CN116618086A - Catalyst and method for preparing olefine aldehyde and olefine acid by oxidizing olefin - Google Patents

Catalyst and method for preparing olefine aldehyde and olefine acid by oxidizing olefin Download PDF

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CN116618086A
CN116618086A CN202310547728.5A CN202310547728A CN116618086A CN 116618086 A CN116618086 A CN 116618086A CN 202310547728 A CN202310547728 A CN 202310547728A CN 116618086 A CN116618086 A CN 116618086A
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catalyst
olefine
carrier
acid
molecular sieve
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吴立娟
项佳珩
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Ningbo Chengzhou Chemical Engineering Technology Co ltd
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Ningbo Chengzhou Chemical Engineering Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7807—A-type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a kind of deviceThe catalyst for preparing olefine aldehyde and olefine acid by using olefine oxide is formed from carrier and active component supported on the carrier, and the chemical general formula of the described active component is MoBi a Co b Ca x B c O y Wherein Mo is molybdenum, bi is bismuth, co is cobalt, ca is calcium, B is boron, and O is oxygen; a. b, c, x and y are molar ratios of the elements; wherein 0.2 +.a +. 0.65,0.3 +.b +.1.0, 1.5 +.x +. 3,0.4 +.c +.1.5, y is determined by the oxidation degree of each other element and is the number of moles of oxygen atoms needed to satisfy the valence of each other element; the carrier is composed of molecular sieve powder, graphite and C 60 Mixing to obtain the final product. The catalyst of the invention has high olefin conversion rate, high yield of olefine aldehyde and olefine acid, good stability and long service life.

Description

Catalyst and method for preparing olefine aldehyde and olefine acid by oxidizing olefin
Technical Field
The invention relates to the field of industrial synthesis of acrylic acid, in particular to a catalyst and a method for preparing olefine aldehyde and olefine acid by oxidizing olefin.
Background
Acrylic acid is an important organic chemical raw material, is mainly used for manufacturing multifunctional polymer materials such as acrylic esters and the like, and is widely applied to the fields of papermaking, leather, paint, textile, plastics, rubber, oil additives, petroleum exploitation and the like, and in recent years, the market demand of the acrylic acid is in short supply. Therefore, how to efficiently and high-quality produce acrylic acid with increased or decreased heat has been studied.
At present, propylene is commonly used as a raw material for preparing acrylic acid in industry by oxidation, and the method comprises two stages, namely, firstly, the propylene is subjected to gas-phase catalytic oxidation to generate acrolein, and then, the acrolein is oxidized to acrylic acid. In the process of preparing acrylic acid by the method, the performance of the catalyst directly determines the conversion rate of propylene and the yield of acrolein or acrylic acid, and the catalyst is used as one of important consumables in the production system, so that the use stability and the service life period of the catalyst obviously influence the economic benefit of enterprises, and therefore, various researches and improvements are continuously carried out by domestic and foreign enterprises for many years.
The catalysts disclosed in Japanese patent publication No. 50 (19750) -1330A1, japanese patent publication No. 50-47915A1 and the like contain at least one element selected from potassium, rubidium and cesium as a main component, and molybdenum, bismuth, iron, antimony and nickel are blended. TW518253B discloses a composite oxide catalyst comprising not only tungsten, bismuth, iron, but also other elements of the A-E series, A being at least one element selected from nickel or cobalt; b is at least one element selected from sodium, potassium, rubidium, cesium and thallium; c is at least one element selected from alkaline earth metals; d is at least one element selected from the group consisting of phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc; e is at least one element selected from the group consisting of silicon, aluminum, titanium and zirconium. The composition of the catalysts disclosed in these patents is relatively complex, there is a large space for reducing the cost of the catalysts, and in addition, the yields of acrylic acid and acrolein are still to be improved.
The present invention therefore aims to provide a novel catalyst which is relatively simple in composition and is expected to reduce cost, and which has a catalytic effect which is no worse than that of the prior art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel catalyst for preparing olefine aldehyde and olefine acid by oxidizing olefin.
The invention provides a catalyst for preparing olefine aldehyde and olefine acid by oxidizing olefin, which consists of a carrier and active components loaded on the carrier, wherein the chemical general formula of the active components is as follows:
MoBi a Co b Ca x B c O y
mo is molybdenum, bi is bismuth, co is cobalt, ca is calcium, B is boron, and O is oxygen; a. b, c, x and y are molar ratios of the elements; wherein 0.2 +.a +. 0.65,0.3 +.b +.1.0, 1.5 +.x +. 3,0.4 +.c +.1.5, y is determined by the oxidation degree of each other element and is the number of moles of oxygen atoms needed to satisfy the valence of each other element; the carrier is composed of molecular sieve powder, graphite and C 60 Mixing to obtain the final product.
As one way, the catalyst has an active component content of 10 to 35wt% based on the weight.
As one approach, the molecular sieve powder is selected from one or more of a type a molecular sieve, an X type molecular sieve, a Y type molecular sieve, ZSM-5, SAPO-34, beta molecular sieve, or SAPO-11 in combination.
As a mode, the addition amount of the graphite accounts for 2-8wt% of the total weight of the carrier, and C 60 The addition amount of the catalyst is 0.05-0.5 wt% of the total weight of the carrier.
As one mode, the preparation method of the catalyst comprises the following steps: preparing a mixed solution containing active component elements and the carrier, immersing the carrier in the mixed solution of the active component elements, molding and roasting to obtain the catalyst.
As one way, the molecular sieve powder is prepared in a mixture of 8 to 15wt% hf and 10 to 20wt% hydrochloric acid according to 1: treating in mixed acid of 45-55 deg.c for 2-5 hr, washing with clear water, and drying.
As one mode, the conditions of the firing are: calcining at 460-650 deg.c for 3-8 hr.
The invention also provides a process for preparing alkenals and alkenoic acids by oxidation of olefins using a catalyst according to any of the above.
As one mode, the olefin is propylene, the enal is acrolein, and the olefmic acid is acrylic acid.
Compared with the prior art, the invention has the following advantages:
1. the constituent elements of the catalyst are relatively simple and easy to obtain, and the production cost of the catalyst is reduced.
2. The catalyst has high propylene conversion rate, high yield of acrolein and acrylic acid, good stability and long service life, can reduce the dosage and improve the economic benefit.
3. The active components in the catalyst and the carrier perform synergistic effect, so that better catalytic effect is achieved, the stability of the catalyst is improved, and the service life is prolonged.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention are clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
Example 1
(1) Preparation of a mixture comprising active ingredient elements
The raw materials used are shown in the following table:
active component element The specific raw materials used Usage amount
Mo Ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ) 0.1mol
Bi Bismuth nitrate (Bi (NO) 3 ) 3 ) 0.14mol
Co Cobalt nitrate (Co (NO) 3 ) 2 ) 0.7mol
Ca Calcium chloride (CaCl) 2 ) 2.1mol
B Ammonium borate (NH) 4 HB 4 O 7 ·3H 2 O) 1.05mol
According to the above formula, ammonium paramolybdate, cobalt nitrate, calcium chloride and ammonium borate were dissolved in 2L of deionized water (50 ℃ C.) to obtain solution A; 50 g of 60wt% nitric acid and 200mL of deionized water are taken and mixed uniformly, and bismuth nitrate is added for full dissolution, so as to obtain solution B; and uniformly mixing the solution A and the solution B to obtain a mixed solution containing active component elements.
In the prepared mixed solution, the element composition in the active component is MoBi 0.2 CoCa 3 B 1.5 O 9.55 The mass is 340.15g.
(2) Preparation of the vector
2984.82g of molecular sieve A powder, 61.23g of graphite (2 wt% of the carrier) and 15.31g of C were weighed out 60 (0.5 wt% of the carrier) and uniformly mixing to form the carrier.
(3) Dipping and molding
Dispersing the carrier in the mixed solution containing the active component elements, stirring and soaking for 14h, evaporating water to a state suitable for extrusion molding, and extruding into spherical particles with the particle size of 5 mm.
(4) Drying and roasting
Drying the spherical particles at 110 ℃ for 4 hours, and calcining at 650 ℃ for 3 hours.
The composition of the obtained catalyst is as follows, based on the weight of the catalyst: 10wt% MoBi 0.2 CoCa 3 B 1.5 O 9.55 +90wt% carrier.
Example 2
The only difference from example 1 is that the molecular sieve powder of example 1 is purchased in the market for direct use, whereas the molecular sieve powder of the present case is subjected to the following optimization treatments:
the reaction was carried out with 10% by weight of HF and 20% by weight of hydrochloric acid according to 1: treating in mixed acid obtained by mixing in a volume ratio of 1 at 55 ℃ for 2 hours, washing with clear water, and drying for later use.
Others remain the same as in example 1.
Example 3
The difference from example 1 was that the active component content in the catalyst was 35% and the carrier was 65% by weight.
The active ingredient was prepared as in example 1.
The carrier was composed of 580.85g of molecular sieve A powder, 50.54g of graphite (8 wt% of the carrier) and 0.32g of C 60 (0.05 wt% of the carrier) and uniformly mixed.
The composition of the obtained catalyst is as follows, based on the weight of the catalyst: 35wt% MoBi 0.2 CoCa 3 B 1.5 O 9.55 +65wt% carrier.
Example 4
(1) Preparation of a mixture comprising active ingredient elements
The raw materials used are shown in the following table:
active component element The specific raw materials used Usage amount
Mo Ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ) 0.1mol
Bi Bismuth nitrate (Bi (NO) 3 ) 3 ) 0.455mol
Co Cobalt nitrate (Co (NO) 3 ) 2 ) 0.21mol
Ca Calcium chloride 1.05mol
B Ammonium borate (NH) 4 HB 4 O 7 ·3H 2 O) 0.28mol
According to the formula, dissolving ammonium paramolybdate, cobalt nitrate, calcium chloride and ammonium borate in 3L of deionized water (50 ℃) to obtain solution A; 50 g of 60wt% nitric acid and 200mL of deionized water are taken and mixed uniformly, and bismuth nitrate is added for full dissolution, so as to obtain solution B; and uniformly mixing the solution A and the solution B to obtain a mixed solution containing active component elements.
In the prepared mixed solution, the element composition in the active component is MoBi 0.65 Co 0.3 Ca 1.5 B 0.4 O 6.375 The mass is 291.90g.
(3) Preparation of the vector
1106.87g of ZSM-5 molecular sieve powder, 58.37g of graphite (5 wt% of the carrier) and 2.34g of C were weighed out 60 (0.2 wt% of the carrier) and uniformly mixing to form the carrier.
(3) Dipping and molding
Dispersing the carrier in the mixed solution containing the active component elements, stirring and soaking for 20 hours, evaporating water to a state suitable for extrusion molding, and extruding into spherical particles.
(4) Drying and roasting
Drying the spherical particles at 130 ℃ for 2 hours, and calcining at 460 ℃ for 8 hours.
The composition of the obtained catalyst is as follows, based on the weight of the catalyst: 20wt% MoBi 0.65 Co 0.3 Ca 1.5 B 0.4 O 6.375 +80wt% carrier.
Example 5
The only difference from example 4 is that the molecular sieve powder of example 4 is purchased in the market for direct use, whereas the molecular sieve powder of the present case is subjected to the following optimization treatments:
15wt% HF and 10wt% hydrochloric acid were mixed according to 1: treating in mixed acid obtained by mixing in a volume ratio of 1 at 50 ℃ for 3 hours, washing with clear water, and drying for later use.
Others remain the same as in example 4.
Example 6
(1) Preparation of a mixture comprising active ingredient elements
The raw materials used are shown in the following table:
active component element The specific raw materials used Usage amount
Mo Ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ) 0.1mol
Bi Bismuth nitrate (Bi (NO) 3 ) 3 ) 0.28mol
Co Cobalt nitrate (Co (NO) 3 ) 2 ) 0.35mol
Ca Calcium chloride (CaCl) 2 ) 1.4mol
B Ammonium borate (NH) 4 HB 4 O 7 ·3H 2 O) 0.7mol
According to the formula, dissolving ammonium paramolybdate, cobalt nitrate, calcium chloride and ammonium borate in 3L of deionized water (50 ℃) to obtain solution A; 50 g of 60wt% nitric acid and 200mL of deionized water are taken and mixed uniformly, and bismuth nitrate is added for full dissolution, so as to obtain solution B; and uniformly mixing the solution A and the solution B to obtain a mixed solution containing active component elements.
In the prepared mixed solution, the element composition in the active component is MoBi 0.4 Co 0.5 Ca 2 BO 7.6 The mass is 295.11g.
(4) Preparation of the vector
665.17g of SAPO-11 molecular sieve powder, 20.66g of graphite (3 wt% of the carrier) and 2.75g of C were weighed out 60 (0.4 wt% of the carrier) and uniformly mixing to form the carrier.
(3) Dipping and molding
Dispersing the carrier in the mixed solution containing the active component elements, stirring and soaking for 24 hours, evaporating water to a state suitable for extrusion molding, and extruding into spherical particles.
(4) Drying and roasting
Drying the spherical particles at 100 ℃ for 4 hours, and calcining at 500 ℃ for 6 hours.
The composition of the obtained catalyst is as follows, based on the weight of the catalyst: 30wt% MoBi 0.4 Co 0.5 Ca 2 BO 7.6 +70wt% carrier.
Comparative example 1
The difference from example 1 is that no graphite is added to the support.
Comparative example 2
The difference from example 1 is that no C is added to the carrier 60 。
Test example 1
1500ml of the catalyst obtained in accordance with the methods of examples 1 to 6 and comparative examples 1 to 2 was charged into a stainless steel reactor having a diameter of 25mm, respectively, and the reaction time was 1800 hours -1 Is introduced into a gas mixture comprising 7v% propylene, 14v% oxygen, 25v% water vapor and 54v% nitrogenThe oxidation reaction was carried out at 310 ℃.
The specific experimental results are shown in table 1, wherein:
conversion (%) = amount of propylene reacted/original total amount of propylene 100%
Yield (%) = total molar amount of acrylic acid and acrolein/original molar amount of propylene 100%.
TABLE 1
Further, the catalysts of examples 1 to 6 and comparative examples 1 to 2 were continuously operated under the above-mentioned conditions for 2000 hours, and then tested for propylene conversion and acrolein+acrylic acid yield and loss rates of molybdenum element and bismuth element, and the appearance of the catalysts was observed. The specific results are shown in Table 2.
TABLE 2
Therefore, after the catalyst of the invention runs continuously for 2000 hours, the propylene conversion rate and the yield of target products are hardly changed obviously, the loss rate of the main active elements Mo and Bi is very low, the performance is more stable, the service life is longer, the catalyst replacement frequency of a production system can be reduced, and the consumable expenditure is saved.
Although the embodiments of the present invention are described above, the embodiments are only used for facilitating understanding of the present invention, and are not intended to limit the present invention. Any person skilled in the art can make any modification and variation in form and detail without departing from the spirit and scope of the present disclosure, but the scope of the present disclosure is to be determined by the appended claims.

Claims (9)

1. The catalyst for preparing olefine aldehyde and olefine acid by using olefine oxide is formed from carrier and active component supported on the carrier, and is characterized by that the chemical general formula of the described active component is:
MoBi a Co b Ca x B c O y
mo is molybdenum, bi is bismuth, co is cobalt, ca is calcium, B is boron, and O is oxygen; a. b, c, x and y are molar ratios of the elements; wherein 0.2 +.a +. 0.65,0.3 +.b +.1.0, 1.5 +.x +. 3,0.4 +.c +.1.5, y is determined by the oxidation degree of each other element and is the number of moles of oxygen atoms needed to satisfy the valence of each other element;
the carrier is composed of molecular sieve powder, graphite and C 60 Mixing to obtain the final product.
2. The catalyst for the preparation of alkenals and alkenoic acids as claimed in claim 1, wherein the active component content of the catalyst is from 10 to 35% by weight.
3. The catalyst for the preparation of alkenals and alkenoic acid from alkylene oxides of claim 1 wherein the molecular sieve powder is selected from one or more of the group consisting of a type a molecular sieve, an X type molecular sieve, a Y type molecular sieve, ZSM-5, SAPO-34, beta molecular sieve and SAPO-11.
4. The catalyst for preparing olefine aldehyde and olefine acid with olefine oxide as claimed in claim 1, wherein the graphite is added in 2-8 wt% of the total carrier weight and C 60 The addition amount of the catalyst is 0.05-0.5 wt% of the total weight of the carrier.
5. The catalyst for the preparation of olefine aldehyde and olefine acid from olefine oxide according to claim 1, wherein the preparation method of the catalyst comprises the following steps: preparing a mixed solution containing active component elements and the carrier, immersing the carrier in the mixed solution of the active component elements, molding and roasting to obtain the catalyst.
6. The catalyst for the preparation of olefine aldehyde and olefine acid from olefine oxide according to claim 5, wherein the molecular sieve powder is prepared by mixing 8 to 15wt% of HF and 10 to 20wt% of hydrochloric acid according to the following formula 1: treating in mixed acid of 45-55 deg.c for 2-5 hr, washing with clear water, and drying.
7. The catalyst for the preparation of alkenals and alkenoic acids as claimed in claim 5, wherein said calcination conditions are: calcining at 460-650 deg.c for 3-8 hr.
8. A process for preparing alkenals and alkenoic acids by oxidation of olefins, characterized in that a catalyst according to any of claims 1 to 7 is used.
9. The method for producing an enal and an enal acid from an alkylene oxide according to claim 8, wherein the alkylene is propylene, the enal is acrolein, and the enal acid is acrylic acid.
CN202310547728.5A 2023-05-16 2023-05-16 Catalyst and method for preparing olefine aldehyde and olefine acid by oxidizing olefin Pending CN116618086A (en)

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