CN102850306B - Production method of maleic anhydride - Google Patents
Production method of maleic anhydride Download PDFInfo
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- CN102850306B CN102850306B CN201110183069.9A CN201110183069A CN102850306B CN 102850306 B CN102850306 B CN 102850306B CN 201110183069 A CN201110183069 A CN 201110183069A CN 102850306 B CN102850306 B CN 102850306B
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Abstract
The inventive production method of maleic anhydride comprises contacting a mixed gas (containing benzene and oxidizing gas) with catalyst bed layers A and B. The catalyst bed layers contain vanadium-containing compound, molybdenum-containing compound, sodium-containing compound, phosphorus-containing compound, and nickel-containing compound. Molar ratio of molybdenum-containing compound to vanadium-containing compound of the catalyst bed layer B is 0.5-0.9 of that of the catalyst bed layer A. Molar ratio of phosphorus-containing compound to vanadium-containing compound of the catalyst bed layer B is 0.4-0.9 of that of the catalyst bed layer A. Molar ratio of nickel-containing compound to vanadium-containing compound of the catalyst bed layer B is 0.4-0.8 of that of the catalyst bed layer A. The invention can increase benzene concentration in the mixed gas material, and sufficiently convert benzene to improve final maleic anhydride yield.
Description
Technical field
The present invention relates to a kind of production method of MALEIC ANHYDRIDE.
Background technology
MALEIC ANHYDRIDE (be called for short cis-butenedioic anhydride, claim maleic anhydride again) is important Organic Chemicals, and it has become the second largest organic acid anhydride that is only second to phthalic anhydride.At present, cis-butenedioic anhydride is mainly for the production of industry such as synthetic resins, food, agricultural chemicals, medicine, papermaking, coating, weavings, and market is growing to the demand of cis-butenedioic anhydride.
Produce cis-butenedioic anhydride mainly taking benzene, normal butane or butylene as raw material, account for 60% of China Maleic Anhydrite ultimate production taking benzene as raw material production cis-butenedioic anhydride at present.Produce cis-butenedioic anhydride in order to make the industrial more effective method by catalytic gas phase oxidation benzene, first require to have highly selective and long-term durable catalyzer, in recent years, require production process energy-conservation and enhance productivity in, to catalyzer also additional requirement its have can be with the ability of a large amount of benzene of air catalytic oxidation of small amount, in other words,, even if production process is while carrying out in the situation that improving in feeding gas benzene concentration, still require catalyzer to there is good selectivity and wearing quality.
Modern maleic anhydride production taking benzene as raw material mainly takes the form of fixed bed reaction to carry out, and the catalyzer that wherein used, taking loaded catalyst as main Types, generally adopts V-Mo system supported catalyst, with V
2o
5and MoO
3for catalytic active substance, and add containing the compound of Na, P, Ni or rare earth element etc. as catalyst adjuvant,, catalytic active substance and catalyst adjuvant are together loaded on carrier and make as carrier with inertia non-porous material.
The invention that the number of patent application of catalyst chemical company of Japan is ZL86102873, wherein, has proposed a kind of production method of maleic anhydride, and technical characteristics is: (1) adopts two section bed techniques, and Reactor inlet side oxide compound is V
2o
5, MoO
3, Na
2o and P
2o
5or some auxiliary agents such as other potassium, caesium, rubidium, wherein regulate activity by reducing the amount of P or increasing the auxiliary agents such as auxiliary agent potassium, caesium, rubidium, and outlet side is equally by regulating P
2o
5or the amount of auxiliary agent potassium, caesium, rubidium regulates, but be to adopt to increase P
2o
5amount or reduce auxiliary agent potassium, caesium, rubidium equivalent and regulate, all the other are identical with inlet section; (2) the two section beds of catalyzer are by the filling of gas feed side direction, and wherein inlet section height accounts for the 30-70% of total height of bed, and outlet section accounts for the 70-30% of total height of bed; (3) catalyzer used carrier is Al
2o
3adopt internal diameter 25mm with mixture (4) reaction evaluating of SiC, the reaction tubes of long 3.6m, 2.5 meters of total height of bed, salt temperature 350-365 DEG C, catalyzer hot(test)-spot temperature is too high, reaches more than 480-500 DEG C, and benzene feed concentration is at 50-70g/Nm
3, yield of maleic anhydride 96-98 % by weight (in benzene), transformation efficiency the unknown of benzene.
Zhong He chemical plant, Tianjin has proposed the preparation method of the high yield maleic anhydride catalyst of a kind of high loading in CN101284242A, and its technical characterstic is: (1) reaction adopts two section bed catalysts, and inlet section is A section, and outlet section is B section, and wherein, A section is with V
2o
5, MoO
3, Na
2o, P
2o
5, NiO and rare earth metal be main active component, B section is by increasing the content of rare earth metal auxiliary agent or reducing P
2o
5content improves the activity of catalyzer; (2) collocation of two sections of beds is highly: A section accounts for the 40-60% of total height of bed, and B section accounts for the 60-40% of total height of bed; (3) evaluating catalyst adopts caliber 21mm, the reaction tubes of long 3.6m, and catalyst bed floor height 3.3m, at salt temperature 350-360 DEG C, benzene feed concentration is at 59-63g/Nm
3under condition, benzene load is 110-180g/Lcath, yield of maleic anhydride 90-98 % by weight (in benzene), the transformation efficiency 98% of benzene.
Summary of the invention
The object of the present invention is to provide one under high density gas-phase benzene condition, to obtain the production method of the MALEIC ANHYDRIDE of high yield.
The production method of MALEIC ANHYDRIDE provided by the invention, the method is included under oxidizing condition, the mixed gas that contains benzene and oxidizing gas is contacted with beds, described beds is by activated rear formation of a kind of catalyzer, described catalyzer comprises carrier and active substance, described active substance contains vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound and nickel compound containing, taking the feedstock direction of the mixed gas that contains benzene and oxidizing gas as benchmark, described beds is divided into beds A and beds B successively, in beds A and beds B, described vanadium-containing compound is with V
2o
5meter, described molybdate compound are with MoO
3meter, described compounds containing sodium are with Na
2o meter, described P contained compound are with P
2o
5meter, described nickel compound containing are in NiO, the mol ratio of described vanadium-containing compound, described molybdate compound, described compounds containing sodium, described P contained compound, described nickel compound containing is 1: 0.3-1.1: 0.001-0.3: 0.002-0.25: 0.001-0.5, wherein, in described beds B, the mol ratio of molybdate compound and vanadium-containing compound is the 0.5-0.9 of the mol ratio of molybdate compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of P contained compound and vanadium-containing compound is the 0.4-0.9 of the mol ratio of P contained compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of nickel compound containing and vanadium-containing compound is the 0.4-0.8 of the mol ratio of nickel compound containing and vanadium-containing compound in described beds A.
Use method production MALEIC ANHYDRIDE provided by the invention, can improve the concentration of benzene in mixture of feed body, increase the benzene load of fixed-bed reactor and fully make benzene transform, make the yield of final MALEIC ANHYDRIDE high.For example, according to the method production MALEIC ANHYDRIDE of embodiment 1, the mixed gas that contains benzene and oxidizing gas is with volume space velocity 2400-2700h
-1enter fixed-bed reactor, in mixed gas, the concentration of benzene is 75g/m
3condition under, the transformation efficiency of benzene is that the yield of 98.5-99.0%, cis-butenedioic anhydride is 106-111 % by weight (with the weighing scale of benzene).And comparative example 1 is under same operation condition, the transformation efficiency of benzene is that the yield of 98.0-98.3%, cis-butenedioic anhydride is 99-103 % by weight (with the weighing scale of benzene).
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of production method of MALEIC ANHYDRIDE, the method is included under oxidizing condition, the mixed gas that contains benzene and oxidizing gas is contacted with beds, described beds is by activated rear formation of a kind of catalyzer, described catalyzer comprises carrier and active substance, described active substance contains vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound and nickel compound containing, taking the feedstock direction of the mixed gas that contains benzene and oxidizing gas as benchmark, described beds is divided into beds A and beds B successively, in beds A and beds B, described vanadium-containing compound is with V
2o
5meter, described molybdate compound are with MoO
3meter, described compounds containing sodium are with Na
2o meter, described P contained compound are with P
2o
5meter, described nickel compound containing are in NiO, described vanadium-containing compound: described molybdate compound: described compounds containing sodium: described P contained compound: the mol ratio of described nickel compound containing can be 1: 0.3-1.1: 0.001-0.3: 0.002-0.25: 0.001-0.5, wherein, in described beds B, the mol ratio of molybdate compound and vanadium-containing compound is the 0.5-0.9 of the mol ratio of molybdate compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of P contained compound and vanadium-containing compound is the 0.4-0.9 of the mol ratio of P contained compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of nickel compound containing and vanadium-containing compound is the 0.4-0.8 of the mol ratio of nickel compound containing and vanadium-containing compound in described beds A.In the preferred case, in described beds B, the mol ratio of molybdate compound and vanadium-containing compound is the 0.5-0.8 of the mol ratio of molybdate compound and vanadium-containing compound in described beds A; In described beds B, the mol ratio of P contained compound and vanadium-containing compound is the 0.4-0.8 of the mol ratio of P contained compound and vanadium-containing compound in described beds A; In described beds B, the mol ratio of nickel compound containing and vanadium-containing compound is the 0.4-0.7 of the mol ratio of nickel compound containing and vanadium-containing compound in described beds A.By controlling the content of vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound and nickel compound containing in beds A and B, and control the content of molybdate compound, P contained compound and nickel compound containing of beds B and the content ratio of molybdate compound, P contained compound and the nickel compound containing of beds A in above-mentioned scope, can make the catalyzer in beds A and B have very high selectivity and obtain higher MALEIC ANHYDRIDE yield the oxidizing reaction of benzene.
Described vanadium-containing compound can be the conventional various vanadium-containing compounds that use in this area, as one or more in ammonium meta-vanadate, Vanadium Pentoxide in FLAKES, vanadium trichloride, vanadic acid sodium.
Described molybdate compound can be the conventional various molybdate compounds that use in this area, as one or more in ammonium molybdate, molybdic oxide, Sodium orthomolybdate.
Described compounds containing sodium can be the conventional various compounds containing sodiums that use in this area, as one or more in sodium phosphate, sodium carbonate, SODIUMNITRATE, sodium-chlor.
Described P contained compound can be the conventional various P contained compounds that use in this area, as one or more in primary ammonium phosphate, phosphoric acid, Vanadium Pentoxide in FLAKES.
Described nickel compound containing can be the conventional various nickel compound containings that use in this area, as one or more in nickelous nitrate, nickel oxide, nickelous chloride, nickelous carbonate, single nickel salt.
According to the production method of MALEIC ANHYDRIDE of the present invention, in order to make the method obtain the transformation efficiency of better catalyst activity and higher benzene, in described beds A and/or beds B, can also contain A1 and/or A2, preferred described beds A and beds B all also contain A1 and A2.Described A1 can be selected from the compound that contains the alkali metal except sodium element, the compound that contains IB group 4 transition metal element, the compound that contains IIB group 4 transition metal element, the compound that contains the IIIB group 4 transition metal element except group of the lanthanides and actinium series, the compound that contains IVB group 4 transition metal element, the compound that contains the VB group 4 transition metal element except v element, the compound that contains the group vib transition metal except molybdenum element, the compound that contains VIIB group 4 transition metal element, one or more in the compound that contains the VIII group 4 transition metal element except nickel element.In the preferred case, described A1 be in the compound that contains Li, K, Rb, Cs, Nb, Mn, Fe, Co, Ag one or more, be specifically as follows one or more in rubidium nitrate, niobium oxides, manganese oxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Silver Nitrate, iron nitrate, saltpetre, cesium nitrate.Described A2 can be selected from one or more in lanthanide metal compound.In the preferred case, described A2 is one or more in the compound of compound, Er of compound, the Ho of compound, the Eu of compound, the Pr of Ce, be specifically as follows Erbium trioxide, Holmium trioxide, europium sesquioxide, Praseodymium trioxide, cerous nitrate, dysprosium oxide, Neodymium trioxide, ytterbium oxide, bismuth oxide etc. one or more.The content of described A1 and A2 can be chosen arbitrarily in a big way, find by research, described A1, A2 are all in metal oxide, the mol ratio of vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound, nickel compound containing, A1, A2 is 1: 0.3-1.1: 0.001-0.3: 0.002-0.25: 0.001-0.5: 0.0001-0.2: when 0.0001-0.01, the catalyzer obtaining has good catalytic performance.In the preferred case, the mol ratio of vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound, nickel compound containing, A1, A2 is 1: 0.3-0.9: 0.01-0.25: 0.005-0.15: 0.005-0.25: 0.0005-0.1: 0.0001-0.001.Need explanation at this, when described A1 and/or A2 are made up of multiple compounds, while calculating the mol ratio of vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound, nickel compound containing, A1, A2, the mole number of described A1 be add in the mole number of the compound of the multiple A1 of being selected from of metal oxide and, the mole number of described A2 be add in the mole number of the compound of the multiple A2 of being selected from of metal oxide and.
According to the production method of MALEIC ANHYDRIDE of the present invention, in order to obtain higher benzene load, improve selectivity to benzene oxidizing reaction of catalyzer in beds A and improve the activity of catalyzer in beds B, preferred described beds A and beds B all also contain A1.The A1 of described beds A can be the oxide compound of Rb and/or Ag.The A1 of beds B is preferably the oxide compound of Co and/or Mn simultaneously.
According to the production method of MALEIC ANHYDRIDE of the present invention, described carrier can be conventional for the production of the various carriers in the catalyzer of MALEIC ANHYDRIDE, for example, described carrier can be the carrier that contains silicon carbide and/or aluminum oxide, and described carrier all can be commercially available.In the preferred case, taking the gross weight of described carrier as benchmark, the content of silicon carbide is 80-99.9 % by weight, and the content of aluminum oxide is 0.1-20 % by weight.The shape of described carrier can be spherical, ring-type or tri-lobed conventionally.For active substance is loaded on carrier more equably, and can make the reaction mass benzene in maleic anhydride production have larger contact area with the catalyzer that uses this carrier, preferably use circular vectors, the external diameter of this carrier can be that 6 millimeters, internal diameter can be 5 millimeters, highly can be 4 to 5 millimeters, and the bulk density of described carrier can be 0.7-0.8 grams per milliliter.
According to the production method of MALEIC ANHYDRIDE of the present invention, the content that loads on the described active substance on carrier can in very large range be chosen arbitrarily, for example, taking the gross weight of the catalyzer in beds as benchmark, the content of described active substance is 3-30 % by weight, the oxidizing reaction of catalysis benzene well of the described active substance at this scope internal burden on carrier; In the preferred case, taking the gross weight of the catalyzer in beds as benchmark, the content of described active substance is 10-20 % by weight.
According to the production method of MALEIC ANHYDRIDE of the present invention, the catalyzer in above-mentioned beds A and B can adopt the preparation method of the various known catalyzer of producing for MALEIC ANHYDRIDE.For example, can be by active substance vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound, nickel compound containing and solvent; Described solvent is as long as have certain solvability to active substance, described solvent can be selected from for example, in the alcohol (can methyl alcohol, in ethanol, ethylene glycol, n-propyl alcohol, Virahol, glycerine, propyl carbinol, isopropylcarbinol one or more), ammoniacal liquor, hydrochloric acid (mass concentration is less than 37.5 % by weight), water of carbonatoms 1 to 4 one or more, from industrial angle, preferred described solvent is water.The surface that the solution that contains active substance is coated to carrier with 100-300 DEG C (preferably with 200-300 DEG C) obtains loaded catalyst after drying and other steps.Above-mentioned active substance, carrier, solvent etc. all can be commercially available.
According to the production method of MALEIC ANHYDRIDE of the present invention, fixed-bed reactor are divided into beds A and beds B by the method, the height of beds A and beds B can be chosen in a big way, for example, taking the total height of beds as benchmark, described beds A can account for 30-70%, and described beds B can account for 30-70%.In the preferred case, taking the total height of beds as benchmark, described beds A accounts for 40-60%, and described beds B accounts for 40-60%.
According to the production method of MALEIC ANHYDRIDE of the present invention, the method can adopt known various devices and operational condition of producing for MALEIC ANHYDRIDE.In order to prevent that in mixed gas, the excessive concentration of benzene sets off an explosion, in the production of MALEIC ANHYDRIDE, in described mixed gas, the concentration of benzene is 30-80g/m conventionally
3; In the preferred case, in described mixed gas, the concentration of benzene is 60-80g/m
3.In the present invention, unless stated otherwise, the volume of gas all refers to the volume of gas under standard state.For ensureing that described benzene can be oxidized into cis-butenedioic anhydride fully, the volume ratio of described benzene and oxidizing gas can be 0.012-0.078: 1; In the preferred case, the volume ratio of described benzene and oxidizing gas is 0.015-0.02: 1, and described oxidizing gas is oxygen or air.In guarantee beds of the present invention, catalyzer can be brought into play under good catalytic efficiency, and the volume space velocity of described mixed gas can be 1500-3500h
-1; In the preferred case, the volume space velocity of described mixed gas is 2000-3000h
-1.In order to obtain transformation efficiency and the yield of maleic anhydride of higher benzene, the temperature of described contact can be 300-500 DEG C; In the preferred case, the temperature of described contact is 330-460 DEG C.The present invention does not do pressurization or decompression operation especially to the device of production MALEIC ANHYDRIDE, and common described device adopts atmospheric operation, and the pressure in described device can be 0.07-0.11MPa.
According to the production method of MALEIC ANHYDRIDE of the present invention, the catalyzer in above-mentioned beds is activated and can adopt various known catalyst activation process.In the preferred case, described activation comprises catalyzer is warming up to 300 ± 5 DEG C and be warming up to 400-500 DEG C with the speed of 25-40 DEG C/h with the speed of 40-70 DEG C/h successively, and maintain 4-12 hour at 400-500 DEG C, preferably, speed with 25-40 DEG C/h is warming up to 420-460 DEG C, and maintains 4-8 hour at 420-460 DEG C; Then be cooled to 25 ± 5 DEG C, the present invention does not limit especially to this cooling rate, preferably lowers the temperature with the speed of 70-150 DEG C/h.Adopt above-mentioned preferred method catalyzer to be activated to the activity and selectivity that can bring into play better catalyzer, thereby improve the performance of high loading catalyzer.
The present invention is described in detail by the following examples.
Unless stated otherwise, in embodiments of the invention and application examples, agents useful for same all can be commercially available.
In the following example and comparative example, fixed-bed reactor adopt salt bath heating, and the pressure in fixed-bed reactor is 0.1 ± 0.01MPa.In beds, catalyzer maximum of temperature in reaction is called catalyzer hot(test)-spot temperature, and use temperature sensor is measured.Benzene load refers to the weight that the catalyzer of time per unit, unit volume can catalyzed oxidation benzene.Following operational condition comprises that the mixed gas that contains benzene and oxidizing gas (in this case air) enters concentration and the salt temperature of benzene in the volume space velocity of fixed-bed reactor, described mixed gas.
Following embodiment and comparative example circular vectors used is made with reference to the proportioning raw materials of embodiment in ZL94107337.8 1, different, makes circular vectors, and the external diameter of carrier is that 6 millimeters, internal diameter are 5 millimeters, are highly 4 to 5 millimeters.
Amount of substance × 100% of transformation efficiency (%)=(amount of substance of amount of substance-unit time reactor outlet benzene of unit time benzene charging)/unit time benzene charging of benzene
The weight of the product cis-butenedioic anhydride obtaining after reacting by chemical titration, calculate yield of maleic anhydride by following formula:
Weight × 100% of weight/unit time benzene charging of yield of maleic anhydride (% by weight)=unit time product cis-butenedioic anhydride
Embodiment 1
(1) preparation of catalyzer in beds A
97.2g oxalic acid, 67.6g ammonium meta-vanadate, 38.5g ammonium molybdate, 4.9g sodium phosphate, 3.12g nickelous nitrate, 1.9g primary ammonium phosphate, 0.1g rubidium nitrate, 0.063g Erbium trioxide and 450ml water are mixed to get to slurries, gained slurries are sprayed at and are placed in the 410g circular vectors of rotating speed as the seed-coating machine of 13-20 rev/min taking 200-300 DEG C, after finishing, spraying is dried to constant mass, obtain 482.3g catalyst A-1, wherein, taking the gross weight of catalyst A-1 as benchmark, the content of active substance is 15 % by weight;
(2) preparation of catalyzer in beds B
According to catalyst B-1 in the method Kaolinite Preparation of Catalyst bed B of step (1), the weight of different is ammonium molybdate is that the weight of 30.5g, nickelous nitrate is 1.42g, replaces 0.1g rubidium nitrate, replaces 0.063g Erbium trioxide, do not add primary ammonium phosphate with 0.042g Holmium trioxide with 1.52g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, obtain catalyst B-1, wherein, taking the gross weight of catalyst B-1 as benchmark, the content of active substance is 16 % by weight;
(3) evaluation of catalyzer (being the production of MALEIC ANHYDRIDE)
Above-mentioned catalyst A-1 and B-1 are independently placed in to closed container separately and activate, be first warming up to 300 DEG C with the speed of 55 DEG C/h, then be warming up to 450 DEG C with the speed of 30 DEG C/h, at 450 DEG C, maintain 8 hours, then 100 DEG C/h are cooled to 25 DEG C, by catalyst A-1 after activation, B-1 successively layering is filled into 120ml fixed-bed reactor (reactor length 60cm, bed total height 36cm, internal diameter 21mm, lower same) in, make the beds A that contains catalyst A-1 account for 40% of fixed-bed reactor bed height, the beds B that contains catalyst B-1 accounts for 60% of fixed-bed reactor bed height, make the mixed gas of benzene and air by this fixed-bed reactor bed, operational condition and experimental result (start sampling analysis after moving continuously 24 hours, every sampling in 5-10 hour once, move altogether 720 hours, lower same) as shown in table 1.
Comparative example 1
(1) preparation of catalyzer in beds A
Obtain in the same manner catalyst A-1 in beds A with embodiment 1 step (1);
(2) preparation of catalyzer in beds
According to catalyst B-D1 in the method Kaolinite Preparation of Catalyst bed B of step (1), different is to replace 0.1g rubidium nitrate, replace 0.063g Erbium trioxide, do not add primary ammonium phosphate with 0.08g Holmium trioxide with 1.52g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, obtain catalyst B-D1, wherein, taking the gross weight of catalyst B-D1 as benchmark, the content of active substance is 14.5 % by weight;
(3) evaluation of catalyzer
Method according to embodiment 1 step (3) is evaluated, and different is to use catalyst B-D1 to replace catalyst B-1, and operational condition and experimental result are as shown in table 1.
Embodiment 2
(1) preparation of catalyzer in beds A
According to catalyst A-2 in the method Kaolinite Preparation of Catalyst bed A of embodiment 1 step (1), different is that 1.6g phosphoric acid (mass concentration is 98 % by weight) replaces 1.9g primary ammonium phosphate, 5.9g Silver Nitrate replaces 0.1g rubidium nitrate, 0.04g europium sesquioxide to replace 0.063g Erbium trioxide, obtain catalyst A-2, wherein, taking the gross weight of catalyst A-2 as benchmark, the content of active substance is 14.0 % by weight;
(2) preparation of catalyzer in beds B
According to catalyst B-2 in the method Kaolinite Preparation of Catalyst bed B of step (1), the weight of different is ammonium molybdate is that the weight of 30.0g, sodium phosphate is that the weight of 4.86g, nickelous nitrate is 1.48g, replaces 5.9g Silver Nitrate, do not add phosphoric acid with 0.056g niobium oxides, obtain catalyst B-2, wherein, taking the gross weight of catalyst B-2 as benchmark, the content of active substance is 14.8 % by weight;
(3) evaluation of catalyzer
Above-mentioned catalyst A-2 and B-2 are independently placed in to closed container separately and activate, be first warming up to 300 DEG C with the speed of 65 DEG C/h, then be warming up to 425 DEG C with the speed of 25 DEG C/h, at 425 DEG C, maintain 10 hours; Then be cooled to 25 DEG C with the speed of 120 DEG C/h; Catalyst A-2 after activation, B-2 successively layering are filled in 120ml fixed-bed reactor, make the beds A that contains catalyst A-2 account for 50% of fixed-bed reactor bed height, the beds B that contains catalyst B-2 accounts for 50% of fixed-bed reactor bed height, and operational condition and experimental result are as shown in table 1.
Embodiment 3
(1) preparation of catalyzer in beds A
According to catalyst A-3 in the method Kaolinite Preparation of Catalyst bed A of embodiment 1 step (1), different is that 1.17g Vanadium Pentoxide in FLAKES replaces 1.9g primary ammonium phosphate, 5.9g Silver Nitrate replaces 0.1g rubidium nitrate, adds 0.039g niobium oxides, obtain catalyst A-3, wherein, taking the gross weight of catalyst A-3 as benchmark, the content of active substance is 13.9 % by weight;
(2) preparation of catalyzer in beds B
According to catalyst B-3 in the method Kaolinite Preparation of Catalyst bed B of step (1), the weight of different is ammonium molybdate is that the weight of 29.8g, sodium phosphate is 4.6g, adds the weight of 0.29g sodium carbonate, nickelous nitrate to be 1.28g, to replace 0.039g niobium oxides and 5.9g Silver Nitrate, do not add Vanadium Pentoxide in FLAKES with 1.49g Manganse Dioxide, obtain catalyst B-3, wherein, taking the gross weight of catalyst B-3 as benchmark, the content of active substance is 16.5 % by weight;
(3) evaluation of catalyzer
Above-mentioned catalyst A-3 and B-3 are independently placed in to closed container separately and activate, be first warming up to 300 DEG C with the speed of 40 DEG C/h, then be warming up to 500 DEG C with the speed of 40 DEG C/h, at 500 DEG C, maintain 5 hours; Then be cooled to 25 DEG C with the speed of 80 DEG C/h; Catalyst A-3 after activation, B-3 successively layering are filled in 120ml fixed-bed reactor, make the beds A that contains catalyst A-3 account for 60% of fixed-bed reactor bed height, the beds B that contains catalyst B-3 accounts for 40% of fixed-bed reactor bed height, and operational condition and experimental result are as shown in table 1.
Embodiment 4
(1) preparation of catalyzer in beds A
97.2g oxalic acid, 67.6g ammonium meta-vanadate, 37.5g ammonium molybdate, 4.9g sodium phosphate, 3.12g nickelous nitrate, 1.17g Vanadium Pentoxide in FLAKES and 520ml water are mixed to get to slurries, gained slurries are sprayed at and are placed in the inertia circular vectors of rotating speed as the seed-coating machine of 15-20 rev/min taking 220-260 DEG C, spraying finishes rear dry catalyst A-4 that obtain, wherein, taking the gross weight of catalyst A-4 as benchmark, the content of active substance is 15.5 % by weight;
(2) preparation of catalyzer in beds B
According to catalyst B-4 in the method Kaolinite Preparation of Catalyst bed B of step (1), the weight of different is ammonium molybdate is that the weight of 31.0g, nickelous nitrate is 1.42g, does not add Vanadium Pentoxide in FLAKES, obtain catalyst B-4, wherein, taking the gross weight of catalyst B-4 as benchmark, the content of active substance is 14.2 % by weight;
(3) evaluation of catalyzer
Method according to embodiment 1 step (3) is evaluated, and different is that catalyst A-4 replace catalyst A-1, catalyst B-4 to replace catalyst B-1, and operational condition and experimental result are as shown in table 1.
Comparative example 2
(1) preparation of catalyzer in beds A
Obtain in the same manner catalyst A-4 in beds A with embodiment 4 steps (1);
(2) preparation of catalyzer in beds B
According to catalyst B-D2 in the method Kaolinite Preparation of Catalyst bed B of step (1), different is not add Vanadium Pentoxide in FLAKES, obtains catalyst B-D2, and wherein, taking the gross weight of catalyst B-D2 as benchmark, the content of active substance is 15.3 % by weight;
(3) evaluation of catalyzer
Method according to embodiment 4 steps (3) is evaluated, and different is that catalyst B-D2 replaces catalyst B-4, and operational condition and experimental result are as shown in table 1.
Embodiment 5
(1) preparation of catalyzer in beds A
Obtain in the same manner catalyst A-1 in beds A with embodiment 1 step (1);
(2) preparation of catalyzer in beds B
Obtain in the same manner catalyst B-1 in beds B with embodiment 1 step (2);
(3) evaluation of catalyzer
Method according to embodiment 1 step (3) is evaluated, and different is is placed in respectively separately fixed-bed reactor by above-mentioned catalyst A-1 and B-1 and activates, and the mixed gas of benzene and air is with volume space velocity 2000h
-1pass into fixed-bed reactor, (first stage is warming up to 300 DEG C with 100 DEG C in temperature programming, then subordinate phase is warming up to 420 DEG C with 50 DEG C/h) and keep 12-24 hour at 420 DEG C, then be cooled to 25 DEG C, operational condition and experimental result are as shown in table 1.
Table 1
In table 1, by the data comparison of embodiment 1-3 and comparative example 1, in comparative example 1, adopt the technical scheme of CN101284242A, the content that has reduced P contained compound in beds B has improved the content of rare earth compound simultaneously, and embodiment 1-3 adopts the production method of MALEIC ANHYDRIDE provided by the invention, adjusted molybdate compound in beds B simultaneously, P contained compound, the mol ratio of nickel compound containing and vanadium-containing compound, making the mol ratio of molybdate compound and vanadium-containing compound in beds B is the 0.5-0.9 of the mol ratio of molybdate compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of P contained compound and vanadium-containing compound is the 0.4-0.9 of the mol ratio of P contained compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of nickel compound containing and vanadium-containing compound is the 0.4-0.8 of the mol ratio of nickel compound containing and vanadium-containing compound in described beds A, and this production method can fully make benzene transform, increase the yield of MALEIC ANHYDRIDE under the mixed gas condition of high density gas-phase benzene in fixed-bed reactor.Data comparison by embodiment 1 with embodiment 4, can find out the selectivity that contains A1 and A2 in beds and can improve catalyst activity and the oxidizing reaction to benzene.Data comparison by embodiment 1 with embodiment 5, can find out that the catalytic efficiency that adopts activation method of the present invention can make catalyzer improves.
Claims (16)
1. the production method of a MALEIC ANHYDRIDE, the method is included under oxidizing condition, the mixed gas that contains benzene and oxidizing gas is contacted with beds, described beds is by activated rear formation of a kind of catalyzer, described catalyzer comprises carrier and active substance, described active substance contains vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound and nickel compound containing, taking the feedstock direction of the mixed gas that contains benzene and oxidizing gas as benchmark, described beds is divided into beds A and beds B successively, in beds A and beds B, described vanadium-containing compound is with V
2o
5meter, described molybdate compound are with MoO
3meter, described compounds containing sodium are with Na
2o meter, described P contained compound are with P
2o
5meter, described nickel compound containing are in NiO, described vanadium-containing compound: described molybdate compound: described compounds containing sodium: described P contained compound: the mol ratio of described nickel compound containing is 1:0.3-1.1:0.001-0.3:0.002-0.25:0.001-0.5, it is characterized in that, in described beds B, the mol ratio of molybdate compound and vanadium-containing compound is the 0.5-0.9 of the mol ratio of molybdate compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of P contained compound and vanadium-containing compound is the 0.4-0.9 of the mol ratio of P contained compound and vanadium-containing compound in described beds A, in described beds B, the mol ratio of nickel compound containing and vanadium-containing compound is the 0.4-0.8 of the mol ratio of nickel compound containing and vanadium-containing compound in described beds A.
2. method according to claim 1, wherein, in described beds B, the mol ratio of molybdate compound and vanadium-containing compound is the 0.5-0.8 of the mol ratio of molybdate compound and vanadium-containing compound in described beds A; In described beds B, the mol ratio of P contained compound and vanadium-containing compound is the 0.4-0.8 of the mol ratio of P contained compound and vanadium-containing compound in described beds A; In described beds B, the mol ratio of nickel compound containing and vanadium-containing compound is the 0.4-0.7 of the mol ratio of nickel compound containing and vanadium-containing compound in described beds A.
3. method according to claim 1, wherein, in described beds A and/or beds B, also contain A1 and/or A2, wherein, described A1 is selected from the compound that contains the alkali metal except sodium element, the compound that contains IB group 4 transition metal element, the compound that contains IIB group 4 transition metal element, the compound that contains the IIIB group 4 transition metal element except group of the lanthanides and actinium series, the compound that contains IVB group 4 transition metal element, the compound that contains the VB group 4 transition metal element except v element, the compound that contains the group vib transition metal except molybdenum element, the compound that contains VIIB group 4 transition metal element, one or more in the compound that contains the VIII group 4 transition metal element except nickel element, described A2 is selected from one or more in lanthanide metal compound, described A1, A2 are all in metal oxide, and the mol ratio of described vanadium-containing compound, described molybdate compound, described compounds containing sodium, described P contained compound, described nickel compound containing, A1, A2 is 1:0.3-1.1:0.001-0.3:0.002-0.25:0.001-0.5:0.0001-0.2:0.00 01-0.01.
4. method according to claim 3, wherein, the mol ratio of described vanadium-containing compound, described molybdate compound, described compounds containing sodium, described P contained compound, described nickel compound containing, A1, A2 is 1:0.4-1:0.01-0.25:0.005-0.15:0.005-0.25:0.0005-0.1:0.000 1-0.001.
5. according to the method described in claim 3 or 4, wherein, described A1 be in the compound that contains Li, K, Rb, Cs, Nb, Mn, Fe, Co, Ag one or more, one or more in the compound of the compound of the compound that described A2 is Ce, the compound of Pr, Eu, the compound of Ho, Er.
6. method according to claim 5, wherein, described beds A and beds B all contain A1, and A1 in described beds A is the oxide compound of Rb and/or Ag; A1 in described beds B is the oxide compound of Co and/or Mn.
7. method according to claim 1, wherein, described carrier is the carrier that contains silicon carbide and/or aluminum oxide, being shaped as of described carrier is spherical, ring-type or tri-lobed.
8. method according to claim 7, wherein, taking the gross weight of described carrier as benchmark, the content of silicon carbide is 80-99.9 % by weight, the content of aluminum oxide is 0.1-20 % by weight; Described carrier be shaped as ring-type.
9. method according to claim 1, wherein, taking the gross weight of the catalyzer in beds as benchmark, the content of described active substance is 3-30 % by weight.
10. method according to claim 9, wherein, taking the gross weight of the catalyzer in beds as benchmark, the content of described active substance is 10-20 % by weight.
11. methods according to claim 1, wherein, taking the total height of beds as benchmark, described beds A accounts for 30-70%, and described beds B accounts for 30-70%.
12. methods according to claim 11, wherein, taking the total height of beds as benchmark, described beds A accounts for 40-60%, and described beds B accounts for 40-60%.
13. methods according to claim 1, wherein, in described mixed gas, the concentration of benzene is 30-80g/m
3, the volume ratio of described benzene and oxidizing gas is 0.012-0.078:1, the volume space velocity of described mixed gas is 1500-3500h
-1, the temperature of described contact is 300-500 DEG C.
14. methods according to claim 13, wherein, in described mixed gas, the concentration of benzene is 60-80g/m
3, the volume ratio of described benzene and oxidizing gas is 0.015-0.02:1, the volume space velocity of described mixed gas is 2000-3000h
-1, the temperature of described contact is 330-460 DEG C.
15. methods according to claim 1, wherein, the method that described catalyzer is activated comprises catalyzer is warming up to 300 ± 5 DEG C and be warming up to 400-500 DEG C with the speed of 25-40 DEG C/h with the speed of 40-70 DEG C/h successively, and maintain 4-12 hour at 400-500 DEG C, be then cooled to 25 ± 5 DEG C.
16. methods according to claim 15, wherein, the method that described catalyzer is activated comprises catalyzer is warming up to 420-460 DEG C with the speed of 25-40 DEG C/h successively, and maintain 4-8 hour at 420-460 DEG C.
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| CN105457686A (en) * | 2015-12-14 | 2016-04-06 | 天津市天环精细化工研究所 | Method for activating benzene-method maleic anhydride catalyst outside reactor |
| CN109201095A (en) * | 2017-07-04 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof |
| CN112439436A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride by benzene oxidation and preparation method thereof |
| CN112684832B (en) * | 2019-10-17 | 2022-01-28 | 中国石油化工股份有限公司 | Method and equipment for overcoming temperature reaction lag of silicon carbide annular carrier |
| CN113842934B (en) * | 2020-06-28 | 2023-07-21 | 中国石油化工股份有限公司 | Oxidation catalyst and preparation method and application thereof |
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| CN1250050A (en) * | 1999-09-15 | 2000-04-12 | 北京市艾实华标准技术公司 | Production process of maleic anhydride |
| CN101134750A (en) * | 2006-05-18 | 2008-03-05 | 巴斯福股份公司 | Process for the preparation of maleic anhydride in a microchannel reactor |
| CN101284242A (en) * | 2008-06-06 | 2008-10-15 | 天津市天环精细化工研究所 | Catalyst for producing maleic anhydrid(e) by benzene gas-phase oxidation with high load and high yield |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1250050A (en) * | 1999-09-15 | 2000-04-12 | 北京市艾实华标准技术公司 | Production process of maleic anhydride |
| CN101134750A (en) * | 2006-05-18 | 2008-03-05 | 巴斯福股份公司 | Process for the preparation of maleic anhydride in a microchannel reactor |
| CN101284242A (en) * | 2008-06-06 | 2008-10-15 | 天津市天环精细化工研究所 | Catalyst for producing maleic anhydrid(e) by benzene gas-phase oxidation with high load and high yield |
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