CN103691467B - A kind of Catalysts and its preparation method and application - Google Patents
A kind of Catalysts and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of Catalysts and its preparation method, the method comprises: (1) is under Redox Condition, make vanadium-containing compound, phosphorus-containing compound, zinc compound, contact in liquid reaction medium with the simple substance of rare earth element and/or compound containing the compound of elements A, be separated after contact and remove liquid reaction medium, obtain catalyst precursor; (2) by described catalyst precursor and shaping assistant mixing aftershaping, described shaping assistant comprises lubricant, expanding agent and adhesive.The catalyst that method of the present invention prepares is used for during preparing cis-anhydride by n-butane oxidation produces, there is the conversion ratio of higher normal butane, Selectivity of maleic anhydride and yield of maleic anhydride, and the intensity of this catalyst is higher can steady in a long-term use.
Description
Technical field
The preparation method that the present invention relates to a kind of catalyst of conversion ratio, Selectivity of maleic anhydride and the yield of maleic anhydride that can improve normal butane and the catalyst prepared by the method, and the application of this catalyst in preparing cis-anhydride by n-butane oxidation.
Background technology
As everyone knows, maleic anhydride (also known as maleic anhydride, being called for short cis-butenedioic anhydride) is important Organic Chemicals, and it has become the second largest organic acid anhydride being only second to phthalic anhydride.Be widely used in the industries such as the various unsaturated polyester (UP) of preparation, coating, food, agricultural chemicals, medicine and weaving at present, the demand of market to cis-butenedioic anhydride is growing, the output of China's cis-butenedioic anhydride is also increasing rapidly in recent years, and current China Maleic Anhydrite annual production reaches nearly 1,000,000 tons/year.
The production method of cis-butenedioic anhydride mainly contains benzene method and normal butane method.Because the current price of n-butane feedstock is lower than benzene raw materials, add that normal butane reaction environmental pollution is little, and the reaction of preparing cis-anhydride by n-butane oxidation has more Atom economy than benzene method, therefore, the production method of cis-butenedioic anhydride mainly normal butane method in the world, the production of China's cis-butenedioic anhydride is also changing to normal butane method.
No matter adopt which kind of method to produce cis-butenedioic anhydride, in its explained hereafter, the preparation of catalyst is all crucial.There is a lot of bibliographical information to cross and produced at gas molecule in space oxygen catalytic oxidation normal butane the catalyst used in the process of cis-butenedioic anhydride.Such as, disclose a kind of V-P-O series catalysts in CN1345630A, this catalyst uses isobutanol as the high-concentration phosphoric acid of liquid reaction medium and 90-110%, and add Zn, third and fourth and the BSA such as Mo and Er, obtain butane maleic anhydride catalyst presoma, to the binding agent of the shaping employing modified starch of presoma and polyvinyl alcohol, be shaped to ring catalyst, the better performances of catalyst.But there is following shortcoming in this kind of catalyst: the activity and selectivity (conversion ratio of normal butane, Selectivity of maleic anhydride and yield of maleic anhydride etc.) of (1) catalyst need further raising; (2) the evaluation salt temperature of catalyst is higher, and heat dissipation capacity is slow, and catalyst loading improves difficulty; (3) intensity of catalyst is general, and service life can reduce.
Summary of the invention
The preparation method that the object of the present invention is to provide a kind of catalyst of conversion ratio, Selectivity of maleic anhydride and the yield of maleic anhydride that can improve normal butane and the catalyst prepared by the method, and the application of this catalyst in preparing cis-anhydride by n-butane oxidation.
The preparation method of catalyst provided by the invention, the method comprises the following steps:
(1) under Redox Condition, make vanadium-containing compound, phosphorus-containing compound, zinc compound, contact in liquid reaction medium with the simple substance of rare earth element and/or compound containing the compound of elements A, in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.5-2:0.01-0.25:0.001-0.05:0.0001-0.02, be separated after contact and remove liquid reaction medium, obtain catalyst precursor; Described elements A is selected from least one in IA race element, IB race element, VB race element, group vib element, VIIB race element and VIII element except v element; Described liquid reaction medium is selected from least one in the alcohol of C1-C12, the monoalky lether of the dihydroxylic alcohols of C2-C12 and N-alkylamide;
(2) by described catalyst precursor and shaping assistant mixing aftershaping, described shaping assistant comprises lubricant, expanding agent and adhesive, it is one or more in the polystyrene of 1000-10000 that described expanding agent to contain in molecule containing the compound of two or more hydroxyl, number-average molecular weight, and with the total amount of expanding agent for benchmark, the compound containing two or more hydroxyl in described molecule, number-average molecular weight are one or more the total amount in the polystyrene of 1000-10000 is more than 10 % by weight.
The catalyst that the present invention also provides said method to prepare, wherein, the specific area of this catalyst is 15-50m
2/ g, most probable pore size is 10-1000nm.
The present invention further provides the application of above-mentioned catalyst in butane oxidation maleic anhydride process.
Adopt the catalyst that method of the present invention prepares, prepare in cis-butenedioic anhydride for catalysis n butane oxidation, the conversion ratio of normal butane, Selectivity of maleic anhydride and yield of maleic anhydride can be improved, such as, salt temperature be 370-420 DEG C, the volumetric concentration of normal butane be 2.0% and volume space velocity be 1500-2000h
-1condition under, adopt the catalyst that the embodiment 1 of method provided by the invention prepares, the conversion ratio of normal butane is 83-90%, Selectivity of maleic anhydride is 56-68%, yield of maleic anhydride is 85-101 % by weight, and adopting the catalyst that the method for comparative example 1 prepares, the conversion ratio of normal butane is 76-83%, Selectivity of maleic anhydride is 50-58%, yield of maleic anhydride is 76-88 % by weight.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
First, the invention provides a kind of preparation method of catalyst, the method comprises the following steps: (1) is under Redox Condition, make vanadium-containing compound, phosphorus-containing compound, zinc compound, contact in liquid reaction medium with the simple substance of rare earth element and/or compound containing the compound of elements A, in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.5-2:0.01-0.25:0.001-0.05:0.0001-0.02, be separated after contact and remove liquid reaction medium, obtain catalyst precursor; Described elements A is selected from least one in IA race element, IB race element, VB race element, group vib element, VIIB race element and VIII element except v element; Described liquid reaction medium is selected from least one in the alcohol of C1-C12, the monoalky lether of the dihydroxylic alcohols of C2-C12 and N-alkylamide; (2) by described catalyst precursor and shaping assistant mixing aftershaping, described shaping assistant comprises lubricant, expanding agent and adhesive, it is one or more in the polystyrene of 1000-10000 that described expanding agent to contain in molecule containing the compound of two or more hydroxyl, number-average molecular weight, and with the total amount of expanding agent for benchmark, the compound containing two or more hydroxyl in described molecule, number-average molecular weight are one or more the total amount in the polystyrene of 1000-10000 is more than 10 % by weight.
As in molecule containing the compound of two or more hydroxyl, the carbon number that can replace for the polyalcohol of C2-C12, two or more hydroxyl be at least 3 aldehyde and the ketone that replaces of two or more hydroxyl at least one.
As the polyalcohol of C2-C12, can be C2-C12 aliphatic polyol, C3-C12 alicyclic polyol or C7-C12 aromatic polyol.The monohydric alcohol of C2-C12 can be enumerated: ethanol, normal propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 2-methyl-2-butanols, 3-methyl-1-butanol, 3-methyl-2-butanols, neopentyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 2 methyl-2-amylalcohols, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2,2-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 1-heptanol, 2-enanthol, 3-enanthol, 4-enanthol, 2-methyl-2-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-octanol, 1 nonyl alcohol, 1-decyl alcohol, laruyl alcohol, 3-butene-1-ol, 3-butene-2-ol, 1-POL, 2-amylene-1-ol, 3-amylene-2-alcohol, 4-amylene-1-ol, 4-amylene-2-alcohol, 1-hexene-3-ol, 2-hexen-1-ol, blatter alcohol, 4-hexen-1-ol, 5-hexen-1-ol, the aliphatic alcohols such as 5-hexen-2-ol, the alicyclic alcohols such as cyclobutanol, cyclopentanol, cyclohexanol, suberol, 2-cyclohexene-1-alcohol, the aromatic alcohols such as phenmethylol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, benzyl carbinol, phenylpropanol, 1-phenyl-n-butyl alcohol, 2-phenyl-2-butanols, 3-phenyl-n-butyl alcohol, 4-phenyl-n-butyl alcohol, 4-phenyl-2-butanols, 1-phenyl-2-amylalcohol, 6-phenyl-1-hexanol, 1-phenyl-2-propylene-1-alcohol.The material that C2-C12 polyalcohol can be optionally substituted by a hydroxyl group at least one hydrogen atom being applicable to being substituted on the carbon atom in the monohydric alcohol of the above-mentioned C2-C12 enumerated, adducible material like this comprises: ethylene glycol, 1, 2-propane diols, 1, ammediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 1, 5-hexylene glycol, 1, 6-hexylene glycol, 1, 7-heptandiol, 1, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-ring pentanediol, 1, 4-cyclohexanediol, 1, 2-benzene dimethanol, 1, 1, 1-trimethylolethane, trimethylolpropane, pentaerythrite etc.
The carbon number replaced as two or more hydroxyl is at least the aldehyde of 3, can enumerate: the aldehyde of the aldehyde of the aldehyde of D-glyceraldehyde, 1,2,3-trihydroxy-butyraldehyde and isomer, ribose and isomer, glucose and isomer.
As the ketone that two or more hydroxyl replaces, can enumerate: dihydroxyacetone (DHA), D-revive the ketone of the ketone of the ketone of ketose and isomer, ribulose and isomer, fructose and isomer.
As the compound containing two or more hydroxyl in molecule, can also be the polyethylene glycol of 1000-10000 for number-average molecular weight.
In the preparation process in accordance with the present invention, compound containing two or more hydroxyl in described molecule is preferably one or more in the polyethylene glycol of 1000-10000 containing the polyalcohol of C2-C12 and number-average molecular weight, more preferably containing 1,1,1-trimethylolethane, trimethylolpropane, number-average molecular weight are one or more in the polyethylene glycol of 1000-10000.
In addition, one or more in the described expanding agent acid anhydrides that can also optionally be formed containing the aromatic hydrocarbons of C6-C12, the organic carboxyl acid of carbon number 1-20, above-mentioned organic carboxyl acid and the unsubstituted ketone of hydroxyl.
As the aromatic hydrocarbons of C6-C12, can enumerate: benzene, toluene, ethylbenzene, n-proplbenzene, isopropylbenzene, n-butylbenzene, dimethylbenzene, naphthalene etc.
Organic carboxyl acid can be one or more in aliphatic carboxylic acid, alicyclic carboxylic acid and aromatic carboxylic acid.
As the aliphatic carboxylic acid of carbon number 1-20, can be monocarboxylic acid or polybasic carboxylic acid, can enumerate: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, hendecanoic acid, dodecylic acid, tetradecanoic acid, stearic acid, butenoic acid, malonic acid, 1,4-succinic acid, 1,5-adipic acid, 1,6-adipic acid, 1,7-pimelic acid, 1,8-suberic acid etc.
As the alicyclic carboxylic acid of carbon number 4-12, can be monocarboxylic acid or polybasic carboxylic acid, can enumerate: cyclopropanecarboxylic acid, cyclopentane-carboxylic acid, 3-cyclopentanepropanoiacid acid, 3-cyclohexyl-1-formic acid, 3-cyclohexylpropionic acid, cyclohexane valeric acid, 3-aleprolic acid, 3-cyclohexene-1-caproic acid, 1,3-cyclohexyl dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid, cyclohexyl succinic acid etc.
As the aromatic carboxylic acid of carbon number 7-20, can be monocarboxylic acid or polybasic carboxylic acid, can enumerate: benzoic acid, phenylacetic acid, diphenyl acetic acid, 3-benzenpropanoic acid, 1-naphthoic acid, 2-naphthoic acid, methyl α-naphthyl acetate, cinnamic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) etc.
As the acid anhydrides that above-mentioned carboxylic acid is formed, can be the acid anhydrides that two carboxylic acids take off the formation of a part water, the acid anhydrides that also can be formed for a part water de-between two carboxyls in polybasic carboxylic acid.The acid anhydrides those skilled in the art that above-mentioned substance can be formed can know, do not enumerate at this.
As the unsubstituted ketone of hydroxyl, can enumerate: acetone, 2-butanone, cyclobutanone, 2 pentanone, propione, cyclopentanone, methyl-n-butyl ketone, 3-hexanone, 3-methyl-2 pentanone, 4-methyl-2 pentanone, 2-methyl-propione, cyclohexanone, acetophenone, propiophenone, 1-Phenyl 2 butanone, benzene pentanone etc.
In the preferred case, described expanding agent can also contain stearic acid.Special restriction is not had for stearic consumption, under preferable case, with the gross weight of expanding agent for benchmark, the compound containing two or more hydroxyl in molecule and/or number-average molecular weight are the content of the polystyrene of 1000-10000 is 10-90 % by weight, and stearic content is 10-90 % by weight.
In the present invention, for preparing lubricant that normal butane catalyst for preparing cis-anhydride uses and adhesive has no particular limits, known various material can be used.
As lubricant, can enumerate: graphite, carbon black etc., be preferably graphite.
As adhesive, use modified starch and water-soluble resin adhesive.Wherein the weight ratio of modified starch and water-soluble resin adhesive can be 1-125:1, is preferably 2-100:1.
The preparation of modified starch is known, be obtained by reacting by starch and modifier, wherein, starch can use at least one in tapioca, farina, cornstarch, wheaten starch and rice starch, and modifier can use at least one in formaldehyde, epoxychloropropane, cis-butenedioic anhydride, sodium metaphosphate, ammonium dihydrogen phosphate (ADP), niter cake, diammonium hydrogen phosphate and POCl3; The weight ratio of starch and modifier is preferably 1:0.01-0.5, is more preferably 1:0.05-0.25.
As water-soluble resin adhesive, can be selected from POLYPROPYLENE GLYCOL, polyacrylic acid, polyvinyl acetate and polyvinyl alcohol one or more.The above-mentioned number-average molecular weight enumerating material is preferably 1000-20000, and more preferably number-average molecular weight is that the polyvinyl alcohol of 1000-10000 or polyvinyl acetate use as water-soluble resin adhesive.
In the preparation process in accordance with the present invention, the consumption of lubricant, expanding agent and adhesive can be chosen in a big way, such as, relative to the described catalyst precursor of 100 weight portions, the consumption of lubricant is 0.5-5 weight portion, the consumption of expanding agent is 0.5-10 weight portion, and the consumption of adhesive is 1-25 weight portion.In the preferred case, relative to the described catalyst precursor of 100 weight portions, the consumption of lubricant is 0.5-1.5 weight portion, and the consumption of expanding agent is 1-10 weight portion, and the consumption of adhesive is 1-20 weight portion.
In the preparation process in accordance with the present invention, vanadium-containing compound, phosphorus-containing compound, zinc compound, can choose in a big way containing the consumption of the compound of elements A, the simple substance of rare earth element and/or compound.Such as meet: in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.6-2:0.01-0.15:0.005-0.025:0.0001-0.015.In the preferred case, in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.6-1.5:0.01-0.05:0.005-0.01:0.0001-0.01.
Vanadium-containing compound can be selected from least one in vanadic anhydride, ammonium metavanadate.
Phosphorus-containing compound can be the various phosphorus-containing compounds that this area routine uses, such as, be selected from least one in the phosphoric acid of mass concentration 85-110%, pyrophosphoric acid, polyphosphoric acids and phosphorus pentoxide.In the preferred case, phosphorus-containing compound is preferably at least one in the phosphoric acid of mass concentration 90-105%, pyrophosphoric acid and polyphosphoric acids.
Zinc compound can be the various zinc compounds that this area routine uses, such as, be selected from containing the sulfate of Zn-ef ficiency, nitrate, carbonate or their mixture, can enumerate: zinc sulfate, zinc nitrate, zinc carbonate etc.
As the compound containing elements A, wherein, preferred elements A is selected from one or more in Li, Rb, Mo, Co, Mn, Nb, Ag and Fe.More preferably elements A is selected from one or more in Mo and Li, Co and Fe, and one or more the mass ratio wherein in Mo and Li, Co and Fe does not specially require.Compound containing elements A can use with the form containing the oxide of element A, sulfate, nitrate or carbonate, also can use with other suitable form, thus the described compound containing elements A can use one or more in molybdenum oxide, cobalt oxide, di-iron trioxide, silver oxide, niobium oxide, manganese dioxide, manganese sulfate, ferric sulfate, rubidium nitrate, cobalt nitrate, silver nitrate, lithium carbonate, LiMn2O4, lithium molybdate.
As simple substance and/or the compound of rare earth element, the compound of rare earth element to use containing the form of the oxide of rare earth element, chloride, sulfate, nitrate or carbonate, also can use with other suitable form.From the viewpoint of raw material sources and cost, preferably use the simple substance of rare earth element and/or the oxide of rare earth element.In addition, rare earth element is preferably Er, Ho, Pr or Gd.
As the alcohol of the C1-C12 of liquid reaction medium, be preferably the monohydric alcohol of C1-C12, can enumerate thus: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 2-methyl-2-butanols, 3-methyl-1-butanol, 3-methyl-2-butanols, neopentyl alcohol, 1-hexanol, 2-hexanol-, 3-hexanol, 2-methyl-1-pentene alcohol, 2 methyl-2-amylalcohols, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2,2-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 1-heptanol, 2-enanthol, 3-enanthol, 4-enanthol, 2-methyl-2-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-octanol, 1 nonyl alcohol, 1-decyl alcohol, phenmethylol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, benzyl carbinol, phenylpropanol, 1-phenyl-n-butyl alcohol, 2-phenyl-2-butanols, 3-phenyl-n-butyl alcohol, 4-phenyl-n-butyl alcohol, 4-phenyl-2-butanols etc., above-mentioned substance can be used alone, two or more may be used in combination.
As the monoalky lether of the dihydroxylic alcohols of the C2-C12 of liquid reaction medium, wherein, alkyl is preferably the alkyl of carbon number 1-4, the alkyl of carbon number 1-4 can be enumerated: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, in the monoalky lether of the dihydroxylic alcohols of described C2-C12 thus, representational material can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, 1, the single ether of 2-propane diols-1-monomethyl ether, 1,3-PD monomethyl ether, 1,2-PD-1-etc.
As the N-alkylamide of liquid reaction medium, wherein, the carbon number of the alkyl that preferred nitrogen atom replaces is the alkyl that 1-4, nitrogen-atoms replace can be one or two, thus can enumerate: N-METHYLFORMAMIDE, N-ethyl-formamide, N, dinethylformamide (DMF), N-methylacetamide, N-ethyl acetamide, DMA, N-methyl-benzamide etc.
In the present invention, as liquid reaction medium, particular methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols, isobutanol, phenmethylol, glycol monoethyl ether, 1, 2-propane diols-1-monomethyl ether, 1, ammediol monomethyl ether and N, at least one in dinethylformamide, more preferably 1-propyl alcohol, 2-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols, isobutanol, phenmethylol, glycol monoethyl ether, 1, 2-propane diols-1-monomethyl ether and 1, at least one in ammediol monomethyl ether, preferred 1-propyl alcohol further, 2-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols, at least one in isobutanol and phenmethylol, further be preferably isopropyl alcohol, at least one in isobutanol and phenmethylol.
In the present invention, the consumption for liquid reaction medium has no particular limits, and reaction can be made to carry out smoothly, such as the weight ratio 1-40:1 of liquid reaction medium and described vanadium-containing compound, is preferably 2-20:1.
In the present invention, for Redox Condition, can adopt the various Redox Conditions that the v element in vanadium-containing compound can be reduced to lower valence state of this area routine, such as, described Redox Condition comprises: temperature is 90-200 DEG C, the time is 4-24 hour.In the preferred case, described Redox Condition comprises: temperature is 90-150 DEG C, the time is 4-20 hour.
In the step (1) of preparation method of the present invention, for vanadium-containing compound, phosphorus-containing compound, zinc compound, the mode that contacts in liquid reaction medium containing the compound of elements A and the simple substance of rare earth element and/or compound, there is no particular limitation.Can following manner be adopted: (a) under Redox Condition, in liquid reaction medium regardless of order add vanadium-containing compound, phosphorus-containing compound, zinc compound, containing the compound of elements A and the simple substance of rare earth element and/or compound; B contact is divided into two stages by (), first make vanadium-containing compound, phosphorus-containing compound and zinc compound in liquid reaction medium, carry out the first stage to contact, then make to contact gained material with the first stage containing the compound of elements A, the simple substance of rare earth element and/or compound and carry out second stage contact; C contact is divided into two stages by (), first make vanadium-containing compound, phosphorus-containing compound, zinc compound and in liquid reaction medium, carry out the first stage containing the compound of elements A to contact, then make the simple substance of rare earth element and/or compound contact gained material with the first stage to carry out second stage contact.In addition, preferably carry out the contact of aforesaid way in the presence of a mineral acid, described inorganic acid can one or more in the concentrated sulfuric acid of the concentrated hydrochloric acid of service property (quality) concentration more than 37%, the red fuming nitric acid (RFNA) of mass concentration more than 65% and mass concentration more than 85%, the consumption of acid does not specially require, and those skilled in the art can specifically select according to actual needs.For contacting the mode (b) and mode (c) that are divided into two stages to carry out, total time spent by two stage contacts is 4-24 hour, wherein, the time of contact first stage can be 2-12 hour, and the time of second stage contact can be 2-12 hour; In addition, the temperature of two stage contacts can be identical or different, as long as in the scope of 90-200 DEG C (preferred 90-150 DEG C), in order to simplify the operation, preferably the temperature of two stage contacts is identical.In the above-mentioned way of contact (a) to (c), preferred embodiment (c), and in mode (c), preferably vanadium-containing compound, zinc compound and the compound containing elements A are first added, phosphorus-containing compound adds subsequently, or phosphorus-containing compound is progressively added with being added in pilot process of above-mentioned substance, the butanes conversion of the butane oxidation catalyst for preparing cis-anhydride prepared, Selectivity of maleic anhydride and yield of maleic anhydride are improved further.
In the step (1) of preparation method of the present invention, be separated and remove liquid reaction medium, the process obtaining catalyst precursor comprises: described contact is filtered afterwards and obtained moistening solid, then use the alcohol of C1-C12 (if step (1) uses the alcohol of C1-C12 as liquid reaction medium, then preferably use identical alcohol washing) washing solid, washing after preferred at 100-150 DEG C dry 2-20 hour, dry roasting obtains catalyst precursor.
In the step (2) of preparation method of the present invention, as long as catalyst precursor and shaping assistant mix by described mixing, can carry out catalyst precursor and shaping assistant mixing in presence of water, the consumption for water has no particular limits, and mixture can be made shaping.Known method can be adopted shaping to said mixture, the formers such as preferred use banded extruder (kneader) are shaping to said mixture, shape after shaping can be cylinder, ring-type, spherical, tri-lobed (also comprises special-shaped tri-lobed, also be called that abnormity is cylindric, refer to and remove outer peripheral symmetrical three cylindrical shape, wherein the bottom center of three cylinders of connected symmetrical dendrimer is equilateral triangle), wheel shape, Special-Shaped Column etc., shape after preferably shaping is ring-type and special-shaped column, size after shaping can be Φ 5-10mm(diameter) × 4-6mm(height) × 1-5mm(thickness).
The catalyst prepared by above-mentioned method, the specific area of this catalyst is 15-50m
2/ g, most probable pore size is 10-1000nm.
The catalyst that said method prepares may be used for preparing cis-anhydride by n-butane oxidation.The catalyst filling prepared by said method enters in fixed bed reactors etc., uses salt bath to heat, passes into the mist of normal butane and oxidizing gas, can carry out the production of cis-butenedioic anhydride with certain speed and concentration to beds.The production of above-mentioned cis-butenedioic anhydride can adopt known working condition (as see CN1345630A), and the present invention preferably adopts working condition to comprise: the volume space velocity that salt temperature is 360-420 DEG C, the volumetric concentration of normal butane (with the cumulative volume of mist for benchmark) is 1.0-2.0%, mist is 500-2500h
-1, in addition, oxidizing gas can adopt oxygen or air; Pressure in fixed bed reactors is generally 0.07-0.11MPa.In the present invention, unless stated otherwise, the volume of gas all refers to the volume of gas under standard state.
In addition, be used for, in preparing cis-anhydride by n-butane oxidation, preferably activating catalyst in advance at the catalyst that said method is prepared.Activation process is similar to the production process of above-mentioned cis-butenedioic anhydride, but difference is to adopt temperature-programmed mode to control salt temperature, and first loading in fixed bed reactors by catalyst, take volume space velocity as 500-2500h
-1pass into the mist containing normal butane of volumetric concentration 0.5-1.5%, first be warming up to 200-300 DEG C with the speed of 50-100 DEG C/h, then 400-500 DEG C is warming up to the speed of 10-50 DEG C/h, then 2-24 hour is maintained at this temperature, namely the activation to catalyst is completed, and then under normal salt temperature, stable maleic anhydride production can be carried out.
The present invention is described in detail by the following examples.
Unless stated otherwise, in embodiments of the invention, comparative example and test case, agents useful for same all can be commercially available.
The specific area of catalyst and Estimation of Pore Size carry out on the automatic physical adsorption appearance of MicromeriticsASAP2020 type, and catalyst sample is in high purity N
2in with 10 DEG C of min
-1temperature programming, to 350 DEG C, vacuumizes 4h at this temperature and carries out pretreatment, at 0-1mmHg, carries out N to material
2adsorption and desorption isotherms complete analysis.The elementary analysis of catalyst sample is at SEM-EDX(FEIXL-30 type Flied emission environmental scanning electronic microscope instrument) on measure.
Embodiment 1
(1) in the there-necked flask with agitating device and reflux condenser, 37.18gV is added
2o
5, 3.3g zinc sulfate, 0.4gMoO
3, 3mL concentrated hydrochloric acid (mass concentration 36-37%), 400mL isobutanol and 17g mass concentration be 105% phosphoric acid (manufacturer: Beijing You Peng Fine Chemical Co., Ltd), be uniformly mixed and be warming up to 105 DEG C of back flow reaction 4 hours, backward there-necked flask in add 0.1g erbium and continue back flow reaction 6 hours at 105 DEG C, obtain the suspension of turquoise, suspension is cooled to room temperature, filter and use isobutanol to wash 2 times to filter cake, then by filter cake 100 DEG C of oven dry, obtain catalyst precursor A1.In this catalyst precursor A1, with the mole of v element for benchmark, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.61:0.048:0.0067:0.0014.
(2) above-mentioned steps (1) is adopted to prepare 100g catalyst precursor A1, by itself and 2g1,1,1-trimethylolethane, 1g graphite, 10g modified starch (manufacturer: Beijing You Peng Fine Chemical Co., Ltd), 6g polyvinyl alcohol (manufacturer: Chemical Reagent Co., Ltd., Sinopharm Group, number-average molecular weight 2000,) and suitable quantity of water mix, kneader is used this mixture to be shaped to the ring-type of Φ 6mm × 4mm × 1.5mm, called after catalyst Cat-1.The most probable pore size of this catalyst Cat-1 porose for hole that 50-600nm(most probable pore size is 50-100nm accounts for 71%), BET specific surface area is 30m
2/ g.
Comparative example 1
With the step (1) of embodiment 1.
(2) stearic acid is used to replace 1,1,1-trimethylolethane, mixture is shaped to the ring-type of Φ 6mm × 5mm × 2mm, in addition, operate in the same manner as the step (2) of embodiment 1, obtain catalyst Cat-D1, the most probable pore size of this catalyst Cat-D1 porose for hole that 50-500nm(most probable pore size is 50-100nm accounts for 50%), BET specific surface area is 25m
2/ g.
Embodiment 2
(1) in the there-necked flask with agitating device and reflux condenser, 38.00gV is added
2o
5, 0.8g zinc sulfate, 0.8gCo (NO
3)
26H
2o, 0.2gMoO
3, the phosphoric acid (manufacturer: Beijing You Peng Fine Chemical Co., Ltd) of 4mL hydrochloric acid (mass concentration 36%), 450mL phenmethylol and 37g mass concentration 95%, is uniformly mixed and is warming up to 140 DEG C of back flow reaction 6 hours, backward there-necked flask in add 0.6gHo
2o
3continue back flow reaction 5 hours at 140 DEG C, obtain the suspension of turquoise, suspension is cooled to room temperature, filter and also use isobutanol to wash 2 times to filter cake, then by filter cake 130 DEG C of oven dry, obtain catalyst precursor A2.In this catalyst precursor A2, with the mole of v element for benchmark, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:1.18:0.097:0.0096:0.0072.
(2) according to the method for embodiment 1 step (2), except by using catalyst precursor A2 to replace catalyst precursor A1, use kneader to be shaped to by this mixture except the ring-type of Φ 6mm × 4mm × 1.5mm, obtain catalyst Cat-2.This catalyst Cat-2 most probable pore size porose for hole that 50-600nm(most probable pore size is 50-100nm accounts for 75%), BET specific surface area is 29m
2/ g.
Embodiment 3
(1) in the there-necked flask with agitating device and reflux condenser, 38.05g ammonium metavanadate, 3.56g zinc nitrate, 0.2g lithium carbonate, 0.2gMoO is added
3, 2mL sulfuric acid (mass concentration 85%), 500mL mixed alcohol (wherein, the volume ratio of isobutanol and phenmethylol is 4:1) and the pyrophosphoric acid (manufacturer: Beijing You Peng Fine Chemical Co., Ltd) of 37.5g mass concentration 100%, be uniformly mixed and be warming up to 90 DEG C of back flow reaction 5 hours, backward there-necked flask in add 0.8gEr
2o
3continue back flow reaction 8 hours at 90 DEG C, obtain the suspension of turquoise, suspension is cooled to room temperature, filter and also use isobutanol to wash 2 times to filter cake, then by filter cake 110 DEG C of oven dry, obtain catalyst precursor A3.In this catalyst precursor A3, with the mole of v element for benchmark, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:1.6:0.111:0.02:0.01.
(2) according to the method for embodiment 1 step (2), except by using catalyst precursor A3 to replace catalyst precursor A1, use kneader to be shaped to by this mixture except the ring-type of Φ 6mm × 4mm × 2mm, obtain catalyst Cat-3.This catalyst Cat-3 most probable pore size porose for hole that 100-700nm(most probable pore size is 50-100nm accounts for 69%), BET specific surface area is 28m
2/ g.
Embodiment 4
(1) in the there-necked flask with agitating device and reflux condenser, 37.18gV is added
2o
5, 14g zinc sulfate, 2.35gMoO
3, 3mL hydrochloric acid (mass concentration 36%), 1.15g erbium, 400mL isobutanol and 20g mass concentration 85% phosphoric acid (manufacturer: Beijing You Peng Fine Chemical Co., Ltd), be uniformly mixed and be warming up to 105 DEG C of back flow reaction 4 hours, obtain the suspension of turquoise, suspension is cooled to room temperature, filter and use isobutanol to wash 2 times to filter cake, then by filter cake 100 DEG C of oven dry, obtain catalyst precursor A4.In this catalyst precursor A4, with the mole of v element for benchmark, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.56:0.21:0.036:0.016.
(2) according to the method for embodiment 1 step (2), except by using catalyst precursor A4 to replace catalyst precursor A4, use kneader to be shaped to by this mixture except the ring-type of Φ 6mm × 4mm × 2mm, obtain catalyst Cat-4.This catalyst Cat-4 most probable pore size porose for hole that 50-400nm(most probable pore size is 50-100nm accounts for 65%), BET specific surface area is 21m
2/ g.
Embodiment 5
With the step (1) of embodiment 1.
(2) 5g1 is used, 1,1-trimethylolethane and 5g polyethylene glycol (manufacturer: Beijing You Peng Fine Chemical Co., Ltd, number-average molecular weight 4000) replace 2g1,1,1-trimethylolethane, mixture is shaped to the ring-type of Φ 6mm × 5mm × 2mm, in addition, operate in the same manner as the step (2) of embodiment 1, obtain catalyst Cat-5, the most probable pore size of this catalyst Cat-5 porose for hole that 100-800nm(most probable pore size is 50-100nm accounts for 75%), BET specific surface area is 31m
2/ g.
Embodiment 6
With the step (1) of embodiment 1.
(2) 1g trimethylolpropane and 1g stearic acid is used to replace 2g1,1,1-trimethylolethane, mixture is shaped to the ring-type of Φ 6mm × 5mm × 2mm, in addition, operate in the same manner as the step (2) of embodiment 1, obtain catalyst Cat-6, the most probable pore size of this catalyst Cat-6 porose for hole that 100-600nm(most probable pore size is 50-100nm accounts for 72%), BET specific surface area is 29m
2/ g.
Embodiment 7
With the step (1) of embodiment 1.
(2) 2g polystyrene (number-average molecular weight 4000) and 4g stearic acid is used to replace 2g1,1,1-trimethylolethane, mixture is shaped to the ring-type of Φ 6mm × 5mm × 1.5mm, in addition, operate in the same manner as the step (2) of embodiment 1, obtain catalyst Cat-7, the most probable pore size of this catalyst Cat-7 porose for hole that 100-600nm(most probable pore size is 50-100nm accounts for 68%), BET specific surface area is 29m
2/ g.
Embodiment 8
With the step (1) of embodiment 1.
(2) 2g acetic acid and 4g stearic acid is used to replace 2g1,1,1-trimethylolethane, mixture is shaped to the ring-type of Φ 6mm × 4mm × 1mm, in addition, operate in the same manner as the step (2) of embodiment 1, obtain catalyst Cat-8, the most probable pore size of this catalyst Cat-8 porose for hole that 70-700nm(most probable pore size is 50-100nm accounts for 65%), BET specific surface area is 30m
2/ g.
Embodiment 9
With the step (1) of embodiment 4.
(2) above-mentioned steps (1) is adopted to prepare 100g catalyst precursor A1, by itself and 0.8g1, 1, 1-trimethylolethane, 2g graphite, 14g modified starch (producer: Beijing You Peng Fine Chemical Co., Ltd), 7g polyvinyl acetate (manufacturer: Beijing You Peng Fine Chemical Co., Ltd) and suitable quantity of water mix, kneader is used this mixture to be shaped to the ring-type of Φ 6mm × 4mm × 2mm, called after catalyst Cat-9, the most probable pore size of this catalyst Cat-9 porose for hole that 100-600nm(most probable pore size is 50-100nm accounts for 70%), BET specific surface area is 29m
2/ g.
Test case 1
The ZQJ-II type Intelligent testing machine for particle using large connection intelligent testing machine factory to manufacture measures, and measures the transverse strength of catalyst Cat-9 and Cat-D1 and vertical intensity.The transverse strength of catalyst Cat-9 is 200N/cm, vertical intensity is 200N/cm, and the transverse strength of catalyst Cat-D1 is 100N/cm, vertical intensity is 100N/cm.
Test case 2
Use fixed bed reactors respectively loading catalyst Cat-1 ~ Cat-9 and Cat-D1 in this test case, carry out the production of cis-butenedioic anhydride, can be used for the performance of evaluate catalysts simultaneously.The weight of the product cis-butenedioic anhydride obtained after being reacted by chemical titration; Adopt gas chromatography (manufacturer: Varian, model: the content 3800) analyzing gaseous component in raw material and tail gas.
Amount of substance × 100% of conversion ratio (%)=(amount of substance of the amount of substance-unit interval reactor outlet normal butane of unit interval n-butane feed)/unit interval n-butane feed of normal butane
Yield of maleic anhydride is calculated by following formula:
Weight × 100% of the weight/unit interval n-butane feed of yield of maleic anhydride (% by weight)=unit interval product cis-butenedioic anhydride
Selectivity of maleic anhydride (%)=cis-butenedioic anhydride product yield/butane feed stock conversion × 100%
Fixed bed reactors adopt salt bath heating, and the pressure in fixed bed reactors is 0.1 ± 0.01MPa.
According to following steps, catalyst is activated, by packed catalyst in 120mL fixed bed reactors, continue with volume space velocity 500h
-1the volumetric concentration passing into normal butane is the mist of 0.5% (oxidizing gas is air), first with the speed of 70 DEG C/h, salt temperature is increased to 300 DEG C by room temperature, then with the speed of 30 DEG C/h, salt temperature is increased to the temperature by the needs shown in table 1 by 300 DEG C and maintains 12 hours.
After activation process terminates, proceed the production of cis-butenedioic anhydride according to the condition shown in table 1, result is also as shown in table 1.
Table 1
Can be found out by table 1, according to catalyst prepared by the preparation method of catalyst provided by the invention, compared with the catalyst adopting stearic acid to prepare as expanding agent with prior art, in preparing cis-anhydride by n-butane oxidation reaction, there is higher n-butane conversion, yield of maleic anhydride and Selectivity of maleic anhydride.
Claims (13)
1. a preparation method for catalyst, the method comprises the following steps:
(1) under Redox Condition, make vanadium-containing compound, phosphorus-containing compound, zinc compound, contact in liquid reaction medium with the simple substance of rare earth element and/or compound containing the compound of elements A, in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.5-2:0.01-0.25:0.001-0.05:0.0001-0.02, be separated after contact and remove liquid reaction medium, obtain catalyst precursor; Described elements A be selected from Li, Rb, Mo, Co, Mn, Nb, Ag and Fe one or more; Described rare earth element is Er, Ho, Pr or Gd; Described liquid reaction medium is selected from least one in the monoalky lether of the dihydroxylic alcohols of C2-C12, the alcohol of C1-C12 and N-alkylamide; Described Redox Condition comprises: temperature is 90-200 DEG C, the time is 4-24 hour;
(2) by described catalyst precursor and shaping assistant mixing aftershaping, described shaping assistant comprises lubricant, expanding agent and adhesive, it is one or more in the polystyrene of 1000-10000 that described expanding agent to contain in molecule containing the compound of two or more hydroxyl, number-average molecular weight, and with the total amount of expanding agent for benchmark, the compound containing two or more hydroxyl in described molecule, number-average molecular weight are one or more the total amount in the polystyrene of 1000-10000 is more than 10 % by weight.
2. method according to claim 1, wherein, is selected from 1,1,1-trimethylolethane containing the compound of two or more hydroxyl in described molecule, trimethylolpropane, number-average molecular weight is one or more in the polyethylene glycol of 1000-10000.
3. method according to claim 1 and 2, wherein, described expanding agent is also containing stearic acid, with the gross weight of expanding agent for benchmark, compound containing two or more hydroxyl in molecule and/or number-average molecular weight are the content of the polystyrene of 1000-10000 is 10-90 % by weight, and stearic content is 10-90 % by weight.
4. method according to claim 1, wherein, relative to the described catalyst precursor of 100 weight portions, the consumption of lubricant is 0.5-5 weight portion, and the consumption of expanding agent is 0.5-10 weight portion, and the consumption of adhesive is 1-25 weight portion.
5. method according to claim 1, wherein, in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.6-2:0.01-0.15:0.005-0.025:0.0001-0.015.
6. method according to claim 5, wherein, in mole, v element: P elements: Zn-ef ficiency: elements A: rare earth element=1:0.6-1.5:0.01-0.05:0.005-0.01:0.0001-0.01.
7. method according to claim 1, wherein, elements A be Mo be selected from Li, Co and Fe one or more.
8. method according to claim 1, wherein, liquid reaction medium is selected from least one in 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isobutanol and phenmethylol.
9. method according to claim 8, wherein, liquid reaction medium is at least one in 2-propyl alcohol, isobutanol and phenmethylol.
10. method according to claim 1, wherein, described Redox Condition comprises: temperature is 90-150 DEG C, the time is 4-20 hour.
11. according to the method in claim 1 and 5-10 described in any one, wherein, contact described in step (1) comprises two stages, first make vanadium-containing compound, phosphorus-containing compound, zinc compound and in liquid reaction medium, carry out the first stage containing the compound of elements A to contact, the first stage condition of contact comprises: temperature is 90-150 DEG C, the time is 2-12 hour; Make the simple substance of rare earth element and/or compound contact gained material with the first stage again and carry out second stage contact, the condition of second stage contact comprises: temperature is 90-150 DEG C, the time is 2-12 hour.
12. 1 kinds of catalyst prepared by the method in claim 1-11 described in any one, is characterized in that, the specific area of this catalyst is 15-50m
2/ g, most probable pore size is 10-1000nm.
The application of catalyst in preparing cis-anhydride by n-butane oxidation technique described in 13. claims 12.
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| EP0876212B1 (en) * | 1995-10-02 | 2004-11-17 | Huntsman Petrochemical Corporation | Molybdenum-modified vanadium-phosphorus oxide catalysts for the production of maleic anhydride |
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| CN1345630A (en) * | 2000-09-29 | 2002-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
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