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WO2004067170A1 - V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance - Google Patents

V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance Download PDF

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Publication number
WO2004067170A1
WO2004067170A1 PCT/CN2004/000085 CN2004000085W WO2004067170A1 WO 2004067170 A1 WO2004067170 A1 WO 2004067170A1 CN 2004000085 W CN2004000085 W CN 2004000085W WO 2004067170 A1 WO2004067170 A1 WO 2004067170A1
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Prior art keywords
catalyst precursor
maleic anhydride
catalyst
phosphorus
rate
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PCT/CN2004/000085
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English (en)
French (fr)
Inventor
Renshui Lan
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New Tianjin T and D Co Ltd
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New Tianjin T and D Co Ltd
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Priority to US10/543,807 priority Critical patent/US7547655B2/en
Publication of WO2004067170A1 publication Critical patent/WO2004067170A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/06—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing

Definitions

  • the invention relates to a catalyst for preparing maleic anhydride (abbreviated as maleic anhydride, commonly known as maleic anhydride). More specifically, the present invention relates to a solid catalyst precursor for preparing maleic anhydride from butane through catalytic oxidation, and more particularly to a vanadium-phosphorus-silicon composite oxide fixed bed or fluidized bed solid catalyst precursor for preparing maleic anhydride. .
  • Maleic anhydride is an important organic chemical raw material. It is widely used in the production of thermosetting resins, unsaturated polyester resins, pesticides and fine chemical products. Previously, maleic anhydride was produced from benzene. Due to benzene's toxicity, unsafety and environmental harm, butene was used instead of benzene as a raw material to produce maleic anhydride. In the 1960s, a device for the catalytic oxidation of butene to produce maleic anhydride was established. Since butene is expensive, since the 1970s, it has gradually shifted to the production of maleic anhydride from cheap and easily available butane-substituted benzene and butene.
  • CN1059297A discloses a method for preparing a V-P-O series catalyst for the oxidation of n-butane in a fluidized bed to produce maleic anhydride.
  • the method uses industrial-grade vanadium pentoxide and 85% phosphoric acid as raw materials, and uses isobutanol As a reducing agent, a reduction reaction is performed under heating conditions, and then a microsphere catalyst is obtained through hot filtration, modification treatment, addition of a metal cocatalyst, slurry adjustment, and spray drying. In this method, a metal co-catalyst and modification treatment are added.
  • the preparation process is long and the activity of the catalyst is long. Sex and selectivity are not high.
  • CN1133755A discloses a preparation method for preparing cis catalyst by fluidized bed n-butane catalytic oxidation.
  • the method includes the preparation of a catalyst precursor and a post-processing process.
  • the preparation of the precursor uses vanadium pentoxide and phosphoric acid as raw materials, hydrazine hydrate as a reducing agent, and a mixed solution of benzyl alcohol and isobutanol as a solvent, and iron ions or zirconium ions are added during the reaction.
  • the silica sol and gelling agent are used to make a supported catalyst slurry, which is then dried and dehydrated, activated at a certain atmosphere and temperature, and finally formed and sieved to obtain a catalyst finished product.
  • This method also has the disadvantages of long process flow and complicated activation process.
  • CN1282631A suggests a method for preparing a vanadium-phosphorus-oxygen catalyst.
  • the method involves heating vanadium pentoxide and concentrated hydrochloric acid under reflux, adding phosphoric acid to continue refluxing, and adding zirconium nitrate, ammonium molybdate and zinc acetate after cooling.
  • the composition of this catalyst is complex, but its catalytic activity and selectivity are not high.
  • CN1303741A describes a method for preparing a composite vanadium-phosphorus-oxygen catalyst for the oxidation of n-butane to maleic anhydride.
  • the method is to increase the amount of available oxygen in the catalyst system by adding an oxygen storage body cerium dioxide-based composite oxide to a VPO catalyst
  • the catalyst prepared by this method has complex components, and expensive rare earth oxides are added.
  • US5108974 discloses a method for preparing a vanadium-phosphorus-oxide catalyst precursor. The method is to reduce vanadium pentoxide to dioxotetraoxide by heating in the presence of an alkyl orthosilicate and phosphoric acid mixture in an alcohol solvent. Vanadium (v 2 o 4 ), in the presence of alkyl orthosilicate, the product precipitates with the remaining phosphoric acid.
  • US4294722 discloses a method for preparing an oxidation catalyst containing vanadium-phosphorus mixed oxide catalyst which is particularly effective for the oxidation of n-butane.
  • the method is to dissolve vanadium pentoxide in isobutanol and heat it under reflux for about 16 hours; The osmic acid was dissolved in isobutanol and added to the above-mentioned filtrate, and the resulting mixture was heated under reflux for 8 hours; the precipitate was collected by cooling to obtain a catalyst precursor.
  • the selectivity and yield of maleic anhydride are low.
  • US4062873 suggests a method for preparing vanadium-phosphorus-silicon-oxide.
  • the method is to co-precipitate vanadium oxide and alkyl orthosilicate in an organic medium to generate vanadium oxide and Co-precipitated precursor of silicon oxide; Phosphorus co-precipitated with vanadium oxide and alkyl orthosilicate at the same time or subsequent co-precipitation to obtain a catalyst precursor; calcining the catalyst precursor to obtain a silicon oxide-containing catalyst.
  • the catalysts for the production of maleic anhydride prepared by the methods of the prior art also have disadvantages such as low maleic anhydride yield and selectivity, and long preparation process.
  • the inventors found after long-term and in-depth research that after reducing the pentavalent vanadium compound in an organic medium, the reduction product and phosphoric acid were reacted under heating conditions, and the product was then heated with the alkyl silicon. The reaction is performed under conditions to generate a catalyst precursor.
  • the catalyst precursor has a suitable pore size distribution, a small pore volume, and a high bulk density.
  • the catalyst prepared from this catalyst precursor has more catalytically active components per unit volume than the existing catalysts described above, has a higher conversion rate of maleic anhydride, and can further increase the yield of maleic anhydride based on n-butane.
  • the present invention has been completed.
  • an object of the present invention is to provide a precursor of a vanadium-phosphorus-silicon composite oxide catalyst for preparing cis ⁇ by catalytic oxidation of butane, especially a vanadium-phosphorus-silicon composite oxide catalyst for a fixed bed or a fluidized bed. Precursor.
  • Another object of the present invention is to provide a vanadium-phosphorus-silicon composite oxide catalyst precursor for preparing maleic anhydride by catalytic oxidation of butane, especially a method for preparing a fixed-bed or fluid-bed catalyst precursor.
  • a third object of the present invention is to provide an improved method for preparing maleic anhydride from the catalytic oxidation of butane.
  • the vanadium-phosphorus-silicon composite oxide catalyst precursor for preparing maleic anhydride by catalytic oxidation of butane in the present invention is composed of a compound oxygen compound of vanadium, phosphorus, and silicon.
  • Vanadium: phosphorus : Silicon (molar ratio) 0.77-1.1: 1: 0.1-1;
  • the pore size distribution detected by the ASAP2405 adsorber is: More than 90% of pores with a pore size greater than 100A, and less than 10% of pores with a pore size less than 100 A 130-180 A.
  • the pore volume is 0.01-0.10 ml / g, preferably the pore volume is 0.02-0.06 ml / g.
  • the catalyst precursor of the present invention has a suitable pore size distribution, so that the pore volume of the catalyst is smaller than the pore volume of the catalyst in the prior art, and the bulk density is high, so the effective active site of the catalytic oxidation per unit catalyst is high. Therefore, the molar yields of cis-butane based on the catalyst of the present invention are 5 mol% and 10 mol% higher in the fixed bed and the fluidized bed than the catalysts in the prior art, respectively.
  • the preparation method of the catalyst precursor of the present invention includes:
  • step (2) adding the oxygen-containing acid to the product of step (1) at a rate of 1.0-10 g / min under the condition of reflux heating, and continuing the reflux heating for 0.5-5 hours;
  • step (3) under the condition of reflux heating, adding alkyl silicon to the product of step (2) at a rate of 0.5-5 g / min, and continuing the reflux heating for 6-12 hours;
  • the method for preparing the catalyst precursor of the present invention is characterized in that the raw materials are added stepwise and the reduction reaction is performed stepwise. That is, the vanadium compound is first added to the mixed alcohol, and heated under reflux to reduce V + 5 to V + 4 at least partially, and then the phosphorus oxyacid is added dropwise after the addition of the alkyl silicon.
  • Another feature of the present invention is that the phosphorus oxyacid and alkyl silicon are added dropwise at different rates, so that the reaction proceeds slowly, and the crystals grow at a certain rate, so that the catalyst precursor has a suitable pore size, pore volume and bulk density.
  • the pentavalent vanadium compound used in the present invention is not particularly limited, but vanadium pentoxide is preferred. To accelerate the reaction, it is preferred that the vanadium pentoxide is ground to a particle size of less than 100 microns, and more preferably less than 30 microns.
  • the phosphorus oxyacid used in the present invention is also not particularly limited, but phosphoric acid is preferred. More preferred is 85% by weight phosphoric acid.
  • the organosilicon compound used in the present invention is not particularly limited, but tetramethoxysilane and tetraethylsilane are preferred.
  • the reduction reaction of vanadium pentoxide with an organic medium that is, an alcohol is performed under reflux heating, and the reaction time is usually 0.5-2 hours, preferably 1-2 hours.
  • the stirring speed is 100 to 1000 rpm, preferably 300 to 800 rpm.
  • the addition rate of phosphorus oxyacid, preferably osmic acid is not particularly limited, and is usually 1.0-10 g / min, preferably 1-9 g / min, and more preferably 3-8 g / min.
  • the addition rate of the alkyl silicon is also not particularly limited, but is usually 0.5 to 5.0 g / min, preferably 1.0 to 5.0 g / min, and more preferably 1.0 to 4.5 g / min.
  • the phosphorus oxyacid and the alkyl silicon are added separately, and the addition rate of the two may be the same or different. It is preferable that the addition rate of the phosphorus oxyacid is higher than that of the alkyl silicon. ) 2 H 4 P 2 0 9 crystals can be grown at a desired rate.
  • the catalyst precursor After the catalyst precursor is obtained according to the method of the present invention, it can be formed into a sheet shape by adding known binders commonly used in the technical field and forming the sheet by using the knowledge known to those skilled in the art and the molding methods commonly used in the technical field. Any suitable shape such as columnar, pellet, ring, spherical, granular, etc.
  • Example 1 Except that no alkyl silicon was added, the same as in Example 1 was obtained, and about 110 g of product was obtained.
  • the preparation conditions and performance evaluation results are shown in Table 1.
  • Example 1 Except that the mixed solution of vanadium pentoxide, alcohol and the whole alkyl silicon was subjected to reduction reaction, and then phosphoric acid was added dropwise, otherwise, the same as Example 1 was obtained, and about 110 g of a product was obtained.
  • the preparation conditions and performance evaluation results are shown in Table 1.
  • Example 1 Except that the feeding rate of the phosphoric acid was not controlled by the pouring reactor, the same as Example 1 was obtained, and about 110 g of product was obtained.
  • the preparation conditions and performance evaluation results are shown in Table 1.
  • Table 1 indicate that when the total composition of the raw materials is the same, the raw materials are gradually added to the mixed alcohol and heated under reflux to reduce v + s to v + 4 at least partially. Then, under reflux conditions, phosphoric acid and alkyl silicon are sequentially added dropwise, and the reaction rate is controlled to make the reaction proceed slowly, so as to obtain a vanadium-rhenium-silicon composite oxide catalyst with suitable pore size distribution, small pore volume, and high bulk density. Precursor.
  • the precursor of the vanadium-phosphorus-silicon composite oxide catalyst can be used as a catalyst for the catalytic oxidation of butane to maleic anhydride after being molded by molding techniques well known in the technical field, especially as a catalyst for catalytic oxidation of butane.
  • the present invention provides a vanadium-phosphorus-silicon composite oxide catalyst precursor for preparing maleic anhydride from butane through catalytic oxidation, a preparation method thereof, and a catalyst precursor for preparing maleic anhydride in catalytic oxidation of butane. application. It is clear that those skilled in the art can also make modifications and improvements to the present invention, and these modifications and improvements are all within the scope of the present invention without departing from the spirit of the present invention. The scope of the invention is set forth in the following claims.

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Description

用于丁烷氧化制顺丁烯二酸酐的
V- P- S . 复合氧化物催化剂前驱体 技术领域
本发明涉及一种制备顺丁烯二酸酐（简称顺酐， 俗称马来酐） 的 催化剂。 更具体地说， 本发明涉及一种由丁烷经催化氧化制备顺酐的 固体催化剂前驱体， 特别是涉及制备顺酐的钒-磷-硅复合氧化物固 定床或流化床固体催化剂前驱体。
背景技术
顺酐是重要的有机化工原料， 大量用于生产热固性树脂、 不饱和 聚酯树脂、 农药和精细化工产品。 以前， 用苯作原料生产顺酐。 由于 苯的毒性、 不安全性和对环境的危害性， 人们采用丁烯代替苯作原料 生产顺酐， 于 60年代建立了由丁烯催化氧化生产顺酐的装置。 由于丁 烯昂贵， 自 70年代以来， 逐渐转向以价廉且易得到的丁烷取代苯和丁 烯作为原料生产顺酐。
对生产顺酐的不同方法进行比较认为， 以正丁烷为原料生产顺 g 要比用苯和丁烯经济， 可采用固定床和 /或流化床。
目前， 对用丁烷作原料的固定床或流化床法制备顺酐催化剂的研 究非常重视， 已有许多专利文献报道， 其中对流化床法中的许多问题 进行了深入广泛地研究。 但是， 对流化床法用催化剂的研究集中在钒 -磷-氧化物前驱体的组成和制备方法方面， 提出了许多催化剂前驱 体的制备方法。
CN1059297A公开了一种用于流化床正丁烷氧化制备顺酐的 V - P - O 系催化剂的制备方法， 该方法是以工业级五氧化二钒和 85 %磷 酸为原料， 以异丁醇为还原剂， 在加热的条件下进行还原反应， 再经 热滤、 改性处理、 添加金属助催化剂、 调浆、 喷雾干燥得到微球催化 剂。 该方法要加金属助催化剂和改性处理， 制备流程长， 催化剂的活 性和选择性不高。
CN1133755A 披露了一种用于流体床正丁烷催化氧化制备顺酑催 化剂的制备方法，该方法包括催化剂前驱体的制备和后处理加工过程。 前驱体的制备以五氧化二钒和磷酸为原料， 以水合肼为还原剂， 以苯 甲醇和异丁醇的混合液为溶剂， 在反应过程中加入铁离子或锆离子， 得到的前体与硅溶胶和胶凝剂制成负载型催化剂浆液，再经干燥脱水， 在一定的气氛和温度下活化， 最后成型筛分得到催化剂成品。 该方法 同样具有流程长和活化工艺复杂的缺点。
CN1282631A 提示了一种钒 -磷-氧催化剂的制备方法， 该方法 是将五氧化二钒与浓盐酸加热回流后， 再加入磷酸继续回流， 冷却后 加入硝酸锆、 钼酸铵和乙酸锌。 这种催化剂成分复杂， 而催化活性和 选择性不高。
CN1303741A 描述了一种正丁烷氧化制顺酐的复合钒-磷-氧催 化剂的制备方法，该方法是通过向 VPO催化剂添加储氧体二氧化铈基 复合氧化物来增加催化剂体系的可用氧量， 该方法制备的催化剂成分 复杂， 且添加了昂贵的稀土氧化物。
US5108974公开了一种钒 -磷-氧化物催化剂前体的制备方法， 该方法是通过在正硅酸烷基酯和磷酸混合物存在下， 在醇溶剂中将五 氧化二钒加热还原成四氧化二钒（v2o4 )， 在正硅酸烷基酯的存在下， 产物与其余的磷酸生成沉淀。
US4294722公开了一种含钒磷混合氧化物催化剂的对正丁烷的氧 化特别有效的氧化催化剂的制备方法， 该方法是将五氧化二钒溶于异 丁醇中， 回流加热约 16小时； 将嶙酸溶于异丁醇中并加入上述的滤液 中， 得到的混合物加热回流 8小时； 冷却收集沉淀物得到催化剂前体。 顺酐的选择性和收率均较低。
US4062873提示了一种钒 -磷-硅-氧化物的制备方法， 该方法 是在有机介质中， 共沉淀钒氧化物和正硅酸烷基酯， 生成钒氧化物和 氧化硅的共沉淀物前体； 磷与钒氧化物和正硅酸烷基酯的共沉淀物同 时或其后共沉淀得到催化剂前驱体； 煅烧该催化剂前驱体， 得到含氧 化硅的催化剂。
如上所述， 由现有技术的方法制备的用于生产顺酐的催化剂还存 在顺酐产率和选择性不高、 制备过程长等缺点。 为克服这些不足， 本 发明人经过长期而深入地研究发现， 将五价钒化合物在有机介质中还 原后， 使还原产物与磷酸在加热条件下进行反应， 其生成物再与烷基 硅在加热条件下进行反应生成催化剂前驱体， 这种催化剂前驱体孔径 分布适宜， 孔容小， 堆密度大。 因此， 由这种催化剂前驱体制备的催 化剂比上述现有催化剂单位体积上具有更多的催化活性组分， 对顺酐 具有高的转化率， 能够进一步提高顺酐基于正丁烷的收率， 从而完成 了本发明。
发明内容
因此， 本发明的目的是提供一种由丁烷催化氧化制备顺酑的钒- 磷 -硅复合氧化物催化剂前驱体， 特别是固定床或流化床用的钒-磷 -硅复合氧化物催化剂前驱体。
本发明的另一目的是提供丁烷催化氧化制备顺酐的钒 -磷-硅复 合氧化物催化剂前驱体， 特别是固定床或流化床催化剂前驱体的制备 方法。
本发明的第三个目的是提供一种由丁烷催化氧化制备顺酐的改进 方法。
本发明的丁烷催化氧化制备顺酐的钒 -磷-硅复合氧化物催化剂 前驱体， 特别是固定床或流化床催化剂前驱体是由钒、 磷和硅的复合 氧 物组成， 钒： 磷： 硅（摩尔比） = 0.77-1.1:1:0.1-1; 由 ASAP2405 吸附仪检测孔径分布为： 孔径大于 100A的孔占 90 %以上， 孔径小于 100 A的孔占 10 %以下， 平均孔径为 130 - 180 A。 孔容为 0.01-0.10 毫升 /克， 优选孔容为 0.02-0.06毫升 /克。 堆密度为 0.80-1.00克 /厘米 3, 优选为 0.85-0.90克 /厘米 3。
如上所述， 本发明的催化剂前体具有适宜的孔径分布， 致使催化 剂的孔容比现有技术中催化剂的孔容小， 堆密度高， 因而单位催化剂 中的催化氧化有效活性位高。 因此， 使用本发明催化剂的顺酑基于丁 烷的摩尔收率在固定床和流化床上比现有技术中的催化剂分别高 5摩 尔％和 10摩尔％以上。
本发明的催化剂前体的制备方法包括：
( 1 ) 将五氧化二钒加入混合醇 [异丁醇 /苯甲醇 (体积比 = 2.5-5.0)] 中， 回流加热 0.5-2小时；
( 2 ) 在回流加热条件下， 向步驟（ 1 ) 的生成物中以 1.0-10 克 / 分的速率加入祷含氧酸， 继续回流加热 0.5-5小时；
( 3 ) 在回流加热的条件下， 向步骤（2 ) 的生成物中以 0.5-5克 / 分的速率加入烷基硅， 继续回流加热 6 - 12小时；
( 4 )冷却、 过滤、 用有机溶剂洗涤滤饼、 干燥得到催化剂前驱体。 本发明的催化剂前驱体的制备方法的特征在于， 原料分步加入， 还原反应分步进行。 即先将钒化合物加入混合醇中， 回流加热， 使 V + 5至少部分还原成 V+ 4, 然后在回流状态下加完磷含氧酸后再滴加烷基 硅。
本发明的另一特征是磷含氧酸和烷基硅以不同的速率滴加， 使反 应缓慢进行， 晶体以一定的速度生长， 从而使催化剂前驱体有适宜的 孔径、 孔容和堆密度。
本发明中所使用的有机溶剂是异丁醇和 /或苯甲醇。 如果用苯甲醇 和异丁醇的混合溶液， 则异丁醇:苯甲醇 = 2.5-5.0 (体积比） 。
本发明中所使用的五价钒 合物没有特别限制， 但是优选五氧化 二钒。 为了加速反应， 优选五氧化二钒研磨成粒径小于 100微米， 更 优选小于 30微米。
本发明中所使用的磷含氧酸同样没有特别限制， 但是优选磷酸， 更优选 85重量％磷酸。
本发明中所使用的有机硅化合物也没有特别限制， 但是优选四甲 氧基硅烷和四乙基硅烷。
在本发明中， 五氧化二钒与有机介质即醇类的还原反应是在回流 加热下进行， 反应时间通常为 0.5-2小时， 优选 1 - 2小时。 搅拌速度 为 100 - 1000转 /分， 优选为 300 - 800转 /分。
在本发明中， 对磷含氧酸、 优选嶙酸的加入速率没有特别限制， 通常为 1.0-10克 /分， 优选为 1 - 9克 /分， 更优选为 3 _ 8克 /分。
在本发明中，对烷基硅的加入速率也没有特别限制，通常为 0.5-5.0 克 /分， 优选为 1.0-5.0克 /分， 更优选为 1.0-4.5克 /分。
在本发明中， 磷含氧酸和烷基硅是单独分开添加， 两者的添加速 率可相同， 也可不相同， 优选磷含氧酸的添加速率大于烷基硅的添加 速率， 只要使 (VO)2H4P209晶体以所希望的速度成长即可。
在按本发明的方法得到催化剂前驱体后， 可通过本技术领域内技 术人员公知的知识和本技术领域内通用的成型方法， 添加本技术领域 内常用的粘结剂成型， 制成片状、 柱状、 丸状、 环状、 球形、 颗粒状 等任何适宜的形状。
下面通过实施例更详细地描述本发明， 但是， 本发明不受这些实 施例的限制。 本发明的范围在附属的权利要求书中提出。
实施例 1
在一个 2升的设置有加热器、 机械搅拌器和冷凝器的玻璃反应釜 内， 在搅拌下， 加入 980毫升异丁醇和 200毫升笨甲醇， 然后加入 60 克五氧化二钒， 回流加热 1小时。 此后， 以 2.3克 /分的速率滴加 95克 85 %的磷酸。 此后， 继续以 3克 /分的速率滴加 50克四甲氧基硅烷， 继续回流 12小时后， 冷却到室温， 真空过滤收集沉淀物。 滤饼用 500 毫升异丁醇洗涤后， 于 150X温度下干燥 2小时， 得到约 110克左右 产品。 制备条件和性能评价结果列于表 1。 实施例 2
除不加苯甲醇外， 其它与实施例 1相同， 得到约 110克产品。 制 备奈件和性能评价结果列于表 1。
实施例 3
除不加烷基硅外， 其它与实施例 1相同， 得到约 110克产品„ 制 备条件和性能评价结果列于表 1。
实施例 4
除五氧化二钒与醇及部分磷酸（约 30克） 和烷基硅（ 20克） 的 混合溶液进行还原反应后， 再滴加剩余的嶙酸和烷基硅外， 其它与实 施例 1相同， 得到约 110克产品。 制备条件和性能评价结果列于表 1。 实施例 5
除五氧化二钒与醇和全部烷基硅的混合液进行还原反应后再滴加 磷酸外， 其它与实施例 1相同， 得到约 110克产品。 制备条件和性能 评价结果列于表 1。
实施例 6
除烷基硅采用倒入反应器不控制加料速率外， 其它与实施例 1相 同， 得到约 110克产品。 制备条件和性能评价结果列于表 1。
实施例 7
除磷酸采用倒入反应器不控制加料速率外，其它与实施例 1相同， 得到约 110克产品。 制备条件和性能评价结果列于表 1。
实施例 8
除五氧化二钒与醇和全部磷酸的混合溶液进行还原反应后再滴加 烷基硅外， 其它与实施例 1相同， 得到约 110克产品。 制备条件和性 能评价结果列于表 1。 实施 原料 磷酸、烷基硅 控制加 催化剂前驱体 催化剂固 例 总量 分步加料 料速率 平均孔 孔容 堆密度 定床评价 径 A 毫升 /克 克 /毫升 收率％
1 是 是 是 148 0.03 0.94 62
2 否 是 是 147 0.045 0.80 45
3 否 是 是 129 0.04 0.82 50
4 是 否 是 154 0.07 0.79 57
5 是 否 是 179 0.09 0.52 48
6 是 是 否 160 0.075 0.75 54
7 是 是 否 172 0.08 0.6 50
8 是 否 是 185 0.10 0.48 45
表 1的结果表明， 在总的原料组成相同的情况下， 采用将原料分 步加入混合醇中， 回流加热， 使 v+ s至少部分还原成 v + 4。 然后， 在 回流条件下， 依次滴加磷酸和烷基硅， 并控制其反应速度， 使反应緩 慢进行， 从而得到孔径分布适宜， 孔容小， 堆密度高的钒 -嶙-硅复 合氧化物催化剂前驱体。 该钒 -磷-硅复合氧化物催化剂前驱体经用 本技术领域内众所周知的成型技术成型后， 可用作由丁烷催化氧化制 顺酐的催化剂， 特别是用作由丁烷催化氧化制顺酐的固定床或流化床 催化剂。 该催化剂的催化活性评价表明， 活性高， 选择性好， 与本技 术领域内的传统催化剂相比， 顺酐产率要高 10摩尔％以上。
如上所述， 本发明提供了一种由丁烷经催化氧化制备顺酐的钒- 磷-硅复合氧化物催化剂前驱体及其制备方法和该催化剂前驱体在丁 烷催化氧化制备顺酐中的应用。 十分清楚， 本领域内技术人员还可以 对本发明做出修改和改进， 这些修改和改进在不背离本发明精神的情 况下， 都在本发明的范围内。 本发明的范围由附属的权利要求书提出。

Claims

1. 一种用于生产顺酐催化剂的 V- P- Si 复合氧化物催化剂前驱 体， 其特征在于该催化剂前驱体的孔径分布为： 孔径大于 looA的孔 占 90%以上， 孔径小于 100 A的孔占 10%以下， 孔容为 0.01-0.10毫 升 /克。
2. 根据权利要求 1 所述的催化剂前驱体， 其特征在于孔容为 0.02-0.06毫升 /克。
3. 根据权利要求 1或 2所述的催化剂前驱体， 其特征在于堆密度 为 0.80-1.00克 /厘米 3。
4. 根据权利要求 1所述的催化剂前驱体， 其特征在于 V:P:Si的摩 尔比为 0.77-1.1:1:0.1-1。
5. 根据权利要求 1-4中任一项所述的催化剂前驱体的制备方法， 其特征在于该方法包括如下步骤：
( 1) 将五价钒化合物加入混合醇中， 回流加热 0.5-2小时；
(2)在回流加热条件下， 向步骤（ 1) 的生成物中以 1.0-10克 /分的速 率加入磚含氧酸；
(3) 在回流加热的条件下， 向步骤（2) 的生成物中以 0.5-5克 /分的 速率加入烷基硅， 继续回流加热 6- 12小时；
(4) 冷却、 过滤、 用有机溶剂洗涤滤饼、 干燥得到催化剂前驱体。
6. 根据权利要求 5所述的方法， 其特征在于步驟（2) 和（3) 分 两次进行。
7. 根据权利要求 5所述的方法， 其特征在于五价钒化合物与混合 醇进行还原反应后， 再滴加磷含氧酸。
8. 根据权利要求 5 所述的方法， 其特征在于混合醇是体积比为 2.5-5.0的异丁醇和苯甲醇。
9. 根据权利要求 5 所述的方法， 其特征在于磷含氧酸的滴加速率 为 1-9克 /分。
10. 根据权利要求 9 所述的方法， 其特征在于磷含氧酸的滴加速率 为 3-8克 /分。
11. 根据权利要求 5所述的方法， 其特征在于磷含氧酸为磷酸。
12. 根据权利要求 10所述的方法， 其特征在于磷酸为 85重量％磷 酸。
13. 根据权利要求 5所述的方法， 其特征在于烷基硅的滴加速率为 1.0-5.0克 /分。
14. 根据权利要求 13所述的方法， 其特征在于烷基硅的滴加速率为 1.0-4.5克 /分。
15. 根据权利要求 5所述的方法， 其特征在于烷基硅为四甲氧基硅 烷或四乙氧基硅烷。
16. 根据权利要求 1 - 4中任一项的所述催化剂前驱体在丁烷催化氧 化制备顺酐中的应用。
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