CN113117741B - Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst - Google Patents
Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst Download PDFInfo
- Publication number
- CN113117741B CN113117741B CN202110242347.7A CN202110242347A CN113117741B CN 113117741 B CN113117741 B CN 113117741B CN 202110242347 A CN202110242347 A CN 202110242347A CN 113117741 B CN113117741 B CN 113117741B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zinc
- soluble
- salt
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/26—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydration of carbon-to-carbon triple bonds
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种磷酸铝锌分子筛催化剂的制备方法及其应用，包括如下步骤：(1)把正磷酸加到去离子水中，接着加入可溶性锆盐或可溶性钛盐和分散剂，边搅拌边加热到50‑60℃，然后加入可溶性锌盐，待可溶性锌盐全部溶解后，接着加入拟薄水铝石，搅拌均匀后加入模板剂，并用稀盐酸调节pH为5‑6，连续搅拌形成均匀的胶状物；(2)把上述胶状物移入均相反应釜，边搅拌边老化，接着升温进行恒温晶化反应，得到晶化产物；(3)将上述晶化产物经洗涤和过滤后，干燥后移入煅烧炉，升温到550‑600℃，恒温4‑6h，得到分子筛原粉；(4)将上述分子筛原粉加入到已添加10‑20％铝溶胶的水溶液中，进一步制得磷酸铝锌分子筛催化剂。本发明具有工艺过程简单，生产成本低，安全环保及适合工业规模化生产等优点。The invention discloses a preparation method and application of an aluminum-zinc phosphate molecular sieve catalyst, comprising the following steps: (1) adding orthophosphoric acid to deionized water, then adding soluble zirconium salt or soluble titanium salt and a dispersant, and stirring while Heating to 50-60°C, then adding soluble zinc salt, after all the soluble zinc salt is dissolved, then adding pseudo-boehmite, stirring evenly, adding template agent, and adjusting the pH to 5-6 with dilute hydrochloric acid, stirring continuously to form a uniform (2) move the above-mentioned colloid into a homogeneous reaction kettle, age while stirring, then heat up to carry out a constant-temperature crystallization reaction to obtain a crystallized product; (3) after the above-mentioned crystallized product is washed and filtered , after drying, move it into a calcining furnace, heat up to 550-600 ° C, and keep the constant temperature for 4-6 h to obtain the molecular sieve raw powder; (4) adding the above molecular sieve raw powder to the aqueous solution to which 10-20% aluminum sol has been added to further prepare phosphoric acid Aluminum-zinc molecular sieve catalyst. The invention has the advantages of simple technological process, low production cost, safety and environmental protection, and suitability for industrial scale production.
Description
Technical Field
The invention belongs to the technical field of acetylene catalytic conversion, and particularly relates to a preparation method and application of an aluminum-zinc phosphate molecular sieve catalyst.
Background
Acetaldehyde is a basic chemical raw material, and the application industries comprise pesticides, medicines, food additives, paints, oil products, preservatives and the like. In recent years, downstream products of acetaldehyde are rapidly developed, market demands of acetaldehyde are strongly pulled, and therefore researches on production process routes of acetaldehyde are more and more focused. The synthesis process route of acetaldehyde mainly comprises an ethylene oxidation method, an ethanol dehydrogenation method, an ethanol oxidation method and an acetylene hydration method. The development of processes for the production of acetaldehyde by the direct oxidation of ethylene in the 50's of the 20 th century has made the direct oxidation of ethylene to acetaldehyde a more attractive process in developed countries due to the lower cost and ready availability of ethylene as compared to acetylene. Both the ethanol method and the ethylene method exist in China. With the continuous innovation of the technology for producing acetylene by petroleum and natural gas, the optimization of the acetylene production process by the calcium carbide method, the raw material valence difference of acetylene and ethylene is gradually reduced, and the route for producing acetaldehyde by acetylene hydration is more and more concerned. The breakthrough of the large-scale thermal plasma coal-to-acetylene technology further expands the acetylene production capacity. As a country with rich coal resources, China makes it possible for the acetylene hydration method to become an advantageous route of the acetaldehyde production industry in China.
Acetylene hydration reactions can be divided into gas-solid phase catalytic systems and gas-liquid phase catalytic systems according to the difference of reaction systems. Early researchers studied transition metals (e.g., Cu)2+、Cd2+、Hg2+、Ag+、Ru2+And Zn2+). As an active catalyst in acetylene hydration reactions; it was investigated to use mercury salts and acids as catalysts under liquid phase strongly acidic conditions or cadmium phosphate-calcium phosphate or the like catalysts under gas phase conditions, although both methods showed high activity, Hg2+、Cu2+And Ag+Are more likely to be reduced by acetylene to the respective zero-valent metal, resulting in a reduction in catalyst activity, while the catalysts involved are toxic, thereby limiting their use. Therefore, from the aspects of reaction activity, economic factors, environmental factors and the like, the active zinc is an ideal active ingredient for replacing cadmium in the acetylene hydration process.
In recent years, there have been reports of chemical impregnation methods for preparing Zn/NH2MCM-41 load type catalyst, or zinc salt is loaded on treated calcium phosphate by ion exchange method, or CdAPO-5/ZAPO-5 catalyst synthesized by hydrothermal method is used for producing acetaldehyde by acetylene gas phase hydration. The technical proposal disclosed in CN108993576A adopts zinc salt to dip on the modified molecular sieve to prepare the solid-supported zinc-based catalyst for gas phase hydration reaction, and the technical proposal disclosed in CN111185222A discloses methods of plasma post-treatment and the like for the supported zinc-based catalyst, aiming at enhancing the interaction between ZnO and the carrierThe dispersion of active components is promoted, the loss of Zn species is inhibited, and the conversion rate and the selectivity are improved. Recent studies found that the cationic sites are more active than negatively charged groups in acetylene hydration reactions, while researchers characterized the surface acid centers of the catalyst and suggested by XPS analysis that zn (oh) + might be an active compound. Despite the findings obtained by these prior arts, the reaction mechanism at the molecular level is not theoretically studied, limiting the overall understanding of the reaction.
In summary, although the currently studied acetylene gas phase hydration reaction adopts a non-Cd-based or Hg-based catalyst to avoid the problem of environmental safety, the reaction of the transition metal ion catalyst at high temperature has the problems of high energy consumption, poor conversion rate and selectivity and the like, and the frequent regeneration step is required for recovering the catalytic activity of the catalyst due to the carbon deposition inactivation of the catalyst. In order to meet the requirements of industrialization, optimization and improvement of the catalyst are necessary. Therefore, the development of a high-efficiency high-selectivity stable catalyst and the realization of the stable production of acetaldehyde by acetylene gas phase hydration are of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an aluminum-zinc phosphate molecular sieve catalyst.
The invention also aims to provide application of the aluminum zinc phosphate molecular sieve catalyst.
The technical scheme of the invention is as follows:
a preparation method of an aluminum-zinc phosphate molecular sieve catalyst comprises the following steps:
(1) adding 85% orthophosphoric acid by mass into deionized water, then adding soluble zirconium salt or soluble titanium salt and a dispersing agent, heating to 50-60 ℃ while stirring, then adding soluble zinc salt, adding pseudo-boehmite after the soluble zinc salt is completely dissolved, adding a template agent after stirring uniformly, adjusting the pH to 5-6 by using dilute hydrochloric acid, and continuously stirring to form uniform jelly;
(2) transferring the jelly into a homogeneous reaction kettle, aging for 6-8h at 80-100 ℃ while stirring, and then heating to 160-180 ℃ for carrying out constant temperature crystallization reaction for 24-36h to obtain a crystallized product;
(3) washing and filtering the crystallized product, drying at the temperature of 100-120 ℃ for 6-8h, then transferring into a calcining furnace, heating to the temperature of 550-600 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 4-6h to obtain molecular sieve raw powder;
(4) adding the molecular sieve raw powder into an aqueous solution added with 10-20% of aluminum sol, grinding the mixture into microemulsion by a wet method, wherein the mass ratio of the molecular sieve raw powder to the aqueous solution is 1:2-3, and then carrying out spray granulation to obtain the aluminum-zinc phosphate molecular sieve catalyst with the particle size of 50-150 mu m.
In a preferred embodiment of the invention, the active ingredient of the jelly is aZnO- (1-a) Al2O3-P2O5-bN-cH2O, wherein: a is ZnO and P2O5A is 0.15 to 0.35; b is a template agent and P2O5B is 1.0 to 1.5; c is H2O and P2O5C is 35 to 50; ZrO (ZrO)2Or TiO2The content of the molecular sieve is 3-5wt% of the raw powder of the molecular sieve; the dispersing agent is hydroxypropyl cellulose or hydroxymethyl cellulose, and the addition amount of the dispersing agent is 1-2wt% of the jelly.
In a preferred embodiment of the invention, the soluble zirconium salt is zirconium nitrate or zirconium oxychloride; the soluble titanium salt is titanium sulfate or titanyl sulfate; the soluble zinc salt is zinc acetate or zinc nitrate.
Further preferably, the template agent is triethylamine or tetrapropylammonium hydroxide.
A method for preparing acetaldehyde by acetylene hydration adopts the aluminum-zinc phosphate molecular sieve catalyst prepared by the preparation method and is carried out in a fluidized bed reaction device, the reaction temperature is 400-440 ℃, the reaction pressure is normal pressure, the reaction atmosphere is inert gas or nitrogen atmosphere, the molar ratio of water to acetylene is 2-5, and the space velocity of acetylene is 100-300h-。
The other technical scheme of the invention is as follows:
a preparation method of an aluminum-zinc phosphate molecular sieve catalyst comprises the following steps:
(1) adding 85% orthophosphoric acid by mass into deionized water, then adding soluble zirconium salt or soluble titanium salt and a dispersing agent, heating to 50-60 ℃ while stirring, then adding soluble zinc salt, adding pseudo-boehmite after the soluble zinc salt is completely dissolved, adding a template agent after stirring uniformly, adjusting the pH to 5-6 by using dilute hydrochloric acid, and continuously stirring to form uniform jelly;
(2) transferring the jelly into a homogeneous reaction kettle, aging for 6-8h at 80-100 ℃ while stirring, and then heating to 160-180 ℃ for carrying out constant temperature crystallization reaction for 24-36h to obtain a crystallized product;
(3) washing and filtering the crystallized product, drying at the temperature of 100-120 ℃ for 6-8h, then transferring into a calcining furnace, heating to the temperature of 550-600 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 4-6h to obtain molecular sieve raw powder;
(4) adding the molecular sieve raw powder into an aqueous solution added with 10-20% of alumina sol, putting the mixture into a kneading machine, mixing and grinding the mixture into plastic material masses, extruding the plastic material masses into strips and cutting the strips and the particles into particles to obtain a catalyst precursor with the length of 10-15mm and the diameter of 1-3mm, wherein the mass ratio of the molecular sieve raw powder to the aqueous solution is 1: 1-1.5;
(5) drying the catalyst precursor at the temperature of 100-120 ℃ for 6-8h, then transferring the catalyst precursor into a calcining furnace, heating to the temperature of 500-550 ℃ at the speed of 5-10 ℃/h, and preserving the heat for 4-6h to obtain the aluminum-zinc phosphate molecular sieve catalyst.
In a preferred embodiment of the invention, the active ingredient of the jelly is aZnO- (1-a) Al2O3-P2O5-bN-cH2O, wherein: a is ZnO and P2O5A is 0.15 to 0.35; b is a template agent and P2O5B is 1.0 to 1.5; c is H2O and P2O5C is 35 to 50; ZrO (ZrO)2Or TiO2The content of the molecular sieve is 3-5wt% of the raw powder of the molecular sieve; the dispersing agent is hydroxypropyl cellulose or hydroxymethyl cellulose, and the addition amount of the dispersing agent is 1-2wt% of the jelly.
In a preferred embodiment of the invention, the soluble zirconium salt is zirconium nitrate or zirconium oxychloride; the soluble titanium salt is titanium sulfate or titanyl sulfate; the soluble zinc salt is zinc acetate or zinc nitrate.
Further preferably, the template agent is triethylamine or tetrapropylammonium hydroxide.
A method for preparing acetaldehyde by acetylene hydration adopts the aluminum-zinc phosphate molecular sieve catalyst prepared by the preparation method and is carried out in a fixed bed reaction device, the reaction temperature is 400-440 ℃, the reaction pressure is normal pressure, the reaction atmosphere is inert gas or nitrogen atmosphere, the molar ratio of water to acetylene is 2-5, and the space velocity of acetylene is 100-300h-。
The invention has the beneficial effects that:
1. the invention has the advantages of simple process, low production cost, safety, environmental protection, suitability for industrial large-scale production and the like, is suitable for a fluidized bed reactor (on-line continuous on-line regeneration) and a fixed bed reactor (different reactors can be alternately regenerated).
2. The zinc-based catalyst adopting the aluminum-zinc phosphate molecular sieve (ZAPO-5) is prepared by the invention, and the environmental safety problem caused by Cd-based and Hg-based catalysts is solved.
3. The catalyst prepared by the invention adopts titanium oxide or zirconium oxide as a stabilizing auxiliary agent, maintains the physical property structure of the molecular sieve, weakens the strong acid sites on the surface of the carrier, thereby inhibiting the generation speed of carbon deposit, enhancing the interaction between ZnO and the carrier, promoting the dispersion of active components, inhibiting the loss of Zn species, and improving the selectivity and high-temperature stability of the catalyst.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) 19.6g of 85% by weight orthophosphoric acid were first added to 72.00g of deionized water, followed by 2.48 g of zirconium nitrate (Zr (NO)3)4·5H2O), adding 1.50g of hydroxypropyl cellulose, and heating to 50 ℃ while stirring; 5.95g of zinc nitrate (Zn (NO) was added thereto3)2·6H2O), after the zinc salt is completely dissolved, 14.61g of pseudo-foil is slowly addedDiaspore (Al)2O3Content 60 wt%), stirring well, adding 10.12g triethylamine, adjusting pH to 5.5 with dilute hydrochloric acid, and continuously stirring to form a uniform jelly;
(2) transferring the obtained jelly into a homogeneous reaction kettle, aging at 100 ℃ for 6h, and after aging, heating to 180 ℃ for constant-temperature crystallization reaction for 36h to obtain a crystallized product;
(3) and washing and filtering the obtained crystallized product, drying at 100 ℃ for 6h, transferring into a calcining furnace, heating to 550 ℃ at the speed of 10 ℃/h, and keeping the temperature for 4h to obtain the molecular sieve raw powder.
(4) Adding the molecular sieve raw powder into an aqueous solution added with 10-20% of aluminum sol, uniformly mixing, putting into a kneading machine, mixing and grinding into a plastic material mass, extruding strips and cutting into granules to obtain a catalyst precursor with the length of 10-15mm and the diameter of 1-3mm, wherein the mass ratio of the molecular sieve raw powder to the aqueous solution is 1: 1;
(5) drying the catalyst precursor at 100 deg.C for 6h, transferring into a calcining furnace, heating to 500 deg.C at a rate of 10 deg.C/h, and maintaining the temperature for 4h to obtain the formed aluminum-zinc phosphate molecular sieve catalyst, i.e. Zr-ZAPO-5(0.2) -1 catalyst, wherein (0.2) is labeled with ZnO/P2O5Is 0.2.
(6) 5g of the prepared Zr-ZAPO-5(0.2) -1 catalyst is put into a fixed bed reactor, the temperature is raised to 420 ℃ at the speed of 5-20 ℃/h under the normal pressure, the inert atmosphere or the nitrogen atmosphere, acetylene is introduced into the fixed bed reactor at the airspeed of 150h, the water/acetylene molar ratio is adjusted to be 3, and the constant temperature reaction is carried out for 8h at 420 ℃.
Example 2
Preparation of an aluminophosphate zinc molecular sieve catalyst is similar to example 1 except that 5.95g of zinc nitrate (Zn (NO) was added in step (1) of example 13)2·6H2O) instead, 3.67g of zinc acetate (Zn (CH)3COO)2) The Zr-ZAPO-5(0.2) -2 catalyst can be prepared by other steps and conditions without changing, (0.2) marked ZnO/P2O5Is 0.2.
Example 3
The preparation of the aluminophosphate zinc molecular sieve catalyst is similar to that of example 1,except that 2.48 zirconium nitrate (Zr (NO) was added in step (1) of example 13)4·5H2O), 1.52g of zirconium oxychloride (Cl) was added instead2OZr), the Zr-ZAPO-5(0.2) -3 catalyst can be prepared by other steps and conditions, and the ZnO/P marked (0.2) is2O5Is 0.2.
Example 4
The preparation method of the aluminum zinc phosphate molecular sieve catalyst is similar to that of example 1, except that 10.12g of triethylamine is added in the step (1) in the example 1, 20.33g of tetrapropylammonium hydroxide is added, and the Zr-ZAPO-5(0.2) -4 catalyst and the labeled ZnO/P (0.2) are obtained under the same steps and conditions2O5Is 0.2.
Example 5
Preparation of an aluminophosphate zinc molecular sieve catalyst is similar to example 1, except that zirconium nitrate (Zr (NO) is obtained in step (1) of example 13)4·5H2Changing O) to titanium sulfate (Ti (SO)4)2·8H2O), weighing 2.14g, and preparing the Ti-ZAPO-5(0.2) catalyst by other steps and conditions, wherein the ZnO/P is marked by (0.2)2O5Is 0.2.
Example 6
Preparation of an aluminophosphate zinc molecular sieve catalyst is similar to example 1, except that zirconium nitrate (Zr (NO) is obtained in step (1) of example 13)4·5H2O) is changed into titanyl sulfate (TiOSO 4. XH2SO 4. 8H2O), the Ti-ZAPO-5(0.2) catalyst and (0.2) marked ZnO/P are prepared by weighing 1.43g of titanium and keeping other steps and conditions unchanged2O5Is 0.2.
Example 7
Preparation of an aluminophosphate zinc molecular sieve catalyst is similar to example 1, except that the zinc nitrate (Zn (NO) of step (1) in example 1 is used3)2·6H2O) is changed to 8.92g, and the addition amount of the pseudo-boehmite (Al) is changed to2O360 wt%) of the catalyst is changed into 11.89g, and other steps and conditions are not changed, thus obtaining the Zr-ZAPO-5(0.3) catalyst, (0.3) marked ZnO/P2O5Is 0.3.
Example 8
Preparation of an aluminophosphate zinc molecular sieve catalyst is similar to example 1, except that the zinc nitrate (Zn (NO) of step (1) in example 1 is used3)2·6H2O) is changed to 4.46g, and pseudo-boehmite (Al)2O3Content of 60 wt%) was changed to 14.44g, and other steps and conditions were not changed to obtain Zr-ZAPO-5(0.15) catalyst, and ZnO/P (0.15) was labeled2O5Is 0.15.
Example 9
Preparation of an aluminophosphate zinc molecular sieve catalyst is similar to example 1, except that the zinc nitrate (Zn (NO) of step (1) in example 1 is used3)2·6H2O) is changed to 10.41g, and the addition amount of the pseudo-boehmite (Al) is changed to 10.41g2O360 wt%) of the catalyst was changed to 11.04g, and the other steps and conditions were not changed to obtain Zr-ZAPO-5(0.35) catalyst, and ZnO/P (0.35) was labeled2O5Is 0.35.
Example 10
The preparation method of the aluminophosphate zinc molecular sieve catalyst is similar to that of example 1, except that the reaction temperature of step (5) in example 1 was changed to 440 ℃.
Example 11
(1) 19.6g of 85% by weight orthophosphoric acid were first added to 72.00g of deionized water, followed by 2.48 g of zirconium nitrate (Zr (NO)3)4·5H2O), adding 1.50g of hydroxypropyl cellulose, and heating to 50 ℃ while stirring; 5.95g of zinc nitrate (Zn (NO) was added thereto3)2·6H2O), after the zinc salt is completely dissolved, 14.61g of pseudo-boehmite (Al) is slowly added2O3Content 60 wt%), stirring well, adding 10.12g triethylamine, adjusting pH to 5.5 with dilute hydrochloric acid, and continuously stirring to form a uniform jelly;
(2) transferring the obtained jelly into a homogeneous reaction kettle, aging at 100 ℃ for 6h, and after aging, heating to 180 ℃ for constant-temperature crystallization reaction for 36h to obtain a crystallized product;
(3) and washing and filtering the obtained crystallized product, drying at 100 ℃ for 6h, transferring into a calcining furnace, heating to 550 ℃ at the speed of 10 ℃/h, and keeping the temperature for 4h to obtain the molecular sieve raw powder.
(4) Adding the molecular sieve raw powder into an aqueous solution added with 10-20% of aluminum sol, grinding the mixture into microemulsion by a wet method, wherein the mass ratio of the molecular sieve raw powder to the aqueous solution is 1:2-3, and then carrying out spray granulation to obtain the Zr-ZAPO-5(0.2, microsphere) catalyst with the particle size of 50-150 mu m.
(5) 5g of the prepared Zr-ZAPO-5(0.2, microsphere) catalyst is put into a fluidized reactor, inert gas or nitrogen is used for heating to 420 ℃ at the speed of 5-20 ℃/h, and the space velocity of acetylene is controlled for 150h-Adjusting the water/acetylene molar ratio to be 3, reacting at the constant temperature of 420 ℃ for 8 hours under the normal pressure.
Comparative example 1
The catalyst was prepared in a similar manner to example 1, except that zirconium nitrate (Zr (NO) was not added as a stabilizing additive in step (1) of example 13)4·5H2O), the ZAPO-5(0.2) catalyst can be prepared by other steps and conditions, and ZnO/P is marked by (0.2)2O5Is 0.2.
Comparative example 2
The catalyst was prepared in a similar manner to example 1, except that zirconium nitrate (Zr (NO) was not added as a stabilizing additive in step (1) of example 13)4·5H2O), zinc nitrate (Zn (NO)3)2·6H2Changing O) into cadmium nitrate (Cd (NO)3)2) The adding amount is 4.72 g; the other steps and conditions are not changed to prepare the CdAPO-5(0.2) catalyst, and the CdO/P is marked (0.2)2O5Is 0.2.
Comparative example 3
The preparation method of the catalyst is similar to that of example 1, except that the Zr-ZAPO-5(0.2) catalyst of example 1 is reacted for 24h, replaced by nitrogen and then regenerated for 12h by introducing air at 550 ℃ to obtain the regenerated catalyst Zr-ZAPO-5(0.2, R).
The specific results of the activity evaluation of the above examples and comparative examples are shown in table 1 below:
TABLE 1 evaluation results of acetaldehyde preparation by acetylene hydration reaction
| Conversion of acetylene | Acetaldehyde selectivity | Crotonaldehyde | Selectivity to acetone | Others | |
| Example 1 | 49.5％ | 95.1％ | 2.6％ | 1.1％ | 1.2％ |
| Example 2 | 50.1％ | 95.0％ | 2.5％ | 1.2％ | 1.3％ |
| Example 3 | 49.3％ | 94.6％ | 3.0％ | 1.2％ | 1.2％ |
| Example 4 | 50.5％ | 95.5％ | 3.0％ | 1.2％ | 1.0％ |
| Example 5 | 44.2％ | 95.2％ | 2.5％ | 1.1％ | 1.1％ |
| Example 6 | 44.8％ | 93.8％ | 2.9％ | 2.0％ | 1.3％ |
| Example 7 | 50.2％ | 95.8％ | 2.2％ | 1.0％ | 1.0％ |
| Example 8 | 39.5％ | 93.6％ | 2.6％ | 1.9％ | 1.9％ |
| Example 9 | 48.6％ | 95.3％ | 2.6％ | 1.3％ | 0.8％ |
| Example 10 | 65.1％ | 93.3％ | 2.2％ | 2.5％ | 2.0％ |
| Example 11 | 45.6％ | 96.8％ | 1.9％ | 0.8％ | 0.5％ |
| Comparative example 1 | 40.5％ | 93.6％ | 3.3％ | 2.0％ | 1.1％ |
| Comparative example 2 | 78.6％ | 87.8％ | 5.2％ | 1.6％ | 4.4％ |
| Comparative example 3 | 49.0％ | 94.4％ | 2.8％ | 1.3％ | 1.5％ |
As can be seen from Table 1, the metal oxide (ZrO)2Or TiO2) The aluminum zinc phosphate molecular sieve catalyst (ZAPO-5) serving as a stable auxiliary agent has higher activity and selectivity, and also has higher activity after regeneration. The activity of the catalyst can be improved by properly raising the reaction temperature. The CdAPO-5 catalyst has higher conversion rate but has the problem of environmental safety.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of an aluminum-zinc phosphate molecular sieve catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) adding 85% orthophosphoric acid by mass into deionized water, then adding soluble zirconium salt and a dispersing agent or soluble titanium salt and a dispersing agent, heating to 50-60 ℃ while stirring, then adding soluble zinc salt, adding pseudo-boehmite after the soluble zinc salt is completely dissolved, adding a template agent after stirring uniformly, adjusting the pH to 5-6 by using dilute hydrochloric acid, and continuously stirring to form uniform jelly;
(2) transferring the jelly into a homogeneous reaction kettle, aging for 6-8h at 80-100 ℃ while stirring, and then heating to 160-180 ℃ for carrying out constant temperature crystallization reaction for 24-36h to obtain a crystallized product;
(3) washing and filtering the crystallized product, drying at the temperature of 100-120 ℃ for 6-8h, then transferring into a calcining furnace, heating to the temperature of 550-600 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 4-6h to obtain molecular sieve raw powder;
(4) adding the molecular sieve raw powder into an aqueous solution added with 10-20% of aluminum sol, grinding the mixture into microemulsion by a wet method, wherein the mass ratio of the molecular sieve raw powder to the aqueous solution is 1:2-3, and then carrying out spray granulation to obtain the aluminum-zinc phosphate molecular sieve catalyst with the particle size of 50-150 mu m.
2. The method of claim 1, wherein: the active ingredient of the jelly is aZnO- (1-a) Al2O3-P2O5-bN-cH2O, wherein: a is ZnO and P2O5A is 0.15 to 0.35; b is a template agent and P2O5B is 1.0 to 1.5; c is H2O and P2O5C is 35 to 50; ZrO (ZrO)2Or TiO2The content of the molecular sieve is 3-5wt% of the raw powder of the molecular sieve; the dispersing agent is hydroxypropyl cellulose or hydroxymethyl cellulose, and the addition amount of the dispersing agent is 1-2wt% of the jelly.
3. The method of claim 1, wherein: the soluble zirconium salt is zirconium nitrate or zirconium oxychloride; the soluble titanium salt is titanium sulfate or titanyl sulfate; the soluble zinc salt is zinc acetate or zinc nitrate.
4. The production method according to any one of claims 1 to 3, characterized in that: the template agent is triethylamine or tetrapropylammonium hydroxide.
5. A method for preparing acetaldehyde by acetylene hydration is characterized in that: the preparation method of the aluminophosphate zinc molecular sieve catalyst prepared by the method of any one of claims 1 to 4, and the preparation method is carried out in a fluidized bed reaction device, wherein the reaction temperature is 400-440 ℃, the reaction pressure is normal pressure, the reaction atmosphere is inert gas or nitrogen atmosphere, the molar ratio of water to acetylene is 2-5, and the space velocity of acetylene is 100-300h-1。
6. A preparation method of an aluminum-zinc phosphate molecular sieve catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) adding 85% orthophosphoric acid by mass into deionized water, then adding soluble zirconium salt and a dispersing agent or soluble titanium salt and a dispersing agent, heating to 50-60 ℃ while stirring, then adding soluble zinc salt, adding pseudo-boehmite after the soluble zinc salt is completely dissolved, adding a template agent after stirring uniformly, adjusting the pH to 5-6 by using dilute hydrochloric acid, and continuously stirring to form uniform jelly;
(2) transferring the jelly into a homogeneous reaction kettle, aging for 6-8h at 80-100 ℃ while stirring, and then heating to 160-180 ℃ for carrying out constant temperature crystallization reaction for 24-36h to obtain a crystallized product;
(3) washing and filtering the crystallized product, drying at the temperature of 100-120 ℃ for 6-8h, then transferring into a calcining furnace, heating to the temperature of 550-600 ℃ at the speed of 5-10 ℃/h, and keeping the temperature for 4-6h to obtain molecular sieve raw powder;
(4) adding the molecular sieve raw powder into an aqueous solution added with 10-20% of aluminum sol, putting the mixture into a kneading machine, mixing and grinding the mixture into plastic material masses, extruding the plastic material masses into strips and cutting the strips and the particles into particles to obtain a catalyst precursor with the length of 10-15mm and the diameter of 1-3mm, wherein the mass ratio of the molecular sieve raw powder to the aqueous solution is 1: 1-1.5;
(5) drying the catalyst precursor at the temperature of 100-120 ℃ for 6-8h, then transferring the catalyst precursor into a calcining furnace, heating to the temperature of 500-550 ℃ at the speed of 5-10 ℃/h, and preserving the heat for 4-6h to obtain the aluminum-zinc phosphate molecular sieve catalyst.
7. The method of claim 6, wherein: the active ingredient of the jelly is aZnO- (1-a) Al2O3-P2O5-bN-cH2O, wherein: a is ZnO and P2O5A is 0.15 to 0.35; b is a template agent and P2O5B is 1.0 to 1.5; c is H2O and P2O5C is 35 to 50; ZrO (ZrO)2Or TiO2The content of (A) is 3-5 of the molecular sieve raw powderwt%; the dispersing agent is hydroxypropyl cellulose or hydroxymethyl cellulose, and the addition amount of the dispersing agent is 1-2wt% of the jelly.
8. The method of claim 6, wherein: the soluble zirconium salt is zirconium nitrate or zirconium oxychloride; the soluble titanium salt is titanium sulfate or titanyl sulfate; the soluble zinc salt is zinc acetate or zinc nitrate.
9. The production method according to any one of claims 6 to 8, characterized in that: the template agent is triethylamine or tetrapropylammonium hydroxide.
10. A method for preparing acetaldehyde by acetylene hydration is characterized in that: the preparation method of the aluminophosphate zinc molecular sieve catalyst prepared by the method of any one of claims 6 to 9, and the preparation method is carried out in a fixed bed reaction device, wherein the reaction temperature is 400-440 ℃, the reaction pressure is normal pressure, the reaction atmosphere is inert gas or nitrogen atmosphere, the molar ratio of water to acetylene is 2-5, and the space velocity of acetylene is 100-300h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110242347.7A CN113117741B (en) | 2021-03-04 | 2021-03-04 | Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110242347.7A CN113117741B (en) | 2021-03-04 | 2021-03-04 | Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113117741A CN113117741A (en) | 2021-07-16 |
| CN113117741B true CN113117741B (en) | 2022-03-29 |
Family
ID=76772522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110242347.7A Active CN113117741B (en) | 2021-03-04 | 2021-03-04 | Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113117741B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB842798A (en) * | 1958-04-30 | 1960-07-27 | British Oxygen Res And Dev Ltd | Process for the manufacture of acetaldehyde, catalysts for use therein and processes for the preparation and regeneration of such catalysts |
| JP3887686B2 (en) * | 2004-02-27 | 2007-02-28 | 国立大学法人岐阜大学 | Method for producing crystalline particulate zinc aluminophosphate |
| CN108993576A (en) * | 2018-07-16 | 2018-12-14 | 石河子大学 | A kind of zinc catalyst and preparation method thereof for catalyzing acetylene hydration reaction |
| CN111574344A (en) * | 2020-05-11 | 2020-08-25 | 蒋益波 | Preparation method for producing acetaldehyde by catalyzing acetylene with ZAPO molecular sieve |
-
2021
- 2021-03-04 CN CN202110242347.7A patent/CN113117741B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113117741A (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013125389A1 (en) | Method for producing 1,3-butadiene | |
| CN111097468B (en) | Alkyl pyridine ammoxidation catalyst and preparation method thereof | |
| CN106964396A (en) | RTH type topological structure molecular sieve catalysts for dimethyl ether carbonylation reaction and its preparation method and application | |
| WO2022206673A1 (en) | Molecular sieve catalyst for low-temperature carbonylation, and use thereof | |
| CN108821306B (en) | Preparation method of metal modified hierarchical pore HZSM-5 molecular sieve | |
| CN115920947A (en) | Co @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method and application thereof | |
| CN115722244A (en) | Boron nitride composite carrier copper-loaded catalyst and preparation method and use method thereof | |
| CN113117741B (en) | Preparation method and application of aluminum-zinc phosphate molecular sieve catalyst | |
| CN113751080B (en) | Modified alumina carrier and preparation method and application thereof | |
| CN103464157A (en) | Preparation method of acetic ester hydrogenation catalyst | |
| CN109289831A (en) | Catalyst for dehydrogenation of propane to propylene with high carbon deposition resistance and preparation method thereof | |
| CN112619686B (en) | Supported non-noble metal dehydrogenation catalyst and preparation method and application thereof | |
| CN115814839A (en) | Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof | |
| CN110614118A (en) | Isobutane dehydrogenation catalyst with three-hole sepiolite spherical mesoporous composite material as carrier and preparation method and application thereof | |
| CN100453178C (en) | Catalyst for synthesizing iso-propylbenzene | |
| CN116237054A (en) | Catalyst suitable for hydrogenation of isooctenal to prepare 2-ethylhexanal, preparation method and application thereof | |
| CN115650817A (en) | Method for preparing ethylbenzene by catalyzing ethanol and benzene with nano flaky molecular sieve | |
| CN110732342A (en) | Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof | |
| CN110614111A (en) | Isobutane dehydrogenation catalyst with spherical tri-mesoporous attapulgite composite material as carrier and preparation method and application thereof | |
| CN110496634B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
| CN115722256B (en) | Preparation method of alkylation catalyst, catalyst and application | |
| CN115487853B (en) | Mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and preparation method and application thereof | |
| CN119327440B (en) | A magnesium aluminum erbium composite oxide catalyst and its preparation method and application | |
| CN105566050A (en) | Method for producing ethylbenzene from ethylene and benzene | |
| CN118005493B (en) | Preparation method of 2-ethylhexanal, catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |