WO2019007239A1 - 适用于卤代芳腈生产的流化床催化剂、其制备及应用 - Google Patents
适用于卤代芳腈生产的流化床催化剂、其制备及应用 Download PDFInfo
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- WO2019007239A1 WO2019007239A1 PCT/CN2018/093041 CN2018093041W WO2019007239A1 WO 2019007239 A1 WO2019007239 A1 WO 2019007239A1 CN 2018093041 W CN2018093041 W CN 2018093041W WO 2019007239 A1 WO2019007239 A1 WO 2019007239A1
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- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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Definitions
- the present invention relates to a catalyst suitable for use as a fluidized bed catalyst for producing a halogenated aromatic nitrile, a process for the preparation thereof and an application thereof.
- Halogenated aramids are an important class of aromatic nitrile compounds and can be used in the production of pharmaceuticals, pesticides, dyes, etc., and are important fine chemicals.
- o-chlorobenzonitrile can be used as an important intermediate of azo disperse dyes by 2-nitroaniline reaction; 2-cyano-4-nitroaniline; and biphenyl compound synthesized with halogenated benzene to prepare non-peptide anti-angi Angiotensin can also prepare a variety of anti-inflammatory and bactericidal drugs; p-chlorobenzonitrile and p-bromobenzonitrile are also commonly used as pharmaceutical and pesticide intermediates.
- the production of aromatic nitriles includes chemical synthesis, gas phase ammoxidation and the like. Among them, aromatic nitrogen, ammonia and air are synthesized in one step by gas phase ammoxidation reaction. The process is short and the pollution is small, which is the main method for the production of aromatic nitriles.
- the reaction is characterized in that both the primary and secondary reactions are strongly exothermic. Thus, the choice of catalyst active components and form and the choice of the corresponding reactor are critical.
- the fluidized bed has the advantages of high heat and mass transfer efficiency and easy enlargement, but has high requirements on the physical and chemical properties of the catalyst and the fluidization quality control in the reactor, especially the catalyst.
- Halogenated aramids as a class of aromatic nitriles, also meet the above characteristics.
- vanadium-based oxide catalysts are the most effective catalytic systems, such as VP, V-Cr and other catalytic systems, usually prepared by using alumina, silicon carbide and silica as carriers. Spherical particles of different particle sizes are used in a fluidized bed reactor. Early catalysts generally used oxide systems such as V-P-O and V-Cr-O as simple catalysts, and the problem of low selectivity of aromatic nitriles was ubiquitous. In recent years, the production of aromatic nitrile fluidized bed catalysts mostly uses multi-component vanadium-based oxide catalysts, which improves the selectivity of aromatic nitriles to some extent. However, the development of aromatic nitrile catalysts is mostly directed to aramid compounds such as isophthalonitrile and terephthalonitrile, and less to halogenated aromatic nitriles.
- Chinese patent CN1187320C discloses a fluidized bed catalyst for preparing o-chlorobenzonitrile, which has a composition of VCr a B b X c Y d Z e O m /SiO 2 ;
- Chinese patent CN1223579C discloses a p-chlorobenzene.
- a fluidized bed catalyst of carbonitrile having a composition of VCr a A b B c C d O x /SiO 2 ;
- Chinese Patent CN1252043C discloses a method for preparing p-bromobenzonitrile using an active composition of VCr a A b B a supported catalyst of c C d O x .
- the catalysts disclosed in the above three are all good for a specific halogenated aramid product, and do not involve applicability to other halogenated aramids.
- All of the above fluidized bed catalysts employ a V-Cr-based oxide while adding various components and a silica carrier to effect production of a halogenated aramid.
- a halogenated aromatic hydrocarbon due to the inherent structural characteristics of halogenated aromatic hydrocarbons, the presence of halogenated groups in the molecule makes the activation of the ⁇ -position CH bond more difficult than the aromatic hydrocarbons such as toluene and xylene. Therefore, the ammoxidation process is The catalyst's ability to activate is more demanding.
- the catalysts reported in all of the above-mentioned documents generally have the problem of catalyzing the low ammoxidation activity of the halogenated aromatic hydrocarbons, and the catalyst selectivity is markedly lowered after raising the temperature or increasing the V content in the catalyst in order to enhance the activity. Further improvement in the activity selectivity of the production of halogenated aramids is an important issue for catalyst improvement.
- Chinese Patent Application Publication No. CN1230464A discloses a fluidized bed catalyst suitable for the preparation of 2,6-dichlorobenzonitrile having a composition of V 1.0 P b Na c A d B e O x /SiO 2 .
- Chinese Patent Application Publication No. CN1230465A discloses a fluidized bed catalyst suitable for the preparation of 2,6-dichlorobenzonitrile and o-chlorobenzonitrile having a composition of V 1.0 P a Cr b Mo c O x /SiO 2 .
- both of the disclosed catalysts require the addition of the hazardous chemical ethyl bromide to the reaction feedstock in order to achieve higher reaction conversion and selectivity.
- One of the objects of the present invention is to overcome the problems of low ammoxidation activity of halogenated aromatic hydrocarbons and low selectivity of aromatic nitriles in prior art catalysts, and to provide a novel catalyst suitable for ammoxidation of aromatic hydrocarbons to produce halogenated aromatic nitriles. , its preparation method and application.
- the catalyst has high activity and selectivity in the production of halogenated aramid, and is suitable for fluidized bed operation, and is more environmentally friendly and relatively inexpensive.
- the present invention provides a catalyst suitable for use as a fluidized bed catalyst for producing a halogenated aromatic nitrile, the catalyst comprising an active component and a carrier, the active component being an atom A composite having the following composition:
- A represents at least one metal selected from the group consisting of alkali metals and alkaline earth metals;
- M represents at least one selected from the group consisting of Ti, Zr, Hf, La, Ce, Nb, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, As, Ga, Ge, Sn, and In;
- the value of a ranges from 0 to 1.5.
- b ranges from 0.1 to 1;
- c ranges from 0 to 0.5.
- d ranges from 0-1;
- x is the number of oxygen atoms required to satisfy the valence of each element in the active component
- the carrier is selected from the group consisting of silica and molecular sieves,
- the support is a pure silicon molecular sieve.
- the support is a composite support composed of pure silicon molecular sieves and silica.
- the present invention provides a process for preparing a catalyst which is suitable for use as a fluidized bed catalyst for producing a halogenated aromatic nitrile comprising an active component and a carrier, the active component being atomic ratio
- a composite having the following composition:
- A represents at least one metal selected from the group consisting of alkali metals and alkaline earth metals;
- M represents at least one selected from the group consisting of Ti, Zr, Hf, La, Ce, Nb, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, As, Ga, Ge, Sn, and In;
- the value of a ranges from 0 to 1.5.
- b ranges from 0.1 to 1;
- c ranges from 0 to 0.5.
- d ranges from 0-1;
- x is the number of oxygen atoms required to satisfy the valence of each element in the active component
- the carrier is selected from the group consisting of silica and molecular sieves,
- the method includes the following steps:
- the method comprises the steps of:
- the mixed slurry is dried to obtain a catalyst precursor, and the catalyst precursor is calcined to obtain a final catalyst.
- the catalyst precursor in the step 4) is sequentially pre-baked at 300-350 ° C and calcined at 500-700 ° C to obtain a final catalyst.
- the invention provides a catalyst prepared by the process of the invention.
- the invention provides the use of a catalyst of the invention or a catalyst prepared according to the process of the invention as a fluid bed catalyst for the production of a halogenated aramid.
- the invention provides a process for the production of a halogenated aramid comprising the step of contacting a halogenated arene with a catalyst of the invention or a catalyst prepared according to the process of the invention.
- the contacting reaction is carried out in the absence of ethyl bromide.
- the catalyst of the invention and the catalyst prepared according to the process of the invention have specific XRD peaks and thus exhibit excellent ammoxidation activity, and can be used for the preparation of halogenated aramids without the aid of the dangerous chemical ethyl bromide. Conversion and selectivity are especially suitable for industrial applications.
- a pure silicon mesoporous molecular sieve is used as a carrier, the ammoxidation activity of the halogenated aromatic hydrocarbon can be further significantly enhanced, and when a composite carrier composed of pure silicon molecular sieve and silicon oxide is used, the selectivity of the target product can be further remarkably improved.
- the catalyst of the present invention has good versatility in the ammoxidation of a variety of different halogenated aromatic hydrocarbons.
- Figure 1 is an XRD chart of a catalyst prepared in Example 1 of the present invention.
- the present invention provides a catalyst suitable for use as a fluidized bed catalyst for producing a halogenated aramid, the catalyst comprising an active component and a carrier, the active component having the following atomic ratio as follows Composition of the complex:
- A represents at least one metal selected from the group consisting of alkali metals and alkaline earth metals, preferably at least one selected from the group consisting of alkali metals;
- M represents at least one selected from the group consisting of Ti, Zr, Hf, La, Ce, Nb, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, As, Ga, Ge, Sn, and In;
- the value of a ranges from 0 to 1.5.
- b ranges from 0.1 to 1;
- c ranges from 0 to 0.5.
- d ranges from 0-1;
- x is the number of oxygen atoms required to satisfy the valence of each element in the active component
- the carrier is selected from the group consisting of silica and molecular sieves,
- a in the composition of the composite is not 0; more preferably, a ranges from 0.5 to 1.5; more preferably, a ranges from 0.5 to 1.0.
- b has a value in the range of 0.1 to 0.7, and more preferably, b has a value in the range of 0.1 to 0.6.
- c ranges from 0.01 to 0.5, more preferably, c ranges from 0.01 to 0.3, and even more preferably, c ranges from 0.01 to 0.2.
- d has a value in the range of 0.01 to 0.5.
- a ranges from 0.5 to 1.5, and c ranges from 0.01 to 0.5. Still more preferably, a ranges from 0.5 to 1, b ranges from 0.1 to 0.7, c ranges from 0.01 to 0.3, and d ranges from 0.01 to 0.5.
- A is at least one of Na, K and Ca, more preferably at least one of K and Ca, most preferably K.
- M is selected from at least one of Ti, Nb, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, and Sn, more preferably selected from the group consisting of Mo, Nb, B, and W. At least one of them.
- the active component of the catalyst may further comprise Se and/or Te in a molar ratio to V of from 0.01 to 0.2, preferably from 0.02 to 0.1.
- the amount of carrier in the catalyst is from 20 to 70%, more preferably from 30% to 60% by weight.
- the carrier in the catalyst of the present invention utilizes a molecular sieve material, unlike conventional halogenated aromatic ammoxidation catalysts.
- the carrier is a pure silicon molecular sieve.
- the pure silicon molecules are screened from one of MCM-41, MCM-48, SBA-1, SBA-2, SBA-15, SBA-16, MSU, Silicate-1, SSZ-13 and HMS. Or more, most preferably SSZ-13 molecular sieve.
- the support in the catalyst of the present invention is a composite support composed of pure silicon molecular sieve and silica, wherein the weight ratio of the pure silicon molecular sieve to the silicon oxide is 1:9 to 9:1, It is preferably from 1:4 to 4:1.
- the pure silicon molecules in the composite support are selected from MCM-41, MCM-48, SBA-1, SBA-2, SBA-15, SBA-16, MSU, Silicate-1, SSZ-13 and HMS. One or more of them.
- the support is a composite support of SSZ-13 molecular sieve and silica, and the weight ratio of SSZ-13 molecular sieve to silica in the composite support is preferably from 1:9 to 9:1, more preferably from 1:4 to 4:1.
- the catalyst of the present invention can form a composite phase structure, and its crystal phase composition can be detected and defined by X-ray diffraction (XRD) technology.
- the catalyst of the invention has particularly good catalytic properties.
- the ratio of the main characteristic peak attributed to V 2 O 5 or Cr 2 O 3 to the intensity of the main characteristic peak attributed to CrVO 4 in the XRD spectrum of the catalyst of the present invention is 0-0.5, wherein
- the catalyst of the present invention can be prepared by a mixing method or a dipping method, more preferably, by a mixing method.
- the catalyst can be prepared by a process comprising the following steps:
- the catalyst can be prepared by a process comprising the steps of:
- the mixed slurry is dried to obtain a catalyst precursor, and the catalyst precursor is calcined to obtain a final catalyst.
- the catalyst precursor in step 4) is pre-baked at 300-350 ° C and calcined at 500-700 ° C to obtain the final catalyst.
- an oxide of vanadium pentoxide, phosphoric acid and an element corresponding to A and M in the formula is used as a starting material for the active component of the catalyst of the present invention, or alternatively, it can be converted into a corresponding method by a suitable method.
- Other compounds of the oxide are used as starting materials for the active component of the catalyst of the present invention.
- Examples of useful materials include, but are not limited to:
- Vanadium-containing raw materials vanadium pentoxide, ammonium metavanadate, vanadium sulfate and vanadium organic acids such as vanadium oxalate and vanadium tartrate;
- Chromium-containing material chromium trioxide and a compound which can be converted to chromium oxide by calcination;
- a raw material oxide, nitrate or other soluble compound of A
- M-containing material oxide, nitrate or other soluble compound of M
- Phosphorus-containing materials phosphorus pentoxide, phosphomolybdic acid and phosphotungstic acid.
- the vanadium-containing material is selected from the group consisting of vanadium pentoxide, ammonium metavanadate, vanadium sulfate, and vanadium organic acid;
- the chromium-containing material is selected from the group consisting of chromium trioxide and can be converted to chromium by roasting.
- the M-containing material is selected from the group consisting of oxides, nitrates, or other soluble compounds of M;
- the phosphorus-containing material is selected from the group consisting of phosphorus pentoxide, phosphomolybdic acid, and phosphotungstic acid. .
- the present invention provides a process for preparing a catalyst which is suitable for use as a fluidized bed catalyst for producing a halogenated aromatic nitrile comprising an active component and a carrier, the active component being atomic ratio
- a composite having the following composition:
- A represents at least one metal selected from the group consisting of alkali metals and alkaline earth metals, preferably at least one selected from the group consisting of alkali metals;
- M represents at least one selected from the group consisting of Ti, Zr, Hf, La, Ce, Nb, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, As, Ga, Ge, Sn, and In;
- the value of a ranges from 0 to 1.5.
- b ranges from 0.1 to 1;
- c ranges from 0 to 0.5.
- d ranges from 0-1;
- x is the number of oxygen atoms required to satisfy the valence of each element in the active component
- the carrier is selected from the group consisting of silica and molecular sieves,
- the method includes the following steps:
- the method comprises the steps of:
- the mixed slurry is dried to obtain a catalyst precursor, and the catalyst precursor is calcined to obtain a final catalyst.
- the catalyst precursor in step 4) is pre-baked at 300-350 ° C and calcined at 500-700 ° C to obtain the final catalyst.
- a in the composition of the composite is not 0; more preferably, a ranges from 0.5 to 1.5; more preferably, a ranges from 0.5 to 1.0.
- b has a value in the range of 0.1 to 0.7, and more preferably, b has a value in the range of 0.1 to 0.6.
- c ranges from 0.01 to 0.5, more preferably, c ranges from 0.01 to 0.3, and even more preferably, c ranges from 0.01 to 0.2.
- d has a value in the range of 0.01 to 0.5.
- a ranges from 0.5 to 1.5, and c ranges from 0.01 to 0.5. Still more preferably, a ranges from 0.5 to 1, b ranges from 0.1 to 0.7, c ranges from 0.01 to 0.3, and d ranges from 0.01 to 0.5.
- A is at least one of Na, K and Ca, more preferably at least one of K and Ca, most preferably K.
- M is selected from at least one of Ti, Nb, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, and Sn, more preferably selected from the group consisting of Mo, Nb, B, and W. At least one of them.
- the active component of the catalyst may further comprise Se and/or Te in a molar ratio to V of from 0.01 to 0.2, preferably from 0.02 to 0.1.
- the amount of carrier in the catalyst is from 20 to 70%, more preferably from 30% to 60% by weight.
- the carrier uses a molecular sieve material.
- the support is a pure silicon molecular sieve.
- the pure silicon molecules are screened from one of MCM-41, MCM-48, SBA-1, SBA-2, SBA-15, SBA-16, MSU, Silicate-1, SSZ-13 and HMS. Or more, most preferably SSZ-13 molecular sieve.
- the support is a composite support composed of pure silicon molecular sieves and silica, wherein the weight ratio of the pure silicon molecular sieve to silicon oxide is from 1:9 to 9:1, more preferably 1 : 4 to 4:1.
- the pure silicon molecules in the composite support are selected from MCM-41, MCM-48, SBA-1, SBA-2, SBA-15, SBA-16, MSU, Silicate-1, SSZ-13 and HMS. One or more of them.
- the support is a composite support of SSZ-13 molecular sieve and silica, and the weight ratio of SSZ-13 molecular sieve to silica in the composite support is preferably from 1:9 to 9:1, more preferably from 1:4 to 4:1.
- the vanadium-containing material is selected from the group consisting of vanadium pentoxide, ammonium metavanadate, vanadium sulfate, and vanadium organic acid;
- the chromium-containing material is selected from the group consisting of chromium oxide and can be converted to chromium oxide by roasting.
- the M-containing material is selected from the group consisting of oxides, nitrates, or other soluble compounds of M;
- the phosphorus-containing material is selected from the group consisting of phosphorus pentoxide, phosphomolybdic acid, and phosphotungstic acid.
- the invention provides a catalyst prepared by the process of the invention.
- the invention provides the use of a catalyst according to the invention as a fluidized bed catalyst for the production of a halogenated aramid.
- the present invention provides a process for producing a halogenated aromatic nitrile comprising the step of contacting a halogenated aromatic hydrocarbon with a catalyst according to the present invention.
- the halogenated aryl nitrile is selected from the group consisting of o-chlorobenzonitrile, m-chlorobenzonitrile, p-chlorobenzonitrile, o-bromobenzonitrile, m-bromobenzonitrile, p-bromobenzonitrile.
- dichlorobenzonitrile and dibromobenzonitrile more preferably selected from the group consisting of o-chlorobenzonitrile, m-chlorobenzonitrile, p-chlorobenzonitrile, p-bromobenzonitrile and dichloride
- benzonitriles are particularly preferably p-chlorobenzonitrile and dichlorobenzonitrile.
- the contacting reaction is carried out in the absence of ethyl bromide.
- the present invention provides the following technical solutions:
- Scheme 1 A fluidized bed catalyst for producing a halogenated aromatic nitrile comprising an active component and a carrier; and the active component is a composition having an atomic ratio as follows:
- A is at least one selected from the group consisting of alkali metal or alkaline earth metal elements
- M is at least one selected from the group consisting of Ti, Zr, Hf, La, Ce, Nb, Cr, Mo, W, Co, Zn, Fe, Ni, B, Sb, Bi, As, Ga, Ge, Sn, and In;
- the support is silica or a molecular sieve.
- Scheme 2 A fluidized bed catalyst for producing a halogenated aromatic nitrile as described in Scheme 1, characterized in that the ratio of the main diffraction characteristic peak intensities of V 2 O 5 or Cr 2 O 3 and CrVO 4 in the XRD spectrum of the catalyst is 0-0.5.
- Scheme 4 A fluidized bed catalyst for producing a halogenated aramid as described in Scheme 1, wherein a ranges from 0.5 to 1.5; and/or c ranges from 0.01 to 0.5.
- Scheme 5 The fluidized bed catalyst for producing a halogenated aramonitrile according to Scheme 1, characterized in that A is selected from at least one of alkali metal elements.
- Scheme 6 The fluidized bed catalyst for producing a halogenated aromatic nitrile as described in Scheme 1, wherein a ranges from 0.5 to 1; and/or b ranges from 0.1 to 0.7; and/or c The value ranges from 0.01 to 0.3; and/or d ranges from 0.01 to 0.5.
- Scheme 7 A fluidized bed catalyst for producing a halogenated aramid as described in Scheme 1, characterized in that the support is present in the catalyst in an amount of from 20% to 70% by weight.
- Scheme 8 A fluidized bed catalyst for producing a halogenated aramid as described in Scheme 1, characterized in that the carrier is a molecular sieve.
- Scheme 9 A fluidized bed catalyst for producing a halogenated aramid as described in Scheme 8, characterized in that the support is selected from the group consisting of pure silicon molecular sieves.
- Scheme 10 A fluidized bed catalyst for producing a halogenated aramid as described in Scheme 9, characterized in that pure silicon molecules are screened from MCM-41, MCM-48, SBA-1, SBA-2, SBA-15, SBA- 16. One or at least one of MSU and HMS.
- Scheme 11 A method for producing a halogenated aromatic nitrile, wherein a halogenated aromatic hydrocarbon is contacted with a catalyst according to any one of Schemes 1 to 10 to obtain a halogenated aromatic nitrile.
- halogenated aromatic nitrile selected from (o-, m-, p-) chlorobenzonitrile, (o-, m-, p-) bromide
- nitrile dichlorobenzonitrile, and dibromobenzonitrile.
- the catalyst of the invention can be used in a fluidized bed reactor of conventional design, usually as long as the fluidization quality of the gas flow is ensured, and abnormal fluidization phenomena such as "bubble", "channel flow” and “surge” in the fluidization process are reduced. Produce while minimizing the degree of backflow of the gas stream to increase the selectivity of the reaction.
- the catalyst of the invention can be used for the production of various halogenated aromatic nitriles including, but not limited to, o-chlorobenzonitrile, m-chlorobenzonitrile, p-chlorobenzonitrile, o-bromobenzonitrile, m-bromobenzonitrile, p-bromobenzene Formonitrile, dichlorobenzonitrile and dibromobenzonitrile.
- the catalyst of the present invention is generally used for carrying out the reaction under normal pressure, and can also be used for carrying out the reaction under pressure, but the increase in the reaction pressure is disadvantageous for the improvement of the yield of the halogenated aromatic nitrile product. Therefore, preferably, the pressure of the reaction system should be kept at normal pressure or as close as possible to normal pressure.
- the catalyst of the present invention has a specific XRD peak and thus exhibits superior ammoxidation activity and is more suitable for industrial applications.
- a pure silicon mesoporous molecular sieve is used as a carrier, the ammoxidation activity of the halogenated aromatic hydrocarbon can be further significantly enhanced.
- the active component composition of the catalyst of the invention the high selectivity of the catalyst can be maintained without increasing the vanadium content and reducing the chromium content, thereby solving the problems of both activity and selectivity, and effectively improving the economy of the catalyst and Environmentally friendly.
- a pure silicon molecular sieve and a silica composite support are used as a catalyst carrier, the selectivity of the target product is unexpectedly remarkably improved.
- the performance evaluation of the catalyst of the present invention is The stainless steel fluidized bed reactor was carried out in an amount of 600 g of the catalyst.
- a 20 wt% phosphoric acid solution containing 0.8 mol of phosphoric acid (analytically pure, Chinese medicine reagent) was added to about 215 g of SBA-15 pure silicon molecular sieve, and the mixture was heated and stirred to 75 ° C and stirring was continued for 2 hours to obtain a second mixed solution.
- the solution I was slowly added to the solution II, stirred under heating to form a stable mixed solution, and concentrated to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried in a spray dryer, and the formed catalyst precursor was prebaked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours to obtain an atomic ratio of the catalyst active component in addition to O: VP 0.8 Cr 0.6 K 0.08 Mo 0.1 Nb 0.04 , the XRD spectrum of the catalyst is shown in Figure 1.
- the obtained catalyst is used for the ammoxidation of p-chlorotoluene to p-chlorobenzonitrile, and the reaction process conditions are as follows:
- the reaction pressure is 0.1 MPa (gauge pressure);
- the preparation and evaluation of the catalyst were carried out by the method of Example 1, except that a 20 wt% phosphoric acid solution containing 1.2 mol of phosphoric acid was replaced by a 20 wt% phosphoric acid solution containing 0.8 mol of phosphoric acid, and the amount of the carrier was adjusted accordingly so that the carrier content in the obtained catalyst was constant.
- the evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out in accordance with the method of Example 1, except that the amount of chromium trioxide was increased from 0.3 mol to 0.35 mol, and the amount of the carrier was adjusted accordingly so that the carrier content in the obtained catalyst was unchanged.
- the evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out in accordance with the method of Example 1, except that the amount of potassium nitrate was increased from 0.08 mol to 0.25 mol, and the amount of the carrier was adjusted accordingly so that the carrier content in the obtained catalyst was unchanged.
- the evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out according to the method of Example 1, except that 0.06 mol of calcium nitrate (analytical grade, Chinese medicine reagent) was used instead of the potassium nitrate used, and 0.5 mol of boric acid (analytical grade, national medicine reagent) was used instead of the phosphomolybdic acid used. And replacing the used antimony pentoxide with 0.0067 mol of ammonium tungstate, and adjusting the amount of the carrier accordingly so that the content of the carrier in the obtained catalyst does not change.
- the evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out in accordance with the method of Example 1, except that phosphomolybdic acid and antimony pentoxide were not added, and the amount of the carrier was adjusted accordingly so that the carrier content in the obtained catalyst was unchanged.
- the evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out according to the method of Example 1, except that 0.1 mol of selenium dioxide (analytically pure, Chinese medicine reagent) was used instead of the phosphomolybdic acid used, and no antimony pentoxide was added, and the amount of the carrier was adjusted accordingly.
- the carrier content in the resulting catalyst was kept constant. The evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out by referring to the method of Example 14, except that 0.05 mol of citric acid (analytical grade, Chinese medicine reagent) was used instead of the selenium dioxide used, and the amount of the carrier was adjusted accordingly so that the carrier content in the obtained catalyst was unchanged. .
- the evaluation results are shown in Table 1.
- the preparation and evaluation of the catalyst were carried out in accordance with the method of Example 14, except that the selenium dioxide used was replaced by a combination of 0.02 mol of citric acid and 0.03 mol of selenium dioxide, and the amount of the carrier was adjusted accordingly so that the carrier content in the obtained catalyst was not change.
- the evaluation results are shown in Table 1.
- the solution I was slowly added to the solution II, stirred under heating to form a stable mixed solution, and concentrated to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 .
- the obtained catalyst was used for the ammoxidation of p-chlorotoluene to p-chlorobenzonitrile.
- the reaction process conditions were the same as those in Example 1, and the evaluation results are shown in Table 1.
- the solution I was slowly added to the solution II, stirred under heating to form a stable mixed solution, and concentrated to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 .
- the obtained catalyst was used for the ammoxidation of p-chlorotoluene to p-chlorobenzonitrile.
- the reaction process conditions were the same as those in Example 1, and the evaluation results are shown in Table 1.
- a 20 wt% phosphoric acid solution containing 0.8 mol of phosphoric acid was added to 50 g of SSZ-13 pure silicon molecular sieve, 145 g of silica, and the mixture was heated to 75 ° C with stirring for 2 h to obtain a solution II.
- the solution I was slowly added to the solution II, stirred under heating to form a stable mixed solution, and concentrated to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 .
- the obtained catalyst was used for the ammoxidation of p-chlorotoluene to p-chlorobenzonitrile.
- the reaction process conditions were the same as those in Example 1, and the evaluation results are shown in Table 1.
- the solution I was slowly added to the solution II, stirred under heating to form a stable mixed solution, and concentrated to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 .
- the obtained catalyst was used for the ammoxidation of p-chlorotoluene to p-chlorobenzonitrile.
- the reaction process conditions were the same as those in Example 1, and the evaluation results are shown in Table 1.
- the solution I was slowly added to the solution II, stirred under heating to form a stable mixed solution, and concentrated to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 K 0.08 Mo 0.1 Nb 0.04 .
- the obtained catalyst was used for the ammoxidation of p-chlorotoluene to p-chlorobenzonitrile, and the reaction process conditions were the same as those in Example 1.
- the evaluation results are shown in Table 1.
- vanadium pentoxide 0.5 mol was added to a 50 wt% oxalic acid solution containing 2 mol of oxalic acid, and the mixture was stirred well for 2 hours to obtain a vanadium-containing solution.
- 85 wt% phosphoric acid containing 0.8 mol of phosphoric acid, 0.08 mol of potassium nitrate, phosphomolybdic acid containing 0.1 mol of molybdenum, 0.6 mol of chromium nitrate (analytical grade, Chinese medicine reagent), 0.04 mol of bismuth oxalate (analysis) were sequentially added while maintaining stirring.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 K 0.08 Mo 0.1 Nb 0.04 .
- the obtained catalyst was used for the ammoxidation reaction of p-chlorotoluene under the same evaluation conditions as in Example 1, and the evaluation results are shown in Table 1.
- vanadium pentoxide 0.5 mol was added to a 50 wt% oxalic acid solution containing 2 mol of oxalic acid, and the mixture was stirred well for 2 hours to obtain a vanadium-containing solution.
- 85 wt% phosphoric acid containing 1.5 mol of phosphoric acid, 0.08 mol of potassium nitrate, phosphomolybdic acid containing 0.1 mol of molybdenum, 0.04 mol of lanthanum oxalate and deionized water, and an aluminum sol containing 200 g of alumina were sequentially added while maintaining stirring.
- the obtained catalyst was used for the ammoxidation reaction of p-chlorotoluene under the same evaluation conditions as in Example 1, and the evaluation results are shown in Table 1.
- 0.5 mol of vanadium pentoxide and 0.3 mol of chromium trioxide were added to a 50 wt% oxalic acid solution containing 5 mol of oxalic acid, and the mixture was heated sufficiently to stir at 60 ° C for 2 h to obtain a vanadium chromium solution.
- 85 wt% phosphoric acid containing 0.8 mol of phosphoric acid, 0.08 mol of potassium nitrate, phosphomolybdic acid containing 0.1 mol of molybdenum, 0.04 mol of lanthanum oxalate and deionized water were sequentially added while maintaining stirring, and after stirring for 1 h, about 215 g of dioxide was added.
- the silica sol of silicon was slowly added to the above solution under stirring, stirred to form a stable mixed solution, and then heated to evaporate to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried in a spray dryer, and the formed catalyst precursor was calcined at 650 ° C for 5 hours.
- the obtained catalyst active component was divided by atomic ratio of O: VP 0.8 Cr 0.6. K 0.08 Mo 0.1 Nb 0.04 .
- the obtained catalyst was used for the ammoxidation reaction of p-chlorotoluene under the same evaluation conditions as in Example 1, and the evaluation results are shown in Table 1.
- the mixture was stirred to form a stable mixed solution, and then heated to evaporate to a solid content of 45% by weight to obtain a viscous slurry.
- the slurry was spray-dried and formed in a spray dryer, and the formed catalyst precursor was pre-baked at 300 ° C for 2 hours and then calcined at 650 ° C for 4.5 hours.
- the obtained catalyst active component was divided into O atomic ratio composition: VP. 0.8 Cr 0.6 .
- the obtained catalyst was used for the ammoxidation reaction of p-chlorotoluene under the same evaluation conditions as in Example 1, and the evaluation results are shown in Table 1.
- the catalyst of the present invention according to Example 1-21 has significantly improved catalytic performance, particularly significantly improved product selectivity, as compared to the catalyst of Comparative Examples 1-4.
- the selection of a pure silicon molecular sieve as a carrier is advantageous for further improving the ammoxidation activity of the halogenated aromatic hydrocarbon of the catalyst (see, for example, Examples 1 and 8-12, etc.), and selecting a composite of pure silicon molecular sieve and silicon oxide.
- the carrier can further increase the selectivity of the target product (see, for example, Examples 19-21, etc.).
- the catalyst was prepared by the method of Example 1, and the catalyst was used for the ammoxidation reaction of o-chlorotoluene.
- the reaction conditions were as follows:
- the catalyst was prepared by the method of Example 1, and the catalyst was used for the ammoxidation reaction of m-chlorotoluene.
- the reaction conditions were as follows:
- the catalyst was prepared by the method of Example 1, and the catalyst was used for the ammoxidation reaction of p-toluene toluene.
- the reaction conditions were as follows:
- the catalyst was prepared by the method of Example 1, and the catalyst was used for the ammoxidation reaction of 2,6-dichlorotoluene.
- the reaction conditions were as follows:
- the catalyst was prepared by the method of Example 1, and the catalyst was used for the ammoxidation reaction of 3,4-dichlorotoluene.
- the reaction conditions were as follows:
- the catalyst was prepared by the method of Example 13, and the catalyst was used for the ammoxidation reaction of 2,6-dichlorotoluene.
- the reaction conditions employed were as follows:
- the catalyst was prepared by the method described in Example 1 of Chinese Patent Application Publication No. CN1230465A. 165.7 g of vanadium pentoxide was added to a solution consisting of 360 ml of water and 345 g of oxalic acid, and stirred well to obtain a vanadium oxalate solution. 695.5 g of oxalic acid and 450 ml of aqueous solution were slowly added with 182.2 g of chromium oxide (analytically pure, Chinese medicine reagent) at 50-60 ° C, and stirred to obtain a chromium oxalate solution.
- chromium oxide analytically pure, Chinese medicine reagent
- the vanadium oxalate solution and the chromium oxalate solution are mixed at 50-60 ° C to obtain a vanadium chromium solution.
- Into 1 L of water 160.6 g of ammonium molybdate (analytical grade, Chinese medicine reagent) was added, and 105 g of 85% phosphoric acid was mixed to obtain a molybdenum phosphorus solution.
- the vanadium-chromium solution and the molybdenum-phosphorus solution were thoroughly mixed, and 1250 g of a silica sol containing 40% of silica was added, stirred and heated, and evaporated to a solid content of 38% to obtain a slurry.
- the slurry was spray molded to obtain a catalyst.
- the obtained catalyst active component was composed of an atomic ratio of V 1 Cr 1 P 0.5 Mo 0.5 in addition to O.
- the catalyst was used for the ammoxidation reaction of p-chlorotoluene, and the same reaction process conditions as in Example 1 of the present invention were used for evaluation.
- the evaluation results showed that the conversion of p-chlorotoluene was 90.1%, and the selectivity of p-chlorobenzonitrile was 82.5%.
- the catalyst prepared in Comparative Example 5 was used for the ammoxidation reaction of o-chlorotoluene.
- the reaction conditions were the same as in Example 22.
- the evaluation results showed that the conversion of o-chlorotoluene was 87.9%, and the selectivity of o-chlorobenzonitrile was 80.2%.
- the catalyst prepared in Comparative Example 5 was used for the ammoxidation reaction of 2,6-dichlorotoluene.
- the reaction conditions were the same as in Example 25.
- the evaluation result was that the conversion rate of 2,6-dichlorotoluene was 88.6%, 2,
- the selectivity of 6-dichlorobenzonitrile was 78.5%.
- the catalyst was prepared by the method described in Example 1 of Chinese Patent Application Publication No. CN1187320C. 224 g of vanadium pentoxide was added to a solution of 490 ml of water and 468 g of oxalic acid at a temperature of 80 to 90 ° C, and the mixture was thoroughly stirred to obtain a vanadium oxalate solution. 1250 g of a silica sol having a weight percent concentration of 40% silica was slowly added to the above solution under stirring, and then 864 g of chromium nitrate, 12.4 g of potassium nitrate, and 71.6 g of cobalt nitrate were separately added (analytically pure, Sinopharm reagent).
- the obtained catalyst active component was composed of an atomic ratio of V 1 Cr 0.9 B 0.5 P 0.3 Mo 0.1 Co 0.1 K 0.05 in addition to O.
- the catalyst was prepared by the method described in Example 1 of Chinese Patent Application Publication No. CN1223579C. 224 g of vanadium pentoxide was added to a solution of 490 ml of water and 468 g of oxalic acid at a temperature of 80 to 90 ° C, and the mixture was thoroughly stirred to obtain a vanadium oxalate solution. 1250 g of a silica sol having a weight percent concentration of 40% silica was slowly added to the above solution under stirring, and then a solution consisting of 864 g of chromium nitrate, 12.4 g of potassium nitrate and 500 ml of water, respectively, 76.4 g of boric acid, 85.1 was added.
- the obtained catalyst active component was composed of an atomic ratio of V 1 Cr 0.9 B 0.5 P 0.3 Mo 0.1 K 0.05 in addition to O.
- the catalyst was prepared by the method described in Example 1 of Chinese Patent Application Publication No. CN1252043C. 224 g of vanadium pentoxide was added to a solution of 490 ml of water and 468 g of oxalic acid at a temperature of 80 to 90 ° C, and the mixture was thoroughly stirred to obtain a vanadium oxalate solution.
- the slurry was spray-dried in a spray dryer, and the shaped catalyst precursor was calcined at 650 ° C for 5 h to obtain an active catalyst.
- the obtained catalyst active component was composed of an atomic ratio of V 1 Cr 0.9 B 0.5 P 0.3 K 0.1 in addition to O.
- a vanadium pentoxide was added to a solution of 3000 ml of water and 420 g of oxalic acid at a temperature of 80-90 ° C, and the mixture was stirred well to obtain a vanadium oxalate solution.
- 1250 g of a silica sol containing 40 wt% of silica was slowly added to the above solution under stirring, and then a solution consisting of 798 g of chromium nitrate and 900 ml of water, a solution of 68.6 g of boric acid and 560 ml of water, and 273 g of ammonium molybdate and 200 ml were separately added.
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Abstract
一种适合用作生产卤代芳腈的流化床催化剂、其制备方法及应用。催化剂包括活性组分和载体,活性组分为以原子比计具有如下组成的复合物:VPaCrbAcMdOx 其中A代表选自碱金属和碱土金属中的至少一种金属;M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种。催化剂的XRD衍射图谱中,在2θ=27.8±0.5°和2θ=13.8±0.5°处具有衍射峰,并且在2θ=27.8±0.5°处的衍射峰峰高(I1)和2θ=13.8±0.5°处的衍射峰峰高(I2)的比例I1:I2=3.5~6。该催化剂显示出优异的氨氧化活性,应用于卤代芳腈制备时无需借助危险化学品溴乙烷即可达到较高的反应转化率和选择性。
Description
本发明涉及一种适合用作生产卤代芳腈的流化床催化剂的催化剂、其制备方法及应用。
卤代芳腈是芳腈化合物中的重要一类,可用于生产医药、农药、染料等,是重要的精细化学品。如邻氯苯甲腈经硝化氨解反应可制得多用途偶氮分散染料的重要中间体2-氰基-4-硝苯胺;与卤代苯合成联苯化合物用于制备非肽型抗血管紧张素,还可制备多种消炎杀菌药物;对氯苯甲腈、对溴苯甲腈也常被用做医药和农药中间体等。
芳腈的生产有化学合成、气相氨氧化等方法,其中将芳烃、氨与空气经气相氨氧化反应一步合成芳腈,流程短,污染少,是目前芳腈生产的主要方法。该反应的特点是主副反应都是强放热反应过程。因而,催化剂活性组分及形式的选择和相应反应器的选择就显得至关重要。流化床具有传热传质效率高、易于大型化等优点,但对催化剂物理化学性能和反应器中流态化质量控制尤其是催化剂有较高要求。卤代芳腈作为芳腈中的一类,同样符合上述特点。
在芳烃氨氧化制芳腈的流化床催化剂中,钒系氧化物催化剂是最为有效的催化体系,如V-P、V-Cr等催化体系,通常以氧化铝、碳化硅、氧化硅为载体,制备成不同粒度的球形颗粒在流化床反应器中应用。早期的催化剂通常以简单组成的V-P-O、V-Cr-O等氧化物体系作为催化剂,普遍存在芳腈选择性较低的问题。近年的生产芳腈流化床催化剂,大多采用多组分钒系氧化物催化剂,一定程度上提高了芳腈的选择性。但芳腈催化剂的开发大多针对间苯二甲腈、对苯二甲腈等芳腈化合物,而对卤代芳腈涉及较少。
中国专利CN1187320C中公开了一种制备邻氯苯甲腈的流化床催化剂,其组成为VCr
aB
bX
cY
dZ
eO
m/SiO
2;中国专利CN1223579C公开了一种制对氯苯甲腈的流化床催化剂,其组成为VCr
aA
bB
cC
dO
x/SiO
2;中国专利CN1252043C公开了一种制备对溴苯甲腈的方法,使用活性组成为VCr
aA
bB
cC
dO
x的负载催化剂。但是,以上三者公开的催化剂均为 针对具体的某一种卤代芳腈产品具有较好性能,未涉及对其他卤代芳腈的适用性。
以上这些流化床催化剂均采用V-Cr系氧化物,同时添加多种组分和二氧化硅载体,以实现卤代芳腈的生产。但是,由于卤代芳烃本身固有的结构特点,与甲苯、二甲苯等芳烃相比,其分子中卤代基团的存在,使α位C-H键的活化更为困难,因此其氨氧化过程中对催化剂的活化能力要求更高。上述所有文献报道的这些催化剂,通常存在催化卤代芳烃氨氧化活性较低的问题,而为了提升活性而提升温度或提高催化剂中V含量后,催化剂的选择性则会出现显著下降。进一步改进生产卤代芳腈的活性选择性是催化剂改进的重要问题。
中国专利申请公开CN1230464A公开了一种适用于制备2,6-二氯苯甲腈的流化床催化剂,其组成为V
1.0P
bNa
cA
dB
eO
x/SiO
2。中国专利申请公开CN1230465A公开了一种适用于制备2,6-二氯苯甲腈和邻氯苯甲腈的流化床催化剂,其组成为V
1.0P
aCr
bMo
cO
x/SiO
2。但是,这两者所公开的催化剂在使用时都需要在反应原料中添加危险化学品溴乙烷,藉此才能获得较高的反应转化率和选择性。
发明内容
本发明的目的之一是克服现有技术催化剂的卤代芳烃氨氧化活性较低和/或芳腈选择性较低的问题,提供一种新型的适用于芳烃氨氧化制备卤代芳腈的催化剂、其制备方法及应用。该催化剂用于卤代芳腈生产中时兼具高活性与选择性,且适于流化床操作,同时更加环保、成本也相对低廉。
为了实现上述目的,在一个方面,本发明提供了一种催化剂,其适合用作生产卤代芳腈的流化床催化剂,所述催化剂包括活性组分和载体,所述活性组分为以原子比计具有如下组成的复合物:
VP
aCr
bA
cM
dO
x
其中:
A代表选自碱金属和碱土金属中的至少一种金属;
M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种;
a的取值范围为0-1.5;
b的取值范围为0.1-1;
c的取值范围为0-0.5;
d的取值范围为0-1;
x为满足所述活性组分中各元素化合价所需的氧原子数;
所述载体选自氧化硅和分子筛,
其中在所述催化剂的XRD衍射图谱中,在2θ=27.8±0.5°和2θ=13.8±0.5°处具有衍射峰,并且在2θ=27.8±0.5°处的衍射峰峰高(I
1)和2θ=13.8±0.5°处的衍射峰峰高(I
2)的比例I
1∶I
2为3.5-6。
在一优选的实施方式中,所述载体为纯硅分子筛。
在另一优选的实施方式中,所述载体为由纯硅分子筛和氧化硅组成的复合载体。
在另一方面,本发明提供了一种制备催化剂的方法,所述催化剂适合用作生产卤代芳腈的流化床催化剂,其包括活性组分和载体,所述活性组分为以原子比计具有如下组成的复合物:
VP
aCr
bA
cM
dO
x
其中:
A代表选自碱金属和碱土金属中的至少一种金属;
M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种;
a的取值范围为0-1.5;
b的取值范围为0.1-1;
c的取值范围为0-0.5;
d的取值范围为0-1;
x为满足所述活性组分中各元素化合价所需的氧原子数;
所述载体选自氧化硅和分子筛,
所述方法包括如下步骤:
1)将含钒原料和含铬原料溶于酸后与含M原料的溶液混合得到第一混合溶液;
2)将含磷原料、水和载体混合反应得到第二混合溶液;
3)将第一混合溶液和第二混合溶液合并并浓缩后得到混合浆料;以及
4)将混合浆料干燥、焙烧后得到最终催化剂。
在优选的实施方式中,所述方法包括如下步骤:
1)将一定量的含钒原料和含铬原料溶于加热的酸溶液中,并分别加入除含磷原料以外的助催化元素原料并加热搅拌制成第一混合溶液;
2)在磷酸水溶液中加入载体并充分加热搅拌制成第二混合溶液;
3)将第一混合溶液缓慢加入第二混合溶液中并进行搅拌浓缩得到一定固含量的混合浆料;以及
4)将混合浆料通过干燥成型得催化剂前体,将催化剂前体焙烧后得到最终催化剂。
在进一步优选的实施方式中,所述步骤4)中催化剂前体依次在300-350℃预焙烧和500-700℃焙烧活化得最终催化剂。
在又一方面,本发明提供了按照本发明方法制备得到的催化剂。
在又一方面,本发明提供了本发明催化剂或者按照本发明方法制备的催化剂用作生产卤代芳腈的流化床催化剂的用途。
在再一方面,本发明提供了一种生产卤代芳腈的方法,包括使卤代芳烃与本发明催化剂或者按照本发明方法制备的催化剂接触反应的步骤。
在优选的实施方式中,所述接触反应在不存在溴乙烷的条件下进行。
本发明催化剂和按照本发明方法制备的催化剂具备特定的XRD谱峰,因而显示出优异的氨氧化活性,用于卤代芳腈制备时无需借助危险化学品溴乙烷即可实现较高的反应转化率和选择性,特别适用于工业应用。特别地,当采用纯硅介孔分子筛作为载体时,能够进一步显著提升卤代芳烃氨氧化活性,且采用由纯硅分子筛和氧化硅组成的复合载体时,能够进一步显著提高目标产物的选择性。此外,本发明催化剂在多种不同卤代芳烃的氨氧化反应中具有良好的通用性。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图是用来帮助对本发明的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本发明,但并不构成对本发 明的限制。在附图中:
图1为本发明实施例1制备的催化剂的XRD谱图。
图2为对比例1制备的催化剂的XRD谱图。
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值,而应当理解为还涵盖了接近该精确值的值,即理解为被术语“大约”所修饰。并且,对于所披露的数值范围而言,在该范围的端点值之间、端点值与范围内的具体点值之间,以及各具体点值之间可以任意组合而得到一个或多个新的数值范围,这些新的数值范围也应被视为在本文中具体公开。
在第一方面,本发明提供了一种催化剂,其适合用作生产卤代芳腈的流化床催化剂,所述催化剂包括活性组分和载体,所述活性组分为以原子比计具有如下组成的复合物:
VP
aCr
bA
cM
dO
x
其中:
A代表选自碱金属和碱土金属中的至少一种金属,优选选自碱金属中的至少一种;
M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种;
a的取值范围为0-1.5;
b的取值范围为0.1-1;
c的取值范围为0-0.5;
d的取值范围为0-1;
x为满足所述活性组分中各元素化合价所需的氧原子数;
所述载体选自氧化硅和分子筛,
其中在所述催化剂的XRD衍射图谱中,在2θ=27.8±0.5°和2θ=13.8±0.5°处具有衍射峰,并且在2θ=27.8±0.5°处的衍射峰峰高(I
1)和2θ=13.8±0.5°处的衍射峰峰高(I
2)的比例I
1∶I
2为3.5-6,优选3.5-5。
在优选的实施方式中,所述复合物组成中的a不为0;更优选地,a的取值范围为0.5-1.5;更进一步优选地,a的取值范围为0.5-1.0。
在优选的实施方式中,b的取值范围为0.1-0.7,更优选地,b的取值范围为0.1-0.6。
在优选的实施方式中,c的取值范围为0.01-0.5,更优选地,c的取值范围为0.01-0.3,更进一步优选地,c的取值范围为0.01-0.2。
在优选的实施方式中,d的取值范围为0.01-0.5。
在进一步优选的实施方式中,a的取值范围为0.5-1.5,且c的取值范围为0.01-0.5。更进一步优选地,a的取值范围为0.5-1,b的取值范围为0.1-0.7,c的取值范围为0.01-0.3,且d的取值范围为0.01-0.5。
在优选的实施方式中,A为Na、K和Ca中的至少一种,更优选K和Ca中至少一种,最优选为K。
在优选的实施方式中,M选自Ti、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi和Sn中的至少一种,更优选选自Mo、Nb、B和W中的至少一种。
在某些优选的实施方式中,所述催化剂的活性组分中还可含有Se和/或Te,其与V的摩尔比为0.01-0.2,优选为0.02-0.1。
在优选的实施方式中,所述催化剂中的载体含量以重量百分比计为20-70%,更优选为30%-60%。
在优选的实施方式中,与常见的卤代芳烃氨氧化催化剂不同,本发明催化剂中的载体使用分子筛材料。进一步优选地,所述载体为纯硅分子筛。特别优选地,所述纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、Silicate-1、SSZ-13和HMS中的一种或多种,最优选为SSZ-13分子筛。
在某些优选的实施方式中,本发明催化剂中的载体为由纯硅分子筛和氧化硅组成的复合载体,其中所述纯硅分子筛与氧化硅的重量比为1∶9至9∶1,更优选为1∶4至4∶1。进一步优选地,所述复合载体中的纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、Silicate-1、SSZ-13和HMS中的一种或多种。特别优选地,所述载体为SSZ-13分子筛和氧化硅的复合载体,该复合载体中SSZ-13分子筛与氧化硅的重量比优选为1∶9至9∶1,更优选为1∶4至4∶1。
本发明催化剂可形成复合物相结构,其晶相组成可用X射线衍射 (XRD)技术进行侦测和定义。本发明的催化剂中具有CrVO
4相,当其在2θ=27.8±0.5°处的衍射峰峰高(I
1)和2θ=13.8±0.5°处的衍射峰峰高(I
2)的比例I
1∶I
2为3.5-6、优选3.5-5时,本发明催化剂具有特别良好的催化性能。
在优选的实施方式中,本发明催化剂的XRD谱图中归属于V
2O
5或Cr
2O
3的主要特征峰和归属于CrVO
4的主要特征峰的强度的比值为0-0.5,其中所述“归属于V
2O
5或Cr
2O
3的主要特征峰”是指XRD谱图中归属于V
2O
5或Cr
2O
3的特征峰中峰高最高者,而所述“归属于CrVO
4的主要特征峰”是指归属于CrVO
4的特征峰中峰高最高者,所述特征峰的强度的比值是指其峰高的比值。
在优选的实施方式中,本发明催化剂可通过混浆法或浸渍法制备,更优选地,使用混浆法制备。
在进一步优选的实施方式中,所述催化剂可通过包括如下步骤的方法制备得到:
1)将含钒原料和含铬原料溶于酸后与含M原料的溶液混合得到第一混合溶液;
2)将含磷原料、水和载体混合反应得到第二混合溶液;
3)将第一混合溶液和第二混合溶液合并并浓缩后得到混合浆料;以及
4)将混合浆料干燥、焙烧后得到最终催化剂。
在更进一步优选的实施方式中,所述催化剂可通过包括如下步骤的方法制备得到:
1)将一定量的含钒原料和含铬原料溶于加热的酸溶液中,并分别加入除含磷原料以外的助催化元素原料并加热搅拌制成第一混合溶液;
2)在磷酸水溶液中加入载体并充分加热搅拌制成第二混合溶液;
3)将第一混合溶液缓慢加入第二混合溶液中并进行搅拌浓缩得到一定固含量的混合浆料;以及
4)将混合浆料通过干燥成型得催化剂前体,将催化剂前体焙烧后得到最终催化剂。
特别优选地,步骤4)中催化剂前体依次在300-350℃预焙烧和500-700℃焙烧活化得最终催化剂。
在优选的实施方式中,使用五氧化二钒、磷酸及通式中A、M所对应元素的氧化物作为本发明催化剂活性组分的起始原料,或者也可选择能够经适当方法转化为相应氧化物的其它化合物作为本发明催化剂活性组分的起始原料。
可用原料的例子包括但不限于:
含钒原料:五氧化二钒、偏钒酸铵、硫酸钒和有机酸钒,如草酸钒和酒石酸钒;
含铬原料:三氧化二铬和可通过焙烧转化为铬氧化物的化合物;
含A原料:A的氧化物、硝酸盐或其它可溶化合物;
含M原料:M的氧化物、硝酸盐或其它可溶性化合物;
含磷原料:五氧化二磷、磷钼酸和磷钨酸。
在特别优选的实施方式中,所述含钒原料选自五氧化二钒、偏钒酸铵、硫酸钒和有机酸钒;所含铬原料选自三氧化二铬和可通过焙烧转化为铬氧化物的化合物;所述酸选自草酸;所述含M原料选自M的氧化物、硝酸盐或其它可溶性化合物;且所述含磷原料选自五氧化二磷、磷钼酸和磷钨酸。
在第二方面,本发明提供了一种制备催化剂的方法,所述催化剂适合用作生产卤代芳腈的流化床催化剂,其包括活性组分和载体,所述活性组分为以原子比计具有如下组成的复合物:
VP
aCr
bA
cM
dO
x
其中:
A代表选自碱金属和碱土金属中的至少一种金属,优选选自碱金属中的至少一种;
M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种;
a的取值范围为0-1.5;
b的取值范围为0.1-1;
c的取值范围为0-0.5;
d的取值范围为0-1;
x为满足所述活性组分中各元素化合价所需的氧原子数;
所述载体选自氧化硅和分子筛,
所述方法包括如下步骤:
1)将含钒原料和含铬原料溶于酸后与含M原料的溶液混合得到第一混合溶液;
2)将含磷原料、水和载体混合反应得到第二混合溶液;
3)将第一混合溶液和第二混合溶液合并并浓缩后得到混合浆料;以及
4)将混合浆料干燥、焙烧后得到最终催化剂。
在优选的实施方式中,所述方法包括如下步骤:
1)将一定量的含钒原料和含铬原料溶于加热的酸溶液中,并分别加入除含磷原料以外的助催化元素原料并加热搅拌制成第一混合溶液;
2)在磷酸水溶液中加入载体并充分加热搅拌制成第二混合溶液;
3)将第一混合溶液缓慢加入第二混合溶液中并进行搅拌浓缩得到一定固含量的混合浆料;以及
4)将混合浆料通过干燥成型得催化剂前体,将催化剂前体焙烧后得到最终催化剂。
在进一步优选的实施方式中,步骤4)中催化剂前体依次在300-350℃预焙烧和500-700℃焙烧活化得最终催化剂。
在优选的实施方式中,在所述催化剂的XRD衍射图谱中,在2θ=27.8±0.5°和2θ=13.8±0.5°处具有衍射峰,并且在2θ=27.8±0.5°处的衍射峰峰高(I
1)和2θ=13.8±0.5°处的衍射峰峰高(I
2)的比例I
1∶I
2为3.5-6,优选3.5-5。
在优选的实施方式中,所述复合物组成中的a不为0;更优选地,a的取值范围为0.5-1.5;更进一步优选地,a的取值范围为0.5-1.0。
在优选的实施方式中,b的取值范围为0.1-0.7,更优选地,b的取值范围为0.1-0.6。
在优选的实施方式中,c的取值范围为0.01-0.5,更优选地,c的取值范围为0.01-0.3,更进一步优选地,c的取值范围为0.01-0.2。
在优选的实施方式中,d的取值范围为0.01-0.5。
在进一步优选的实施方式中,a的取值范围为0.5-1.5,且c的取值范围为0.01-0.5。更进一步优选地,a的取值范围为0.5-1,b的取值范围为0.1-0.7,c的取值范围为0.01-0.3,且d的取值范围为0.01-0.5。
在优选的实施方式中,A为Na、K和Ca中的至少一种,更优选K 和Ca中至少一种,最优选为K。
在优选的实施方式中,M选自Ti、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi和Sn中的至少一种,更优选选自Mo、Nb、B和W中的至少一种。
在某些优选的实施方式中,所述催化剂的活性组分中还可含有Se和/或Te,其与V的摩尔比为0.01-0.2,优选为0.02-0.1。
在优选的实施方式中,所述催化剂中的载体含量以重量百分比计为20-70%,更优选为30%-60%。
在优选的实施方式中,所述载体使用分子筛材料。在进一步优选的实施方式中,所述载体为纯硅分子筛。特别优选地,所述纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、Silicate-1、SSZ-13和HMS中的一种或多种,最优选为SSZ-13分子筛。
在某些优选的实施方式中,所述载体为由纯硅分子筛和氧化硅组成的复合载体,其中所述纯硅分子筛与氧化硅的重量比为1∶9至9∶1,更优选为1∶4至4∶1。进一步优选地,所述复合载体中的纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、Silicate-1、SSZ-13和HMS中的一种或多种。特别优选地,所述载体为SSZ-13分子筛和氧化硅的复合载体,该复合载体中SSZ-13分子筛与氧化硅的重量比优选为1∶9至9∶1,更优选为1∶4至4∶1。
在优选的实施方式中,所述含钒原料选自五氧化二钒、偏钒酸铵、硫酸钒和有机酸钒;所含铬原料选自三氧化二铬和可通过焙烧转化为铬氧化物的化合物;所述酸选自草酸;所述含M原料选自M的氧化物、硝酸盐或其它可溶性化合物;且所述含磷原料选自五氧化二磷、磷钼酸和磷钨酸。
在第三方面,本发明提供了按照本发明方法制备得到的催化剂。
在第四方面,本发明提供了根据本发明的催化剂用作生产卤代芳腈的流化床催化剂的用途。
在第五方面,本发明提供了一种生产卤代芳腈的方法,包括使卤代芳烃与根据本发明的催化剂接触反应的步骤。
在优选的实施方式中,所述卤代芳腈选自邻氯苯甲腈、间氯苯甲腈、对氯苯甲腈、邻溴苯甲腈、间溴苯甲腈、对溴苯甲腈、二氯苯甲腈和二溴苯甲腈中的一种或多种,更优选选自邻氯苯甲腈、间氯苯甲 腈、对氯苯甲腈、对溴苯甲腈和二氯苯甲腈中的一种或多种,特别优选为对氯苯甲腈和二氯苯甲腈。
在优选的实施方式中,所述接触反应在不存在溴乙烷的条件下进行。
在某些具体实施方式中,本发明提供了以下的技术方案:
方案1:一种生产卤代芳腈的流化床催化剂,包括活性组分和载体;活性组分为以原子比计如下组成的组合物:
VP
aCr
bA
cM
dO
x
式中:A选自碱金属或碱土金属元素中的至少一种;
M选自Ti、Zr、Hf、La、Ce、Nb、Cr、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn、In中的至少一种;
其中a的取值范围为0-1.5;b的取值范围为0.1-1;c的取值范围为0-0.5;d的取值范围为0-1;x为满足催化剂中各元素化合价所需的氧原子数;
载体为氧化硅或分子筛。
方案2:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于催化剂的XRD谱图中V
2O
5或Cr
2O
3和CrVO
4的主要衍射特征峰强度的比例为0-0.5。
方案3:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于催化剂的XRD衍射图谱中,在2θ=27.8±0.5°处衍射峰峰高(I
1)和2θ=13.8±0.5°处的衍射峰峰高(I
2)比例I
1∶I
2=3.5-6。
方案4:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于a的取值范围为0.5-1.5;和/或c的取值范围为0.01-0.5。
方案5:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于A选自碱金属元素中的至少一种。
方案6:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于a的取值范围为0.5-1;和/或b的取值范围为0.1-0.7;和/或c的取值范围为0.01-0.3;和/或d的取值范围为0.01-0.5。
方案7:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于载体在催化剂中以重量计含量为20%-70%。
方案8:如方案1所述的生产卤代芳腈的流化床催化剂,其特征在于载体为分子筛。
方案9:如方案8所述的生产卤代芳腈的流化床催化剂,其特征在于载体选自纯硅分子筛。
方案10:如方案9所述的生产卤代芳腈的流化床催化剂,其特征在于纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、HMS中的一种或至少一种。
方案11:一种生产卤代芳腈的方法,卤代芳烃与方案1~10任一项所述催化剂接触反应得到卤代芳腈。
方案12:如方案11所述的生产卤代芳腈的方法,其特征在于所述卤代芳腈选自(邻、间、对)氯苯甲腈、(邻、间、对)溴苯甲腈、二氯苯甲腈、二溴苯甲腈中的一种或至少一种。
本发明催化剂可用在常规设计的流化床反应器中,通常只要保证气流的流态化质量,减少流化过程中“气泡”、“沟流”和“腾涌”等非正常流化现象的产生,同时尽量降低气流返混的程度,以提高反应的选择性。
本发明催化剂可用于生产各种卤代芳腈,包括但不限于邻氯苯甲腈、间氯苯甲腈、对氯苯甲腈、邻溴苯甲腈、间溴苯甲腈、对溴苯甲腈、二氯苯甲腈和二溴苯甲腈。
本发明催化剂通常用于在常压下进行反应,也可用于在加压情况下进行反应,但反应压力提高不利于卤代芳腈产品收率的提高。因此,优选地,反应系统的压力应保持常压或尽量接近于常压。
本发明催化剂具备特定的XRD谱峰,因此显示出更优的氨氧化活性,更适用于工业应用。特别地,当采用纯硅介孔分子筛作为载体时,能够进一步显著提升卤代芳烃氨氧化活性。另外,采用本发明催化剂的活性组分组成,可在不增加钒含量且降低铬含量的情况下,保持催化剂的高选择性,解决了活性与选择性兼顾的问题,有效提升催化剂的经济性与环保性。此外,当采用纯硅分子筛与氧化硅复合载体作为催化剂载体时,预料不到地显著提高了目标产物的选择性。
实施例
下面通过实施例对本发明作进一步的阐述,但并不因此而限制本发明范围。
本发明催化剂在实施例中卤代芳烃的转化率、芳腈的选择性和芳 腈收率定义如下:
【实施例1】
催化剂制备:
将0.5mol的五氧化二钒(分析纯,国药试剂)与0.3mol三氧化二铬(分析纯,国药试剂)加入加热至85℃的含2mol草酸(分析纯,国药试剂)的50wt%草酸溶液中,充分搅拌反应2h。在保持搅拌的情况下,加入0.02mol五氧化二铌(2.5N,国药试剂)继续反应1h后在溶液中加入0.08mol硝酸钾(分析纯,国药试剂)、含0.1mol钼的磷钼酸(分析纯,国药试剂)和去离子水并搅拌均匀得到溶液I。
将含0.8mol磷酸(分析纯,国药试剂)的20wt%磷酸溶液中加入约215g SBA-15纯硅分子筛后加热搅拌至75℃并持续搅拌2h得第二混合溶液。
将溶液I缓慢加入溶液II中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6K
0.08Mo
0.1Nb
0.04,催化剂XRD谱图见图1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=4.56。
催化剂评价:
将所得催化剂用于对氯甲苯氨氧化制对氯苯甲腈的反应,反应工艺条件如下:
对氯甲苯∶氨∶空气=1∶4∶35(摩尔);
负荷0.06h
-1(WWH);
反应压力0.1MPa(表压);
反应温度420℃;
结果:对氯甲苯转化率98.3%;
对氯苯甲腈选择性93.7%;
对氯苯甲腈收率92.1%。
【实施例2】
参照实施例1的方法进行催化剂的制备和评价,只是用含1.2mol磷酸的20wt%磷酸溶液替代含0.8mol磷酸的20wt%磷酸溶液,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例3】
参照实施例1的方法进行催化剂的制备和评价,只是将三氧化二铬的用量由0.3mol提高到0.35mol,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例4】
参照实施例1的方法进行催化剂的制备和评价,只是将硝酸钾的用量由0.08mol提高到0.25mol,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例5】
参照实施例1的方法进行催化剂的制备和评价,只是用0.06mol硝酸钙(分析纯,国药试剂)替代所用的硝酸钾,用0.5mol硼酸(分析纯,国药试剂)替代所用的磷钼酸,以及用0.0067mol钨酸铵替代所用的五氧化二铌,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例6】
参照实施例1的方法进行催化剂的制备和评价,只是将SBA-15纯 硅分子筛的用量由215g减少到55g。评价结果见表1。
【实施例7】
参照实施例1的方法进行催化剂的制备和评价,只是不添加磷钼酸和五氧化二铌,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例8】
参照实施例1的方法进行催化剂的制备和评价,只是用215g MCM-41纯硅分子筛替代所用的SBA-15纯硅分子筛。评价结果见表1。
【实施例9】
参照实施例1的方法进行催化剂的制备和评价,只是用215g HMS纯硅分子筛替代所用的SBA-15纯硅分子筛。评价结果见表1。
【实施例10】
参照实施例1的方法进行催化剂的制备和评价,只是用85g SBA-15纯硅分子筛与130g HMS纯硅分子筛的混合物替代所用的SBA-15纯硅分子筛。评价结果见表1。
【实施例11】
参照实施例1的方法进行催化剂的制备和评价,只是用194g MCM-48纯硅分子筛与22g MSU纯硅分子筛的混合物替代所用的SBA-15纯硅分子筛。评价结果见表1。
【实施例12】
参照实施例1的方法进行催化剂的制备和评价,只是用215g Silicate-1纯硅分子筛替代所用的SBA-15纯硅分子筛。评价结果见表1。
【实施例13】
参照实施例1的方法进行催化剂的制备和评价,只是用535g含40%二氧化硅的硅溶胶(试剂级,青岛海洋化工)替代所用的SBA-15 纯硅分子筛。评价结果见表1。
【实施例14】
参照实施例1的方法进行催化剂的制备和评价,只是用0.1mol二氧化硒(分析纯,国药试剂)替代所用的磷钼酸,且不添加五氧化二铌,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例15】
参照实施例14的方法进行催化剂的制备和评价,只是用0.05mol碲酸(分析纯,国药试剂)替代所用的二氧化硒,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例16】
参照实施例14的方法进行催化剂的制备和评价,只是用0.02mol碲酸与0.03mol二氧化硒的组合替代所用的二氧化硒,同时相应地调整载体用量,以使所得催化剂中的载体含量不变。评价结果见表1。
【实施例17】
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液I。
将含0.8mol磷酸的20wt%磷酸溶液中加入约195g SBA-15纯硅分子筛后加热搅拌至75℃并持续搅拌2h得溶液II。
将溶液I缓慢加入溶液II中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=3.90。
将所得催化剂用于对氯甲苯氨氧化制对氯苯甲腈的反应,反应工艺条件同实施例1,评价结果见表1。
【实施例18】
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液I。
将含0.8mol磷酸的20wt%磷酸溶液中加入约195g SSZ-13纯硅分子筛后加热搅拌至75℃并持续搅拌2h得溶液II。
将溶液I缓慢加入溶液II中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=4.16。
将所得催化剂用于对氯甲苯氨氧化制对氯苯甲腈的反应,反应工艺条件同实施例1,评价结果见表1。
【实施例19】
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液I。
将含0.8mol磷酸的20wt%磷酸溶液中加入50g SSZ-13纯硅分子筛、145g氧化硅后加热搅拌至75℃并持续搅拌2h得溶液II。
将溶液I缓慢加入溶液II中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=4.30。
将所得催化剂用于对氯甲苯氨氧化制对氯苯甲腈的反应,反应工艺条件同实施例1,评价结果见表1。
【实施例20】
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h得到溶液I。
将含0.8mol磷酸的20wt%磷酸溶液中加入145g SSZ-13分子筛、50g氧化硅后加热搅拌至75℃并持续搅拌2h得溶液II。
将溶液I缓慢加入溶液II中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=4.27。
将所得催化剂用于对氯甲苯氨氧化制对氯苯甲腈的反应,反应工艺条件同实施例1,评价结果见表1。
【实施例21】
将0.5mol的五氧化二钒与0.3mol三氧化二铬加入加热至85℃的含2mol草酸的50wt%草酸溶液中,充分搅拌反应2h。在保持搅拌的情况下,加入0.02mol五氧化二铌继续反应1h后在溶液中加入0.08mol硝酸钾、含0.1mol钼的磷钼酸和去离子水并搅拌均匀得到溶液I。
将含0.8mol磷酸的20wt%磷酸溶液中加入约54g SSZ-13分子筛、162g氧化硅后加热搅拌至75℃并持续搅拌2h得溶液II。
将溶液I缓慢加入溶液II中,加热搅拌形成稳定混合溶液并浓缩至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6K
0.08Mo
0.1Nb
0.04。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=4.67。
将所得催化剂用于对氯甲苯氨氧化制对氯苯甲腈,反应工艺条件同实施例1,评价结果见表1。
【对比例1】
将0.5mol的五氧化二钒加入含2mol草酸的50wt%草酸溶液中,充分搅拌,反应2h得含钒溶液。在保持搅拌的状态下顺序加入含0.8mol磷酸的85wt%磷酸,0.08mol的硝酸钾、含0.1mol钼的磷钼酸、0.6mol硝酸铬(分析纯,国药试剂)、0.04mol草酸铌(分析纯,国药试剂)和去离子水,并将215g SBA-15纯硅分子筛在搅拌下慢慢加到上述溶液中,搅拌成稳定混合溶液后并加热蒸发至固含量45%(重量),得粘稠浆料。
将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6K
0.08Mo
0.1Nb
0.04。催化剂XRD谱图见图2。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=3.34。
采用与实施例1相同的评价条件将所得催化剂用于对氯甲苯氨氧化反应,评价结果见表1。
【对比例2】
将0.5mol的五氧化二钒加入含2mol草酸的50wt%草酸溶液中,充分搅拌,反应2h得含钒溶液。在保持搅拌的状态下顺序加入含1.5mol磷酸的85wt%磷酸,0.08mol的硝酸钾、含0.1mol钼的磷钼酸、0.04mol草酸铌和去离子水,并将含200g氧化铝的铝溶胶(试剂级,国药试剂)在搅拌下慢慢加到上述溶液中,搅拌成稳定混合溶液后并加热蒸发至固含量45%(重量),得粘稠浆料。将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
1.5K
0.08Mo
0.1Nb
0.04。
采用与实施例1相同的评价条件将所得催化剂用于对氯甲苯氨氧化反应,评价结果见表1。
【对比例3】
将0.5mol的五氧化二钒和0.3mol三氧化二铬加入含5mol草酸的50wt%草酸溶液中,充分加热至60℃搅拌,反应2h得钒铬溶液。在保持搅拌的状态下顺序加入含0.8mol磷酸的85wt%磷酸、0.08mol的硝 酸钾、含0.1mol钼的磷钼酸、0.04mol草酸铌和去离子水,搅拌1h后将含约215g二氧化硅的硅溶胶在搅拌下慢慢加到上述溶液中,搅拌成稳定混合溶液后加热蒸发至固含量45%(重量),得粘稠浆料。将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体在650℃焙烧5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6.K
0.08Mo
0.1Nb
0.04。
采用与实施例1相同的评价条件将所得催化剂用于对氯甲苯氨氧化反应,评价结果见表1。
【对比例4】
将0.5mol的五氧化二钒和0.3mol三氧化二铬加入含5mol草酸的50wt%草酸溶液中,充分加热至60℃搅拌,反应2h得钒铬溶液。在保持搅拌的状态下顺序加入含0.8mol磷酸的85wt%磷酸和去离子水,搅拌反应1h后将含约50g SSZ-13纯硅分子筛和145g二氧化硅的溶液在搅拌下慢慢加到上述溶液中,搅拌成稳定混合溶液后加热蒸发至固含量45%(重量),得粘稠浆料。将上述浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃预焙烧2小时,然后在650℃焙烧4.5小时,所得催化剂活性组分除O外以原子比组成为:VP
0.8Cr
0.6。
采用与实施例1相同的评价条件将所得催化剂用于对氯甲苯氨氧化反应,评价结果见表1。
表1实施例和对比例所得催化剂的性质和性能
从表1的结果可以看出,根据实施例1-21的本发明催化剂与对比例1-4的催化剂相比,具有显著改善的催化性能,特别是显著提高的产物选择性。此外,对于本发明催化剂而言,选择纯硅分子筛作为载体有利于进一步改善催化剂的卤代芳烃氨氧化活性(参见例如实施例1和8-12等),而选择纯硅分子筛与氧化硅的复合载体则可进一步提高目标产物的选择性(参见例如实施例19-21等)。
【实施例22】
使用实施例1方法制备催化剂,将催化剂用于邻氯甲苯的氨氧化反应,所采用的反应工艺条件为:
邻氯甲苯∶氨∶空气=1∶3.5∶20(摩尔)
负荷0.06h
-1(WWH)
反应压力0.1MPa(表压)
反应温度415℃
考评结果邻氯甲苯转化率98.5%,邻氯苯腈选择性92.6%。
【实施例23】
使用实施例1方法制备催化剂,将催化剂用于间氯甲苯的氨氧化反应,所采用的反应工艺条件为:
间氯甲苯∶氨∶空气=1∶4∶20(摩尔)
负荷0.06h
-1(WWH)
反应压力0.1MPa(表压)
反应温度420℃
考评结果间氯甲苯转化率98.8%,间氯苯腈选择性91.0%。
【实施例24】
使用实施例1方法制备催化剂,将催化剂用于对溴甲苯的氨氧化反应,所采用的反应工艺条件为:
对溴甲苯∶氨∶空气=1∶4∶20(摩尔)
负荷0.06h
-1(WWH)
反应压力0.1MPa(表压)
反应温度405℃
考评结果对溴甲苯转化率98.9%,对溴苯腈选择性89.1%。
【实施例25】
使用实施例1方法制备催化剂,将催化剂用于2,6-二氯甲苯的氨氧化反应,所采用的反应工艺条件为:
2,6-二氯甲苯∶氨∶空气=1∶4∶20(摩尔)
负荷0.06h
-1(WWH)
反应压力0.1MPa(表压)
反应温度415℃
考评结果2,6-二氯甲苯转化率98.0%,2,6-二氯苯腈选择性87.9%。
【实施例26】
使用实施例1方法制备催化剂,将催化剂用于3,4-二氯甲苯的氨氧化反应,所采用的反应工艺条件为:
3,4-二氯甲苯∶氨∶空气=1∶4∶20(摩尔)
负荷0.06h
-1(WWH)
反应压力0.1MPa(表压)
反应温度415℃
考评结果3,4-二氯甲苯转化率98.4%,3,4-二氯苯腈选择性88.6%。
【实施例27】
使用实施例13方法制备催化剂,将催化剂用于2,6-二氯甲苯的氨氧化反应,所采用的反应工艺条件为:
2,6-二氯甲苯∶氨∶空气=1∶4∶20(摩尔)
负荷0.06h
-1(WWH)
反应压力0.1MPa(表压)
反应温度415℃
考评结果2,6-二氯甲苯转化率96.8%,2,6-二氯苯腈选择性87.7%。
【对比例5】
采用中国专利申请公开CN1230465A实施例1所述的方法制备催化剂。将165.7g五氧化二钒加到由360ml水和345g草酸组成的溶液中,充分搅拌,得草酸钒溶液。695.5g草酸和450ml水溶液在50-60℃下慢慢加入182.2g氧化铬(分析纯,国药试剂),搅拌得草酸铬溶液。将草酸钒溶液和草酸铬溶液在50-60℃混合,得钒铬溶液。在1L水中加160.6g钼酸铵(分析纯,国药试剂),105g 85%磷酸混合得钼磷溶液。将钒铬溶液和钼磷溶液充分混合,并加入含40%二氧化硅的硅溶胶1250g,搅拌加热,蒸发至固含量38%得浆料。将浆料喷雾成型得催化剂。所得催化剂活性组分除O外以原子比组成为:V
1Cr
1P
0.5Mo
0.5。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=3.05。
将催化剂用于对氯甲苯的氨氧化反应,采用与本发明实施例1相同的反应工艺条件进行考评,考评结果为对氯甲苯转化率90.1%,对氯 苯甲腈选择性82.5%。
【对比例6】
采用对比例5所制备催化剂,将其用于邻氯甲苯的氨氧化反应,反应工艺条件与实施例22相同,考评结果为邻氯甲苯转化率87.9%,邻氯苯甲腈选择性80.2%。
【对比例7】
采用对比例5所制备催化剂,将其用于2,6-二氯甲苯的氨氧化反应,反应工艺条件与实施例25相同,考评结果为2,6-二氯甲苯转化率88.6%,2,6-二氯苯甲腈选择性78.5%。
【对比例8】
采用中国专利申请公开CN1187320C实施例1所述的方法制备催化剂。将224g五氧化二钒加到由490ml水和468g草酸组成的温度80-90℃的溶液中,充分搅拌,反应得草酸钒溶液。将重量百分浓度为40%二氧化硅的硅溶胶1250g在搅拌下慢慢加到上述溶液中,然后分别加入由864g硝酸铬、12.4g硝酸钾、71.6g硝酸钴(分析纯,国药试剂)和500ml水组成的溶液,76.4g硼酸(分析纯,国药试剂)、85.1g 85%磷酸和500ml水组成的溶液及43.5g钼酸铵和100ml水组成的溶液,搅拌,加热蒸发至固含量40%得粘稠浆料。将浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃焙烧2h,然后在650℃焙烧4.5h,得活性催化剂。所得催化剂活性组分除O外以原子比组成为:V
1Cr
0.9B
0.5P
0.3Mo
0.1Co
0.1K
0.05。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=3.12。
将其用于2,6-二氯甲苯的氨氧化反应,反应工艺条件与实施例25相同,考评结果为2,6-二氯甲苯转化率92.6%,2,6-二氯苯甲腈选择性80.5%。
【对比例9】
采用中国专利申请公开CN1223579C实施例1所述的方法制备催化剂。将224g五氧化二钒加到由490ml水和468g草酸组成的温度80-90 ℃的溶液中,充分搅拌,反应得草酸钒溶液。将重量百分浓度为40%二氧化硅的硅溶胶1250g在搅拌下慢慢加到上述溶液中,然后分别加入由864g硝酸铬、12.4g硝酸钾和500ml水组成的溶液,76.4g硼酸、85.1g 85%磷酸和500ml水组成的溶液及43.5g钼酸铵和100ml水组成的溶液,搅拌,加热蒸发至固含量40%得粘稠浆料。将浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体于300℃焙烧2h,然后在650℃焙烧5h,得活性催化剂。所得催化剂活性组分除O外以原子比组成为:V
1Cr
0.9B
0.5P
0.3Mo
0.1K
0.05。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=3.03。
将其用于2,6-二氯甲苯的氨氧化反应,反应工艺条件与实施例25相同,考评结果为2,6-二氯甲苯转化率90.7%,2,6-二氯苯甲腈选择性80.7%。
【对比例10】
采用中国专利申请公开CN1252043C实施例1所述的方法制备催化剂。将224g五氧化二钒加到由490ml水和468g草酸组成的温度80-90℃的溶液中,充分搅拌,反应得草酸钒溶液。将重量百分浓度为40%二氧化硅的硅溶胶1250g在搅拌下慢慢加到上述溶液中,然后分别加入由886g硝酸铬和300ml水组成的溶液,76.3g硼酸和560ml水组成的溶液及85g 85%磷酸和50ml水组成的溶液,最后加入含24.9g硝酸钾的水溶液20ml,搅拌,加热蒸发至固含量40%得粘稠浆料。将浆料在喷雾干燥器中喷雾干燥成形,成形后的催化剂前体在650℃焙烧5h,得活性催化剂。所得催化剂活性组分除O外以原子比组成为:V
1Cr
0.9B
0.5P
0.3K
0.1。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=2.72。
将其用于2,6-二氯甲苯的氨氧化反应,反应工艺条件与实施例25相同,考评结果为2,6-二氯甲苯转化率93.5%,2,6-二氯苯甲腈选择性74.2%。
【对比例11】
将201g五氧化二钒加到3000ml水和420g草酸组成的温度为80-90℃的溶液中,充分搅拌,反应得到草酸钒溶液。将含40wt%二氧化硅 的硅溶胶1250g在搅拌下缓慢加入前述溶液,然后分别加入由798g硝酸铬和900ml水组成的溶液,68.6g硼酸和560ml水组成的溶液,以及273g钼酸铵和200ml水组成的溶液,磷酸溶液0.11mol,最后加入11g硝酸钾和30ml水组成的溶液,搅拌混合,加热蒸发至固含量35wt%,得粘稠浆料。将浆料喷雾成形,成形后的催化剂于120℃下干燥12h,550℃焙烧8h,得活性催化剂。所得催化剂活性组分除O外以原子比组成为:V
1Cr
0.9B
0.5P
0.05Mo
0.45K
0.05。催化剂XRD衍射测试在2θ=27.8°处衍射峰峰高(I
1)和2θ=13.8°处的衍射峰峰高(I
2)比例I
1∶I
2=2.89。
将其用于2,6-二氯甲苯的氨氧化反应,反应工艺条件与实施例25相同,考评结果为2,6-二氯甲苯转化率88.6%,2,6-二氯苯腈选择性81.2%。
表2实施例和对比例所得催化剂的性质和性能
从表2的数据可以看出,现有技术中已知的诸多催化剂在通用性上略显不足,应用于某些卤代芳烃时显示出较低的催化活性(转化率)和选择性。相比之下,根据本发明实施例的催化剂具有更好的通用性, 在各种不同卤代芳烃的氨氧化反应中都显示出良好的催化活性和选择性。
在上文的说明书中,已经参照特定的实施方式描述了本发明的构思。然而,本领域技术人员可以理解,在不脱离所附的权利要求中限定的本发明范围的情况下可以做出各种修改和变更。因此,说明书和附图应认为是说明性的,而不是限制性的,并且所有这类修改和变更应当涵盖在本发明的范围之内。
可以理解,本文为清楚起见以独立的多个实施方式的形式描述的某些特征也可以作为组合提供在单一的实施方式中。相反,为简要起见以单一实施方式的形式描述的多个不同特征也可以单独地或以任何子组合的形式提供。
Claims (18)
- 一种催化剂,其适合用作生产卤代芳腈的流化床催化剂,所述催化剂包括活性组分和载体,所述活性组分为以原子比计具有如下组成的复合物:VP aCr bA cM dO x其中:A代表选自碱金属和碱土金属中的至少一种金属,优选选自碱金属中的至少一种;M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种;a的取值范围为0-1.5;b的取值范围为0.1-1;c的取值范围为0-0.5;d的取值范围为0-1;x为满足所述活性组分中各元素化合价所需的氧原子数;所述载体选自氧化硅和分子筛,其中在所述催化剂的XRD衍射图谱中,在2θ=27.8±0.5°和2θ=13.8±0.5°处具有衍射峰,并且在2θ=27.8±0.5°处的衍射峰峰高(I 1)和2θ=13.8±0.5°处的衍射峰峰高(I 2)的比例I 1∶I 2为3.5-6。
- 如权利要求1所述的催化剂,其中a的取值范围为0.5-1.5,且c的取值范围为0.01-0.5;优选地,a的取值范围为0.5-1,b的取值范围为0.1-0.7,c的取值范围为0.01-0.3,且d的取值范围为0.01-0.5。
- 如权利要求1或2所述的催化剂,其中所述载体为纯硅分子筛,优选地所述纯硅分子筛选自MCM-41、MCM-48、SBA-1、SBA-2、SBA-15、SBA-16、MSU、Silicate-1、SSZ-13和HMS中的一种或多种。
- 如权利要求1或2所述的催化剂,其中所述载体为由纯硅分子筛和氧化硅组成的复合载体,其中所述纯硅分子筛与氧化硅的重量比为1∶9至9∶1,优选1∶4至4∶1;特别优选地,所述复合载体中的纯硅分子筛为SSZ-13分子筛。
- 如权利要求1-4中任一项所述的催化剂,其中所述催化剂可通过包括如下步骤的方法制备得到:1)将含钒原料和含铬原料溶于酸后与含M原料的溶液混合得到第一混合溶液;2)将含磷原料、水和载体混合反应得到第二混合溶液;3)将第一混合溶液和第二混合溶液合并并浓缩后得到混合浆料;以及4)将混合浆料干燥、焙烧后得到最终催化剂。
- 如权利要求5所述的催化剂,其中所述催化剂可通过包括如下步骤的方法制备得到:1)将一定量的含钒原料和含铬原料溶于加热的酸溶液中,并分别加入除含磷原料以外的助催化元素原料并加热搅拌制成第一混合溶液;2)在磷酸水溶液中加入载体并充分加热搅拌制成第二混合溶液;3)将第一混合溶液缓慢加入第二混合溶液中并进行搅拌浓缩得到一定固含量的混合浆料;以及4)将混合浆料通过干燥成型得催化剂前体,将催化剂前体焙烧后得到最终催化剂,优选地,步骤4)中催化剂前体依次在300-350℃预焙烧和500-700℃焙烧活化得最终催化剂。
- 如权利要求5-6中任一项所述的催化剂,其中所述含钒原料选自五氧化二钒、偏钒酸铵、硫酸钒和有机酸钒;所含铬原料选自三氧化二铬和可通过焙烧转化为铬氧化物的化合物;所述酸选自草酸;所述含M原料选自M的氧化物、硝酸盐或其它可溶性化合物;且所述含磷原料选自五氧化二磷、磷钼酸和磷钨酸。
- 一种制备催化剂的方法,所述催化剂适合用作生产卤代芳腈的流化床催化剂,其包括活性组分和载体,所述活性组分为以原子比计具有如下组成的复合物:VP aCr bA cM dO x其中:A代表选自碱金属和碱土金属中的至少一种金属,优选选自碱金属中的至少一种;M代表选自Ti、Zr、Hf、La、Ce、Nb、Mo、W、Co、Zn、Fe、Ni、B、Sb、Bi、As、Ga、Ge、Sn和In中的至少一种;a的取值范围为0-1.5;b的取值范围为0.1-1;c的取值范围为0-0.5;d的取值范围为0-1;x为满足所述活性组分中各元素化合价所需的氧原子数;所述载体选自氧化硅和分子筛,所述方法包括如下步骤:1)将含钒原料和含铬原料溶于酸后与含M原料的溶液混合得到第一混合溶液;2)将含磷原料、水和载体混合反应得到第二混合溶液;3)将第一混合溶液和第二混合溶液合并并浓缩后得到混合浆料;以及4)将混合浆料干燥、焙烧后得到最终催化剂。
- 如权利要求8所述的方法,其中所述方法包括如下步骤:1)将一定量的含钒原料和含铬原料溶于加热的酸溶液中,并分别加入除含磷原料以外的助催化元素原料并加热搅拌制成第一混合溶液;2)在磷酸水溶液中加入载体并充分加热搅拌制成第二混合溶液;3)将第一混合溶液缓慢加入第二混合溶液中并进行搅拌浓缩得到一定固含量的混合浆料;以及4)将混合浆料通过干燥成型得催化剂前体,将催化剂前体焙烧后得到最终催化剂,优选地,步骤4)中催化剂前体依次在300-350℃预焙烧和500-700℃焙烧活化得最终催化剂。
- 如权利要求8-9中任一项所述的方法,其中在所述催化剂的XRD衍射图谱中,在2θ=27.8±0.5°和2θ=13.8±0.5°处具有衍射峰,并且在2θ=27.8±0.5°处的衍射峰峰高(I 1)和2θ=13.8±0.5°处的衍射峰峰高(I 2)的比例I 1∶I 2为3.5-6。
- 如权利要求8-10中任一项所述的方法,其中a的取值范围为0.5-1.5,且c的取值范围为0.01-0.5;优选地,a的取值范围为0.5-1,b的取值范围为0.1-0.7,c的取值范围为0.01-0.3,且d的取值范围为0.01-0.5。
- 如权利要求8-11中任一项所述的方法,其中所述载体为纯硅分子筛,优选地所述纯硅分子筛选自MCM-41、MCM-48、SBA-1、 SBA-2、SBA-15、SBA-16、MSU、Silicate-1、SSZ-13和HMS中的一种或多种。
- 如权利要求8-11中任一项所述的方法,其中所述载体为由纯硅分子筛和氧化硅组成的复合载体,其中所述纯硅分子筛与氧化硅的重量比为1∶9至9∶1,优选1∶4至4∶1;特别优选地,所述复合载体中的纯硅分子筛为SSZ-13分子筛。
- 如权利要求8-13中任一项所述的催化剂,其中所述含钒原料选自五氧化二钒、偏钒酸铵、硫酸钒和有机酸钒;所含铬原料选自三氧化二铬和可通过焙烧转化为铬氧化物的化合物;所述酸选自草酸;所述含M原料选自M的氧化物、硝酸盐或其它可溶性化合物;且所述含磷原料选自五氧化二磷、磷钼酸和磷钨酸。
- 按照权利要求8-14中任一项所述的方法制备得到的催化剂。
- 权利要求1-7和15中任一项所述的催化剂用作生产卤代芳腈的流化床催化剂的用途。
- 一种生产卤代芳腈的方法,包括使卤代芳烃与权利要求1-7和15中任一项所述的催化剂接触反应的步骤,优选地,所述卤代芳腈选自邻氯苯甲腈、间氯苯甲腈、对氯苯甲腈、邻溴苯甲腈、间溴苯甲腈、对溴苯甲腈、二氯苯甲腈和二溴苯甲腈中的一种或多种。
- 如权利要求17所述的方法,其中所述接触反应在不存在溴乙烷的条件下进行。
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