CN1026863C - Process for preparing V-P-Zr mixed oxide catalyst used for producing cis-butene dioic acid anhydride - Google Patents
Process for preparing V-P-Zr mixed oxide catalyst used for producing cis-butene dioic acid anhydride Download PDFInfo
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- CN1026863C CN1026863C CN 92105803 CN92105803A CN1026863C CN 1026863 C CN1026863 C CN 1026863C CN 92105803 CN92105803 CN 92105803 CN 92105803 A CN92105803 A CN 92105803A CN 1026863 C CN1026863 C CN 1026863C
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Abstract
The present invention provides a preparation method for a catalyst for maleic anhydride selectively oxidized by n-butane. The catalyst is vanadium-phosphorus-zirconium mixed oxide. The preparation method is characterized in that the reaction time and the temperature control in the process for preparing precursors are carried out by three stages, and the activation temperature rise rate is controlled in sections according to three different temperature regions in the process for activating the fresh catalyst. The catalyst prepared by the present invention has the advantages of high activity, high strength and good stability, and can be stored for more than two years in an air atmosphere, and the activity, the selectivity and the strength of the catalyst are not damaged if the condition that the temperature exceeds (exceeds 50 to 120 DEG C of the normal use temperature) happens in the process of oxidization reactions.
Description
The present invention relates to vanadium-phosphorus-Zr mixed oxide (V-P-O-Zr) Preparation of catalysts method, this catalyzer is mainly used in n butane oxidation production MALEIC ANHYDRIDE (abbreviation cis-butenedioic anhydride).Its international Patent classificating number is B01J27/00.
The seventies; it is the factory of raw material production cis-butenedioic anhydride with normal butane replacement benzene that the U.S. builds up a family; because n-butane feedstock enriches cheap; nontoxic; be not subjected to reasons such as the strict control of environmental protection department; this technology develops rapidly, and to the eighties middle and later periods, it is raw material that the cis-butenedioic anhydride production of the U.S. all converts to the normal butane.
The key issue of normal butane partial oxidation cis-butenedioic anhydride is the catalyzer of exploitation excellent property, the suitable catalyzer of generally acknowledging is vanadium-phosphorus mixed oxide at present, the domestic and international patent of this catalyst system, as U.S.P.4392986(1983), U.S.P.4435521(1984), U.S.P.4668652(1987) E.P.0151912(1984), CN 85107878A(1987), CN89103946.5(1989) grade has been made a large amount of reports.
The invention relates to activation condition in V-P-O-Zr Preparation of catalysts method and the reactivation process selection, determine and optimize, compare with above-mentioned patent and have visibly different technical characterictic.So-called V-P-O-Zr Preparation of catalysts mainly is meant the preparation process of its precursor, promptly reduces the reflection process.Reaction is to be the reductive agent solvent of holding concurrently with lower aliphatic alcohols (as isopropylcarbinol), adds vanadium-containing compound (as V
2O
5) and P contained compound (as ortho-phosphoric acid) react, its temperature of reaction generally is controlled at 30～300 ℃, 40～50 hours reaction times.This reaction and condition now are familiar with by people, but in reaction process, can help to improve other factors of catalyst activity, for example, determining of order that material adds in the reaction process and temperature spot, and the determining etc. of the temperature in differential responses stage control corresponding relation, be not fully recognized that also that all patent is not appeared in the newspapers so far both at home and abroad.
The activity of this catalyst system is except outside the Pass the preparation process with precursor has, and another important factor in order is the reactivation process of live catalyst.Live catalyst requires to carry out the activation treatment of certain hour, thereby obtain well behaved catalyzer finished product under certain atmosphere and temperature condition.The domestic and international patent report of this part content seldom only briefly touches upon no activating process condition in indivedual patents.
The object of the present invention is to provide the V-P-O-Zr series catalysts of a kind of high reactivity that is used for preparing cis-anhydride by n-butane oxidation, high strength, high stability, increase yield of maleic anhydride.The optimal conditions that this catalyzer uses the present invention to determine is prepared and activation treatment.
For the present invention, not adding the promotor zirconium and not being called catalyst precursor before the moulding, after this be called live catalyst.
One of key problem in technology of the present invention is an adding temperature range of having determined P contained compound in the reduction reaction process, and at the pairing optimal reaction temperature of different step of reaction.The present invention spells out, and wants strict when precursor prepares and carries out the reduction reaction intensification by the heating schedule of setting, and can obtain than precursor great, that intensity good, specific surface is moderate.
Another key problem in technology of the present invention, it is the temperature controlling range when having determined the live catalyst activation, the particularly important is, temperature ranges different between pot-life will be carried out strictness control by different temperature rise rates, can shorten soak time for this reason, and obtain the catalyzer of high reactivity and high productive capacity.Patent CN89103946.5(1989) emphasize live catalyst activation temperature rise rate and activation final temperature, the present invention emphasizes to activate temperature-rise period and wants strictness to carry out stage by stage, and both technical characterictics are inequality.
The preparation process of V-P-O-Zr series catalysts precursor mainly comprises following step:
1. in the absolute alcohol medium, vanadium-containing compound and P contained compound react,
2. after the reaction, the solids that product obtains after filtration carries out hydrothermal treatment consists, obtains catalyst precursor,
3. the drying of catalyst precursor.
The key of catalyst precursor preparation is the reduction reaction process, and this process and condition be, absolute alcohol (as isopropylcarbinol) is added to stir in the reduction kettle earlier and heats up, and adopts anchor stirrer, and 50～300 rev/mins of stirring velocitys add vanadium-containing compound again (as V
2O
5), continue heating and be rapidly heated 60～180 ℃, add moisture phosphorus compound (as the ortho-phosphoric acid of 85Wt%), moisture phosphorus compound adds preferably 80～140 ℃ of fashionable temperature, while azeotropic in reactor removes the water in the reactive system, remove the water yield and account for 20～80% of whole water yields, can in reactor, add a certain amount of fresh absolute alcohol in case of necessity.Entire reaction course can be carried out in 30～300 ℃ of scopes, 40～50 hours reaction times.What pay particular attention to is that in the different temperature of reaction of different steps control of reaction process, this is a key problem in technology of the present invention, is one of key that improves catalyst activity.To this, the present invention particularly points out, and reduction reaction temperature needs to control by three phases.Fs, in 8 hours reaction times, control 70～180 ℃; Subordinate phase, in 16 hours reaction times, controlled temperature is lower 5～10 ℃ than the fs; Phase III, in 24 hours reaction times, be controlled at than low 15～50 ℃ of subordinate phase.Total reaction time is 40～50 hours.After reaction finishes, remove mother liquor with filter method, filter cake send in the humidified blast baking oven in 90～150 ℃ dry 2～8 hours down, remove organic substance and the moisture content such as alcohol that remain in the filter cake, obtain the light blue solid powder of good fluidity.
The blue solid powder is added in the hydrothermal treatment consists still, adds a certain amount of deionized water, hydrothermal treatment consists is 2～12 hours under reflux state, after after filtration, obtain catalyst precursor after the drying.
The preparation of V-P-O-Zr live catalyst: catalyst precursor is added in zirconates (as the Zircosol ZN) aqueous solution for preparing, be mixed into paste, send into drying and dehydrating in the baking oven, get a green block, pulverize the back and add tackiness agent, kneaded and formed is diameter 1.5～3mm, and the strip of long 5～10mm is the V-P-O-Zr live catalyst after the drying.The add-on of zirconium wherein: the atomic ratio of zirconium and vanadium is Zr/V=0.001～0.005/1.The side pressure strength of live catalyst is greater than 1.35kgf/mm.
The activation of V-P-O-Zr live catalyst: place reactor to activate live catalyst, activation phenomenon is that volume ratio is normal butane-air gas mixture of 0.8～1.8%, 1～5 second duration of contact.In order more effectively to improve the premium properties of catalyzer, should be in the reactivation process according to different temperature ranges, strict control temperature rise rate, this is an another key point of the present invention.For this reason, the present invention points out emphatically, and will carry out segmentation control to temperature rise rate by three differing temps intervals in the reactivation process.The fs temperature range is room temperature～250 ℃, and the control temperature rise rate is 125～300 ℃/h, and the subordinate phase temperature range is 250～320 ℃, and the control temperature rise rate is 10～60 ℃/h.The phase III temperature range is 320～500 ℃, and the control temperature rise rate is 5～50 ℃/h.Activation finishes when temperature reaches 350～500 ℃.Promptly obtained having more intact crystalline structure in this way, high reactivity very, n-butane conversion 〉=80%, cis-butenedioic anhydride weight yield 〉=95%, the V-P-O-Zr catalyzer that the normal butane selective oxidation is become cis-butenedioic anhydride during selectivity 〉=72mol% space time yield 〉=85 grams per liters.
Produce and activatory V-P-O-Zr catalyzer is used for production practice by the present invention, it is good obviously to have self intensity, characteristics such as active height, and good stability is stored convenient, can store in air atmosphere does not influence catalyst activity and intensity more than 2 years, particularly, in system cis-butenedioic anhydride oxidation reaction process, run into overtemperature (surpassing 50～120 ℃ of normal use temperatures) situation, do not destroy catalyst activity, selectivity and intensity.
Embodiment 1
8.91KgV
2O
5, the 150kg isopropylcarbinol is added in the reduction reaction still, is stirred and heated to 102 ℃, adds the ortho-phosphoric acid of the 85Wt% of 13.42kg, temperature of reaction is kept 102 ℃ of reactions 8 hours, drops to 95 ℃ then, keeps 16 hours, cool to 50 ℃ and kept 24 hours, reduction reaction finishes, and gets a blue soup compound.After after filtration, hydrothermal treatment consists, soak zirconium, moulding and get φ 2 * 5mm strip fresh (activation) catalyzer.
Live catalyst is put into reactor activate, feed normal butane/air gas mixture during activation, butane concentration is 1.5%, 2.4 seconds duration of contact.Activation temperature segmentation control, room temperature to 250 ℃, 260 ℃/h of temperature rise rate; Before 300～320 ℃, 15 ℃/h of temperature rise rate; Before 400～450 ℃, 10 ℃/h.Be activated to n-butane conversion 〉=80% and finish, carry out normal reaction then.Determination of activity sees Table 1.
Embodiment 2
As embodiment 1,8.91kgV
2O
5Be added in the reactor with the 150kg isopropylcarbinol, stir, be heated to 60 ℃, add the ortho-phosphoric acid of 13.42kg85Wt%.All the other are with embodiment 1.Catalyst activity is listed in the table 1.(table 1 is seen the literary composition back)
Embodiment 3
Precursor prepares process and is same as embodiment 1.During activation, 250 ℃ at the uniform velocity heat up later on, finish until activation.The catalyst activity evaluation is listed in the table 1.
The common ground of patent related to the present invention is, use non-water organic solution, especially isopropylcarbinol when the preparation precursor, working concentration is the ortho-phosphoric acid of 100Wt% or 106Wt%, what the present invention adopted is the moisture ortho-phosphoric acid of 85Wt%, catalyst specific surface and active basic identical with relevant patent.
Table 1 catalyst activity evaluation result
Embodiment temperature of reaction n-butane conversion yield of maleic anhydride selectivity air speed
℃ % wt% mol% h
-1
1 420 82.9 105.8 75.5 1500
416 81.1 102.5 74.8 1500
2 416 59.8 73.5 72.7 1500
3 416 70.2 91.0 76.7 1500
Claims (6)
1, a kind of preparation method who is used for becoming in the normal butane selective oxidation vanadium-phosphorus-Zr mixed oxide catalyst of MALEIC ANHYDRIDE is characterized in that:
(1) in the absolute alcohol medium, make a kind of vanadium-containing compound (Vanadium Pentoxide in FLAKES) and a kind of P contained compound (ortho-phosphoric acid of 85Wt%) that reduction reaction take place, this reduction reflection temperature will be controlled by three phases: the fs, in 8 hours reaction times, control 70～180 ℃; Subordinate phase, in 16 hours reaction times, controlled temperature is lower 5～10 ℃ than the fs; Phase III, 24 hours reaction times, be controlled at than low 15～50 ℃ of subordinate phase, total reaction times is 40～50 hours, generates catalyst precursor;
(2) catalyst precursor that obtains after the reduction reaction carried out hydrothermal treatment consists 2～12 hours under reflux state;
(3) precursor with catalyzer adds in the zirconium saline solution for preparing, wherein the add-on of zirconium: the atomic ratio of zirconium and vanadium is Zr/v=0.001～0.005/1, gets live catalyst;
(4) live catalyst of vanadium-phosphorus-Zr mixed oxide will pass through activation treatment, and it will carry out segmentation control to the activation temperature rise rate by three different temperature ranges: the fs temperature range is room temperature～250 ℃, and the control temperature rise rate is 125～300 ℃/h; The subordinate phase temperature range is 250～320 ℃, and the control temperature rise rate is 10～60 ℃/h; The phase III temperature range is 320～500 ℃, and the control temperature rise rate is 5～50 ℃/h, and activation is until 350～500 ℃ of temperature of reaction.
2, method according to claim 1 is characterized in that adding absolute alcohol (isopropylcarbinol) and vanadium-containing compound (Vanadium Pentoxide in FLAKES) in the reactor earlier, adds P contained compound (85Wt% ortho-phosphoric acid) then.
3, method according to claim 1, the temperature that it is characterized in that adding moisture phosphorus compound (ortho-phosphoric acid of 85Wt%) is 80～140 ℃.
4, method according to claim 1 is characterized in that the zirconates that adds is a Zircosol ZN.
5, method according to claim 1 is characterized in that in preparation precursor reaction process azeotropic sloughs 20～80% of water content in the reactive system.
6, method according to claim 1 is characterized in that preparing that the reduction kettle stirring velocity is 50～300 rev/mins in the precursor process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92105803 CN1026863C (en) | 1992-07-21 | 1992-07-21 | Process for preparing V-P-Zr mixed oxide catalyst used for producing cis-butene dioic acid anhydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92105803 CN1026863C (en) | 1992-07-21 | 1992-07-21 | Process for preparing V-P-Zr mixed oxide catalyst used for producing cis-butene dioic acid anhydride |
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| CN1067189A CN1067189A (en) | 1992-12-23 |
| CN1026863C true CN1026863C (en) | 1994-12-07 |
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| CN 92105803 Expired - Fee Related CN1026863C (en) | 1992-07-21 | 1992-07-21 | Process for preparing V-P-Zr mixed oxide catalyst used for producing cis-butene dioic acid anhydride |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059845C (en) * | 1996-04-25 | 2000-12-27 | 中国石油化工总公司 | Alkane oxidation catalyst and its preparing method |
| CN100446858C (en) * | 2006-10-13 | 2008-12-31 | 南京大学 | Zirconium-base loaded vanadium-phosphor oxide catalyst, and its preparing and use |
| 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 |
| CN112495410A (en) * | 2021-01-19 | 2021-03-16 | 郑州中科新兴产业技术研究院 | Vanadium phosphorus oxygen catalyst, preparation method and application |
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