking any one of 1~15 catalyst
~0.30MPa, catalyst weight load (WWH) are 0.02~0.20 hour-1, meta-xylene: ammonia: mole of air or oxygen
Than being 1: (1~13): reaction generates isophthalodinitrile under conditions of (10~60).
17. a kind of method for preparing o-chlorobenzonitrile is wanted using ortho-chlorotolu'ene, ammonia, air or oxygen as reaction raw materials in right
In the presence of seeking any one of 1~15 catalyst, reaction temperature is 300~500 DEG C, and reaction pressure is normal pressure to 0.30MPa,
Catalyst weight load (WWH) is 0.02~0.20h-1, reaction raw materials molar ratio is ortho-chlorotolu'ene: ammonia: air or oxygen=1
: (1~13): reaction generates o-chlorobenzonitrile under conditions of (10~60).
18. a kind of method for being used to prepare benzonitrile is matched using toluene, ammonia, air or oxygen as raw material in feed molar：
Toluene:Ammonia:Air or oxygen=1:(2~10):(10~50), reaction temperature are 300~500 DEG C, reaction pressure 0.01
~0.1Mpa, catalyst weight load (WWH) are 0.03~0.1 hour-1Under conditions of, raw material is any with claim 1~15
The item catalyst haptoreaction generates benzonitrile.
19. a kind of method for being used to prepare fragrant nitrile, using aromatic hydrocarbons, ammonia, air or oxygen as raw material, in claim 1~15 times
In the presence of one catalyst, matched in feed molar：Aromatic hydrocarbons:Ammonia:Air or oxygen=1:(2~10):(10~
50), reaction temperature be 300~500 DEG C, reaction pressure be 0.01~0.1Mpa, catalyst weight load (WWH) be 0.03~
0.1 hour-1Under conditions of, any one of raw material and claim 1~15 the catalyst haptoreaction generate fragrant nitrile.
20. a kind of method of ammoxidation of aromatic hydrocarbon fragrant nitrile, it is characterised in that the catalyst used is any one of claim 1~15
The catalyst.
21. the method for ammoxidation of aromatic hydrocarbon fragrant nitrile according to claim 20, the crude oil are to be connected with aromatic ring
Carbon atom have hydrogen atom coupled.
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| CN107413372B (en) * | 2017-07-03 | 2020-06-09 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing halogenated aromatic nitrile and using method thereof |
| CN107413371B (en) * | 2017-07-03 | 2020-07-03 | 中国石油化工股份有限公司 | Fluidized bed catalyst for producing halogenated aromatic nitrile and application thereof |
| CN107497466A (en) * | 2017-09-04 | 2017-12-22 | 南通天泽化工有限公司 | A kind of o-chloro benzonitrile catalyst and preparation method thereof |
| CN109876837B (en) * | 2018-12-17 | 2022-02-22 | 中南民族大学 | Special catalyst for preparing o-chlorobenzonitrile by ammoxidation method, preparation method and application thereof |
| CN109876794B (en) * | 2018-12-17 | 2022-02-18 | 中南民族大学 | Special catalyst for preparing isophthalonitrile through ammoxidation reaction, preparation method and application thereof |
| CN112619678B (en) * | 2019-09-24 | 2023-10-31 | 中国石油化工股份有限公司 | Preparation method of aromatic hydrocarbon ammoxidation fluidized bed catalyst |
| CN112624940B (en) * | 2019-09-24 | 2023-04-07 | 中国石油化工股份有限公司 | Method for preparing isophthalonitrile |
| CN113797946A (en) * | 2020-06-15 | 2021-12-17 | 中国石油化工股份有限公司 | Aromatic hydrocarbon ammoxidation catalyst and preparation method thereof |
| CN114100652B (en) * | 2021-12-10 | 2023-10-13 | 北京道思克矿山装备技术有限公司 | Catalyst for producing hydrogen cyanide by methanol gas-phase catalytic ammoxidation and preparation method and application thereof |
| CN114950404B (en) * | 2022-05-19 | 2023-11-17 | 中国科学院兰州化学物理研究所 | Wear-resistant ammonia oxidation catalyst and preparation method and application thereof |
| CN115739141A (en) * | 2022-11-30 | 2023-03-07 | 山东海科创新研究院有限公司 | Mesoporous structure catalyst and preparation method and application thereof |
| CN116273099A (en) * | 2023-02-17 | 2023-06-23 | 中南民族大学 | Silicon-aluminum composite oxide carrier supported catalyst and preparation method and application thereof |
| CN116237038A (en) * | 2023-02-17 | 2023-06-09 | 中南民族大学 | Catalyst for preparing p-bromoxynil by ammoxidation method, preparation method and application |
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