CN102850306A - Production method of maleic anhydride - Google Patents
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- CN102850306A CN102850306A CN2011101830699A CN201110183069A CN102850306A CN 102850306 A CN102850306 A CN 102850306A CN 2011101830699 A CN2011101830699 A CN 2011101830699A CN 201110183069 A CN201110183069 A CN 201110183069A CN 102850306 A CN102850306 A CN 102850306A
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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 take benzene, normal butane or butylene as raw material, account for 60% of China Maleic Anhydrite ultimate production take benzene as the raw material production cis-butenedioic anhydride at present.Produce cis-butenedioic anhydride in order to make industrial more effective method by catalytic gas phase oxidation benzene, at 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 production process is when carrying out in the situation of benzene concentration in improving feeding gas, still require catalyzer to have good selectivity and wearing quality.
Modern maleic anhydride production take benzene as raw material mainly takes the form of fixed bed reaction to carry out, and wherein employed catalyzer generally adopts the V-Mo system supported catalyst take loaded catalyst as main Types, namely with V
2O
5And MoO
3Be catalytic active substance, and add contain Na, P, Ni or rare earth element etc. compound as catalyst adjuvant,, catalytic active substance and catalyst adjuvant together loaded on the carrier and make as carrier with the inertia non-porous material.
The number of patent application of Japan catalyst chemical company is the invention of 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, the amount by reducing P or increase the auxiliary agents such as auxiliary agent potassium, caesium, rubidium and regulate activity wherein, and outlet side is equally by regulating P
2O
5Perhaps the amount of auxiliary agent potassium, caesium, rubidium is regulated, but is 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 the 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) the 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 ℃, the catalyzer hot(test)-spot temperature is too high, reaches more than 480-500 ℃, and benzene feed concentration is at 50-70g/Nm
3, yield of maleic anhydride 96-98 % by weight (in benzene), the transformation efficiency of benzene is unknown.
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, its technical characterstic is: two section bed catalysts are adopted in (1) reaction, and inlet section is the A section, and outlet section is the B section, and wherein, the A section is with V
2O
5, MoO
3, Na
2O, P
2O
5, NiO and rare earth metal be main active component, the B section by increasing the rare earth metal auxiliary agent content or reduce P
2O
5Content improves the activity of catalyzer; (2) collocation of two sections beds highly is: the A section accounts for the 40-60% of total height of bed, and the 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 ℃, benzene feed concentration is at 59-63g/Nm
3Under the condition, the 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 and a kind ofly can under high density gas-phase benzene condition, 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 the 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, take 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, among beds A and the 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, 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 among the described beds A among the 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 among the described beds A among the 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 among the described beds A among the described beds B.
Use method production MALEIC ANHYDRIDE provided by the invention, can improve the concentration of benzene in the mixture of feed body, increase the benzene load of fixed-bed reactor and benzene is transformed, so that the yield of final MALEIC ANHYDRIDE is high.For example according to the method production MALEIC ANHYDRIDE of embodiment 1, contain the mixed gas of benzene and oxidizing gas with volume space velocity 2400-2700h
-1Enter fixed-bed reactor, the concentration of benzene is 75g/m in mixed gas
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 Examples 1 is under the same operation condition, and 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 is used 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 the 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, take 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, among beds A and the 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, 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 among the described beds A among the 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 among the described beds A among the 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 among the described beds A among the described beds B.In the preferred case, 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 among the described beds A among the 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 among the described beds A among the 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 among the described beds A among the described beds B.Content by vanadium-containing compound, molybdate compound, compounds containing sodium, P contained compound and nickel compound containing among control beds A and the B, and the content of molybdate compound, P contained compound and the nickel compound containing of control beds B and the content ratio of molybdate compound, P contained compound and the nickel compound containing of beds A be in above-mentioned scope, can make the catalyzer among beds A and the B that the oxidizing reaction of benzene is had very high selectivity and the higher MALEIC ANHYDRIDE yield of acquisition.
Described vanadium-containing compound can be the conventional various vanadium-containing compounds that use in this area, such as in ammonium meta-vanadate, Vanadium Pentoxide in FLAKES, vanadium trichloride, the vanadic acid sodium one or more.
Described molybdate compound can be the conventional various molybdate compounds that use in this area, such as in ammonium molybdate, molybdic oxide, the Sodium orthomolybdate one or more.
Described compounds containing sodium can be the conventional various compounds containing sodiums that use in this area, such as in sodium phosphate, yellow soda ash, SODIUMNITRATE, the sodium-chlor one or more.
Described P contained compound can be the conventional various P contained compounds that use in this area, such as in primary ammonium phosphate, phosphoric acid, the Vanadium Pentoxide in FLAKES one or more.
Described nickel compound containing can be the conventional various nickel compound containings that use in this area, such as in nickelous nitrate, nickel oxide, nickelous chloride, nickelous carbonate, the single nickel salt one or more.
Production method according to MALEIC ANHYDRIDE of the present invention, in order to make the method obtain the transformation efficiency of better catalyst activity and higher benzene, can also contain A1 and/or A2 among described beds A and/or the beds B, 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, contain in the compound of the VIII group 4 transition metal element except nickel element one or more.In the preferred case, described A1 contains in the compound of Li, K, Rb, Cs, Nb, Mn, Fe, Co, Ag one or more, is specifically as follows in rubidium nitrate, niobium oxides, manganese oxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Silver Nitrate, iron nitrate, saltpetre, the cesium nitrate one or more.Described A2 can be selected from one or more in the 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: during 0.0001-0.01, the catalyzer that obtains has preferably 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 comprised of multiple compounds, when 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 add for the mole number in the compound of the multiple A1 of being selected from of metal oxide and, the mole number of described A2 add for the mole number in the compound of the multiple A2 of being selected from of metal oxide and.
Production method according to MALEIC ANHYDRIDE of the present invention, in order to obtain higher benzene load, improve catalyzer among the beds A to the selectivity of benzene oxidizing reaction and to improve the activity of catalyzer among the 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.
Production method according to MALEIC ANHYDRIDE of the present invention, described carrier can for routine for the production of the various carriers in the catalyzer of MALEIC ANHYDRIDE, for example, described carrier can be for containing the carrier of silicon carbide and/or aluminum oxide, and described carrier all can be commercially available.In the preferred case, take the gross weight of described carrier as benchmark, the content of silicon carbide is the 80-99.9 % by weight, and the content of aluminum oxide is the 0.1-20 % by weight.The shape of described carrier can be spherical, ring-type or tri-lobed usually.In order to make active substance load on more equably on the carrier, and can make the reaction mass benzene in the maleic anhydride production with the catalyzer that uses this carrier larger contact area be arranged, preferably use circular vectors, the external diameter of this carrier can for 6 millimeters, internal diameter can for 5 millimeters, highly can be 4 to 5 millimeters, the bulk density of described carrier can be the 0.7-0.8 grams per milliliter.
Production method according to MALEIC ANHYDRIDE of the present invention, the content that loads on the described active substance on the carrier can in very large range be chosen arbitrarily, for example, the gross weight of the catalyzer in the beds is as benchmark, the content of described active substance is the 3-30 % by weight, in the described active substance of this scope internal burden on the carrier oxidizing reaction of catalysis benzene well; In the preferred case, the gross weight of the catalyzer in the beds is as benchmark, and the content of described active substance is the 10-20 % by weight.
According to the production method of MALEIC ANHYDRIDE of the present invention, the catalyzer among above-mentioned beds A and the B can adopt the preparation method of the various known catalyzer of producing for MALEIC ANHYDRIDE.For example, can be with 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 one or more in the alcohol (for example can methyl alcohol, in the 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, from industrial angle, preferred described solvent is water.The solution that contains active substance is coated to the surface of carrier with 100-300 ℃ (preferably with 200-300 ℃), obtains loaded catalyst through after the drying and other steps.Above-mentioned active substance, carrier, solvent etc. all can be commercially available.
Production method according to MALEIC ANHYDRIDE of the present invention, the method is divided into beds A and beds B with fixed-bed reactor, the height of beds A and beds B can be chosen in a big way, for example, take 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, take 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 for MALEIC ANHYDRIDE production.In order to prevent that the excessive concentration of benzene sets off an explosion in the mixed gas, in the production of MALEIC ANHYDRIDE, the concentration of benzene is 30-80g/m in the described mixed gas usually
3In the preferred case, the concentration of benzene is 60-80g/m in the described mixed gas
3Among the present invention, unless stated otherwise, the volume of gas under the accurate state of the equal index of the volume of gas.For guaranteeing 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.Catalyzer can be brought into play under the good catalytic efficiency in guaranteeing beds of the present invention, and the volume space velocity of described mixed gas can be 1500-3500h
-1In the preferred case, the volume space velocity of described mixed gas is 2000-3000h
-1For transformation efficiency and the yield of maleic anhydride that obtains higher benzene, the temperature of described contact can be 300-500 ℃; In the preferred case, the temperature of described contact is 330-460 ℃.The present invention does not do especially pressurization or decompression operation to the device of production MALEIC ANHYDRIDE, and common described device adopts atmospheric operation, and the pressure in the described device can be 0.07-0.11MPa.
According to the production method of MALEIC ANHYDRIDE of the present invention, the catalyzer in the above-mentioned beds activated to adopt various known catalyst activation process.In the preferred case, described activation comprises catalyzer is warming up to 300 ± 5 ℃ and be warming up to 400-500 ℃ with 25-40 ℃/hour speed with 40-70 ℃/hour speed successively, and under 400-500 ℃, kept 4-12 hour, preferably, be warming up to 420-460 ℃ with 25-40 ℃/hour speed, and under 420-460 ℃, kept 4-8 hour; Then be cooled to 25 ± 5 ℃, the present invention does not limit especially to this cooling rate, preferably lowers the temperature with 70-150 ℃/hour speed.Adopt above-mentioned preferred method that catalyzer is activated 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, agents useful for same all can be commercially available in embodiments of the invention and the application examples.
Fixed-bed reactor adopt salt bath heating in the following example and the Comparative Examples, and the pressure in the fixed-bed reactor is 0.1 ± 0.01MPa.Catalyzer maximum of temperature in reaction is called the catalyzer hot(test)-spot temperature in the beds, and the 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 (being air at this) enters concentration and the salt temperature of benzene in the volume space velocity of fixed-bed reactor, the described mixed gas.
The used circular vectors of following embodiment and Comparative Examples is made with reference to the proportioning raw materials of embodiment among the ZL94107337.8 1, and different is, makes circular vectors, and the external diameter of carrier is that 6 millimeters, internal diameter are 5 millimeters, highly are 4 to 5 millimeters.
The amount of substance of the transformation efficiency of benzene (%)=(amount of substance of the amount of substance of unit time benzene charging-unit time reactor outlet benzene)/unit time benzene charging * 100%
By the weight of the product cis-butenedioic anhydride that obtains after the chemical titration reaction, calculate yield of maleic anhydride by following formula:
The weight of the weight of yield of maleic anhydride (% by weight)=unit time product cis-butenedioic anhydride/unit time benzene charging * 100%
Embodiment 1
(1) preparation of catalyzer among the 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 slurries, the gained slurries are sprayed at take 200-300 ℃ place rotating speed as the 410g circular vectors of 13-20 rev/min seed-coating machine, spraying is dried to constant mass after finishing, obtain 482.3g catalyst A-1, wherein take the gross weight of catalyst A-1 as benchmark, the content of active substance is 15 % by weight;
(2) preparation of catalyzer among the beds B
According to catalyst B-1 among 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 the 0.1g rubidium nitrate, replaces the 0.063g Erbium trioxide, do not add primary ammonium phosphate with the 0.042g Holmium trioxide with the 1.52g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, obtain catalyst B-1, wherein take 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)
Independently place separately closed container to activate above-mentioned catalyst A-1 and B-1, at first be warming up to 300 ℃ with 55 ℃/hour speed, be warming up to 450 ℃ with 30 ℃/hour speed again, under 450 ℃, kept 8 hours; Then 100 ℃/hour are cooled to 25 ℃; With the catalyst A-1 after the activation, B-1 successively layering is filled into 120ml fixed-bed reactor (reactor length 60cm, bed total height 36cm, internal diameter 21mm, together lower) in, account for 40% of fixed-bed reactor bed height so that contain the beds A of catalyst A-1, 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 (begin 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 Examples 1
(1) preparation of catalyzer among the beds A
Obtain in the same manner catalyst A among the beds A-1 with embodiment 1 step (1);
(2) preparation of catalyzer in the beds
According to catalyst B-D1 among the method Kaolinite Preparation of Catalyst bed B of step (1), different is to replace the 0.1g rubidium nitrate, replace the 0.063g Erbium trioxide, do not add primary ammonium phosphate with the 0.08g Holmium trioxide with the 1.52g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, obtain catalyst B-D1, wherein take 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 estimated, 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 among the beds A
According to catalyst A-2 among 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 the 1.9g primary ammonium phosphate, 5.9g Silver Nitrate replaces 0.1g rubidium nitrate, 0.04g europium sesquioxide to replace the 0.063g Erbium trioxide, obtain catalyst A-2, wherein take the gross weight of catalyst A-2 as benchmark, the content of active substance is 14.0 % by weight;
(2) preparation of catalyzer among the beds B
According to catalyst B-2 among 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 the 5.9g Silver Nitrate, do not add phosphoric acid with the 0.056g niobium oxides, obtain catalyst B-2, wherein take the gross weight of catalyst B-2 as benchmark, the content of active substance is 14.8 % by weight;
(3) evaluation of catalyzer
Independently place separately closed container to activate above-mentioned catalyst A-2 and B-2, at first be warming up to 300 ℃ with 65 ℃/hour speed, be warming up to 425 ℃ with 25 ℃/hour speed again, under 425 ℃, kept 10 hours; Then be cooled to 25 ℃ with 120 ℃/hour speed; Catalyst A-2 after the activation, B-2 successively layering are filled in the 120ml fixed-bed reactor, account for 50% of fixed-bed reactor bed height so that contain the beds A of catalyst A-2, 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 among the beds A
According to catalyst A-3 among the method Kaolinite Preparation of Catalyst bed A of embodiment 1 step (1), different is that the 1.17g Vanadium Pentoxide in FLAKES replaces the 1.9g primary ammonium phosphate, 5.9g Silver Nitrate replaces the 0.1g rubidium nitrate, adds the 0.039g niobium oxides, obtain catalyst A-3, wherein take the gross weight of catalyst A-3 as benchmark, the content of active substance is 13.9 % by weight;
(2) preparation of catalyzer among the beds B
According to catalyst B-3 among 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 that 4.6g, the weight that adds 0.29g yellow soda ash, nickelous nitrate are 1.28g, 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 take the gross weight of catalyst B-3 as benchmark, the content of active substance is 16.5 % by weight;
(3) evaluation of catalyzer
Independently place separately closed container to activate above-mentioned catalyst A-3 and B-3, at first be warming up to 300 ℃ with 40 ℃/hour speed, be warming up to 500 ℃ with 40 ℃/hour speed again, under 500 ℃, kept 5 hours; Then be cooled to 25 ℃ with 80 ℃/hour speed; Catalyst A-3 after the activation, B-3 successively layering are filled in the 120ml fixed-bed reactor, account for 60% of fixed-bed reactor bed height so that contain the beds A of catalyst A-3, 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 among the 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 slurries, the gained slurries are sprayed at take 220-260 ℃ place rotating speed as the inertia circular vectors of 15-20 rev/min seed-coating machine, drying obtained catalyst A-4 after spraying finished, wherein take the gross weight of catalyst A-4 as benchmark, the content of active substance is 15.5 % by weight;
(2) preparation of catalyzer among the beds B
According to catalyst B-4 among 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 take 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 estimated, and different is that catalyst A-4 replaces catalyst A-1, catalyst B-4 to replace catalyst B-1, and operational condition and experimental result are as shown in table 1.
Comparative Examples 2
(1) preparation of catalyzer among the beds A
Obtain in the same manner catalyst A among the beds A-4 with embodiment 4 steps (1);
(2) preparation of catalyzer among the beds B
According to catalyst B-D2 among 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 take 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 estimated, 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 among the beds A
Obtain in the same manner catalyst A among the beds A-1 with embodiment 1 step (1);
(2) preparation of catalyzer among the beds B
Obtain in the same manner catalyst B among the beds B-1 with embodiment 1 step (2);
(3) evaluation of catalyzer
Method according to embodiment 1 step (3) is estimated, and different is to place respectively separately fixed-bed reactor to activate above-mentioned catalyst A-1 and B-1, and the mixed gas of benzene and air is with volume space velocity 2000h
-1Pass into fixed-bed reactor, (fs is warming up to 300 ℃ with 100 ℃ in temperature programming, then subordinate phase is warming up to 420 ℃ with 50 ℃/hour) and 420 ℃ of lower maintenances 12-24 hour, be cooled to again 25 ℃, operational condition and experimental result are as shown in table 1.
Table 1
In the table 1, data by embodiment 1-3 and Comparative Examples 1 compare, adopted the technical scheme of CN101284242A in the Comparative Examples 1, the content that has reduced P contained compound among the 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 simultaneously molybdate compound among the beds B, 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 among the beds B is the 0.5-0.9 of the mol ratio of molybdate compound and vanadium-containing compound among the described beds A; 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 among the described beds A among the 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 among the described beds A among the described beds B, 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 by embodiment 1 and embodiment 4 relatively can be found out and contain in the beds that A1 and A2 can improve catalyst activity and to the selectivity of the oxidizing reaction of benzene.Compare with the data of embodiment 5 by embodiment 1, can find out that the catalytic efficiency that adopts activation method of the present invention can make catalyzer improves.
Claims (10)
1. the production method of a MALEIC ANHYDRIDE, the method is included under the 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, take 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, among beds A and the 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 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 among the described beds A among the 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 among the described beds A among the 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 among the described beds A among the described beds B.
2. method according to claim 1, wherein, 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 among the described beds A among the 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 among the described beds A among the 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 among the described beds A among the described beds B.
3. method according to claim 1, wherein, also contain A1 and/or A2 among described beds A and/or the beds B, 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, contain in the compound of the VIII group 4 transition metal element except nickel element one or more; Described A2 is selected from one or more in the lanthanide metal compound; Described A1, A2 is all in metal oxide, described vanadium-containing compound, described molybdate compound, described compounds containing sodium, described P contained compound, described nickel compound containing, A1, the mol ratio of A2 is 1: 0.3-1.1: 0.001-0.3: 0.002-0.25: 0.001-0.5: 0.0001-0.2: 0.0001-0.01, preferably, described vanadium-containing compound, described molybdate compound, described compounds containing sodium, described P contained compound, described nickel compound containing, A1, the mol ratio of A2 is 1: 0.4-1: 0.01-0.25: 0.005-0.15: 0.005-0.25: 0.0005-0.1: 0.0001-0.001.
4. method according to claim 3, wherein, described A1 contains in the compound of Li, K, Rb, Cs, Nb, Mn, Fe, Co, Ag one or more, and 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.
5. according to claim 3 or 4 described methods, wherein, described beds A and beds B all contain A1, and the A1 of described beds A is the oxide compound of Rb and/or Ag; The A1 of described beds B is the oxide compound of Co and/or Mn.
6. method according to claim 1, wherein, described carrier is the carrier that contains silicon carbide and/or aluminum oxide, and preferably, take the gross weight of described carrier as benchmark, the content of silicon carbide is the 80-99.9 % by weight, and the content of aluminum oxide is the 0.1-20 % by weight; Being shaped as of described carrier is spherical, ring-type or tri-lobed, preferably, described carrier be shaped as ring-type.
7. method according to claim 1, wherein, the gross weight of the catalyzer in the beds is as benchmark, the content of described active substance is the 3-30 % by weight, preferably, the gross weight of the catalyzer in the beds is as benchmark, and the content of described active substance is the 10-20 % by weight.
8. method according to claim 1, wherein, take the total height of beds as benchmark, described beds A accounts for 30-70%, described beds B accounts for 30-70%, preferably, and take the total height of beds as benchmark, described beds A accounts for 40-60%, and described beds B accounts for 40-60%.
9. method according to claim 1, wherein, the concentration of benzene is 30-80g/m in the described mixed gas
3, preferably, the concentration of benzene is 60-80g/m in the described mixed gas
3The volume ratio of described benzene and oxidizing gas is 0.012-0.078: 1, and preferably, the volume ratio of described benzene and oxidizing gas is 0.015-0.02: 1; The volume space velocity of described mixed gas is 1500-3500h
-1, preferably, the volume space velocity of described mixed gas is 2000-3000h
-1, the temperature of described contact is 300-500 ℃, preferably, the temperature of described contact is 330-460 ℃.
10. method according to claim 1, wherein, the method that described catalyzer is activated comprises catalyzer is warming up to 300 ± 5 ℃ and be warming up to 400-500 ℃ with 25-40 ℃/hour speed with 40-70 ℃/hour speed successively, and under 400-500 ℃, kept 4-12 hour, preferably, be warming up to 420-460 ℃ with 25-40 ℃/hour speed, and under 420-460 ℃, kept 4-8 hour; Then be cooled to 25 ± 5 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN112684832A (en) * | 2019-10-17 | 2021-04-20 | 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 |
| CN113842934A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Oxidation catalyst and preparation method and application thereof |
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| 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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| 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN112684832A (en) * | 2019-10-17 | 2021-04-20 | 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 |
| 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 |
| CN113842934A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Oxidation catalyst and preparation method and application thereof |
| 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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