CN111437879B - Catalyst and method for preparing methyl acrylate from methyl formate and acetylene - Google Patents
Catalyst and method for preparing methyl acrylate from methyl formate and acetylene Download PDFInfo
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- CN111437879B CN111437879B CN202010355502.1A CN202010355502A CN111437879B CN 111437879 B CN111437879 B CN 111437879B CN 202010355502 A CN202010355502 A CN 202010355502A CN 111437879 B CN111437879 B CN 111437879B
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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
- B01J29/80—Mixtures of different zeolites
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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
- B01J29/40—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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a catalyst and a method for preparing methyl acrylate from methyl formate and acetylene. A catalyst and a method for preparing methyl acrylate by methyl formate and acetylene are disclosed, wherein the catalyst comprises the following components: the composite material comprises, by weight, 0-10 parts of nickel oxide, 3238 parts of ruthenium, 3238 parts of zxft, 0-10 parts of iron carbide, 3262 parts of lanthanum oxide, 3262 parts of zxft And the balance of H-ZMS-5 type molecular sieve, H-ZMS-11 type molecular sieve or a mixture of H-ZMS-5 type molecular sieve and H-ZMS-11 type molecular sieve. The method takes the methyl formate prepared from the synthesis gas as a raw material, has the advantages of low raw material cost, low reaction temperature, low energy consumption, greatly improved methyl formate conversion rate and methyl acrylate selectivity, one-step preparation, simple and efficient process route and remarkable economic advantage.
Description
Technical Field
The invention relates to a catalyst and a method for preparing methyl acrylate from methyl formate and acetylene.
Background
Acrylic acid and methyl acrylate are important organic basic chemical raw materials, are important standards for measuring the national chemical industry level, and the demand of the acrylic acid and the methyl acrylate is continuously increased along with the rapid development of national economy. Acrylic acid is used primarily in the production of acrylates including methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and in the production of polyacrylic acids (salts). The polymer obtained by polymerization reaction of the carbon-carbon double bond of the acrylate is colorless and transparent, has excellent chemical properties and physical properties such as light stability, weather resistance, water resistance, oil resistance, chemical resistance and the like, has strong cohesiveness, good transparency and clear film formation, and is widely applied to the fields of coating, synthetic fiber, synthetic rubber, plastic, leather, papermaking, adhesive, packaging material, water, metallurgy mining, daily chemical products and the like. The use of acrylate in the United states, western Europe and Japan accounts for 85% of the consumption of acrylic acid in the 80 s, and only accounts for about 50% of the consumption of acrylic acid in the 2000 s although the use of acrylate has steadily increased. In the later 70 s, two brand-new application markets of the polypropylene and the acrylic acid copolymer, namely the super absorbent resin and the washing assistant appear, thereby providing bright prospects for the development of acrylic acid application and promoting the development of acrylic acid industry. In 2018, the total consumption of acrylic acid and ester compounds thereof in China reaches 480 ten thousand tons, and the domestic demand is vigorous.
The production method of methyl acrylate includes acrylonitrile hydrolysis method, propylene direct oxidation method and vinyl ketone method.
1. The acrylonitrile hydrolysis method takes acrylonitrile as a raw material, hydrolysis is carried out in the presence of concentrated sulfuric acid, and hydrolyzed acrylamide sulfate and methanol react to obtain methyl acrylate. 860kg of propylene (98%), 960kg of methanol (95%) and 2000kg of sulfuric acid (93%) are consumed by each ton of product of methyl acrylate produced by an acrylonitrile hydration method.
2. The direct propylene oxidation process uses propylene as the starting material and first oxidizes acrolein to acrylic acid. The acrylic acid is reacted with methanol to produce methyl acrylate. Methyl acrylate was produced by the direct oxidation of propylene, consuming 544kg of propylene (95%) per ton of product.
3. Ketene and formaldehyde are condensed by a vinyl ketone method by taking boron trifluoride as a catalyst, quenched by methanol and esterified to generate methyl acrylate.
4. The esterification method of acrylic acid and methanol comprises the steps of sequentially adding acrylic acid, methanol and expandable graphite into a flat-bottomed flask, wherein the mass ratio of the added acrylic acid to the added methanol is 1.15: 1. Connecting the water separator and the reflux condenser pipe, placing on a magnetic heating stirrer for heating and stirring, and cooling after reacting for a period of time. The yield was calculated by saponification (neutralization of the remaining acrylic acid with alkaline solution, saponification by addition of a quantitative KOH solution, and titration of excess KOH with standard HCl solution, the ester yield was calculated). And simultaneously separating ester, distilling the reaction solution, and collecting the distillate at 65-95 ℃ to obtain a crude product. Washing with 5% NaCO3 solution to neutrality, washing with saturated NaCl solution for 2 times, and washing with anhydrous NaSO 4 Drying, distilling, and collecting 72-74 ℃ fractionsAnd obtaining the product.
5. Modification Lei Pofa the modification Lei Pofa is the Romhas method and the Doubas method. The former mainly uses gaseous carbon monoxide to replace 80% of carbon monoxide in nickel carbonyl, and the latter is also called high pressure Lei Po method, and mainly uses tetrahydrofuran as solvent.
(1) The improved Lei Po method. After the reaction of the method is started, carbon monoxide, acetylene and alcohol are used for generating acrylic ester, and the introduced carbon monoxide replaces carbon monoxide in nickel carbonyl, so that the regeneration of the nickel carbonyl and the recovery of nickel can be reduced. The solvent for the reaction is an alcohol. The reaction temperature is 30 to 50 ℃, the pressure is 0.1 to 0.2MPa, the ratio of acetylene to carbon monoxide is (1.01 to 1.10) to 1 (molar ratio), and the ratio of methanol to total carbon monoxide is (1.1 to 3) to 1 (molar ratio). The acid amount is kept between 80 and 99 percent (mol ratio) of the nickel carbonyl so as to inhibit the generation of the chloropropionic acid. The method is characterized by operating at normal pressure, and the equipment is easy to solve, but the poisonous nickel carbonyl still needs to be prepared.
(2) High pressure Lei Po. Tetrahydrofuran is used as a solvent, palladium chloride is used as a catalyst, copper chloride is used as an accelerating agent, and the reaction is carried out at the temperature of 200 to 225 ℃ and the pressure of 8.11 to 10.13MPa. And (3) washing unreacted acetylene gas at the top of the reactor to remove acrylic acid, recycling, and evaporating tetrahydrofuran to obtain acrylic acid from the acrylic acid and tetrahydrofuran solution at the bottom of the reactor. The yield of acrylic acid is about 90 percent by acetylene and about 85 percent by carbon monoxide, and then the acrylic acid is esterified with methanol in sulfuric acid or ion exchange resin medium to obtain the methyl acrylate. For example, continuous esterification is carried out by using an acid catalyst when producing higher esters above butyl ester, and the acrylic ester is obtained by using ion exchange resin as a catalyst when producing ethyl acrylate. The process features that tetrahydrofuran is used as solvent and acetylene needed for reaction is first dissolved in tetrahydrofuran to reduce the risk of high pressure treatment of acetylene, and nickel salt is used as catalyst instead of carbonyl nickel. However, the operating pressure of this method is high, so the material requirement of the equipment is high.
As the propylene resource is increasingly tense and the price is continuously high, the development of low-cost and non-propylene method for preparing acrylic acid and ester compounds thereof has practical value. Acetylene has the advantages of wide source, low cost, no restriction of petroleum and the like, simultaneously has high activity, terminal hydrogen activity can generate various chemical reactions, and the preparation of methyl acrylate by taking acetylene as a raw material has good prospect, but the traditional Reppe method for preparing acrylic acid and then esterifying the acrylic acid to prepare methyl acrylate mainly adopts homogeneous reaction, has the defects of low product selectivity, methyl propionate byproduct existence, difficult separation, high catalyst cost and the like, and is eliminated. Therefore, it is of great significance to develop a process route for preparing methyl acrylate by reacting acetylene with low-cost methyl formate prepared from synthesis gas.
Disclosure of Invention
The invention aims to solve the problems and provides a catalyst used in a process of preparing methyl acrylate from methyl formate and acetylene and a method for preparing methyl acrylate from methyl formate and acetylene by using the catalyst.
The technical scheme of the invention is as follows:
the invention provides a catalyst for preparing methyl acrylate from methyl formate and acetylene, which comprises the following components: 0 to 10 parts of nickel oxide, 0~2 parts of ruthenium, 0 to 10 parts of iron carbide and 0~2 parts of lanthanum oxide, wherein the parts of nickel oxide, ruthenium, iron carbide and lanthanum oxide are not 0 part; the balance of H-ZMS-5 type molecular sieve or H-ZMS-11 type molecular sieve or the mixture of H-ZMS-5 type molecular sieve and H-ZMS-11 type molecular sieve.
Preferably, the preparation process of the H-ZMS-5 type molecular sieve is as follows: roasting the ZSM-5 molecular sieve at 500-550 ℃ for 3-5 h to burn out the template agent, exchanging the template agent with 0.6-0.8 mol/L ammonium nitrate solution at 60-80 ℃, drying, and roasting at 500-550 ℃ for 3-5 h to prepare the modified ZSM-5 molecular sieve.
Or preferably, the preparation process of the H-ZMS-11 type molecular sieve is as follows: roasting the ZSM-11 molecular sieve at 500-550 ℃ for 3-5H to burn out the template agent, exchanging the template agent with 0.6-0.8 mol/L ammonium nitrate solution at 60-80 ℃, drying, and roasting at 500-550 ℃ for 3-5H to prepare the H-ZMS-11 type molecular sieve.
The preparation method of the catalyst comprises the following steps: the main catalyst and the molecular sieve are prepared by a mechanical mixing method.
The invention provides a method for preparing methyl acrylate by methyl formate and acetylene, which is characterized in that a catalyst bed layer formed by the catalyst is filled in a fixed bed reaction, the methyl formate and the acetylene are used as raw materials, the methyl formate and the acetylene pass through a fixed bed reactor filled with the catalyst bed layer under the conditions of reaction temperature of 120-150 ℃, reaction pressure of 0.1-2 MPa and weight space velocity of 1-3 h < -1 >, acetylene and the catalyst react in the fixed bed reactor to generate acetylene hydrocarbon negative ions, so that alpha position of the methyl formate is activated, and the methyl acrylate is generated by coupling the collision of the catalyst surface and alpha carbon of the methyl formate. The molar selectivity of the product methyl acrylate is more than 96 percent, and the conversion rate of the methyl formate is more than 90 percent.
The invention has the technical effects that:
1) The method takes the methyl formate prepared from the synthesis gas as a raw material, has low raw material cost, low reaction temperature, low energy consumption, greatly improved methyl formate conversion rate and methyl acrylate selectivity, one-step preparation, simple and efficient process route and remarkable economic advantage;
2) Advanced technical route, no three-waste discharge, no greenhouse gas discharge and zero process pollution: methyl formate and acetylene are used as raw materials, and the product is mainly methyl acrylate. The problem of large amount of carbon monoxide circulation in the traditional Reppe method process is avoided, and zero emission to the environment is realized;
3) The separation and purification are simple, and the product selectivity is high: methyl formate is adopted as a raw material, a component which is difficult to separate methyl propionate in the conventional acetylene homogeneous phase acrylic acid preparation process is not needed, the composition of reactants is simple, and the cost of the separation and purification process is low.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
The catalyst used in this example comprises, in terms of weight fraction after calcination, 10 parts of nickel oxide, 1 part of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-5 type molecular sieve. Wherein the H-ZMS-5 type molecular sieve is prepared by a 550 ℃ roasting method. The catalyst number is YCSY-01;
the catalyst performance was evaluated in a fixed bed reactor, and the catalyst bed layer constituted as described above was packed in the fixed bed reactor. The raw materials of methyl formate and acetylene in equal molar are preheated and passed through adiabatic catalyst bed layer, and then coupled to produce methyl acrylate, and the reaction conditions and results are shown in Table 1.
Example 2
The catalyst used in this example comprises, in terms of weight fraction after calcination, 8 parts of nickel oxide, 1 part of ruthenium, 1 part of iron carbide, 2 parts of lanthanum oxide, and the balance of H-ZMS-5 type molecular sieve. Wherein the preparation process of the H-ZMS-5 type molecular sieve is the same as that of example 1. The catalyst is numbered YCSY-02;
the catalyst performance evaluation was carried out in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 3
The catalyst used in this example comprises, in terms of weight fraction after calcination, 6 parts of nickel oxide, 1 part of ruthenium, 2 parts of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-5 type molecular sieve. Wherein the preparation process of the H-ZMS-5 type molecular sieve is the same as that of example 1. The catalyst number is YCSY-03;
the catalyst performance evaluation was carried out in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 4
The catalyst used in this example comprises, in terms of weight fraction after calcination, 5 parts of nickel oxide, 2 parts of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-5 type molecular sieve. Wherein the preparation process of the H-ZMS-5 type molecular sieve is the same as that of example 1. The catalyst number is YCSY-04;
the catalyst performance evaluation was carried out in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 5
The catalyst used in this example comprises, in terms of weight fraction after calcination, 3 parts of nickel oxide, 2 parts of ruthenium, 1 part of iron carbide, 2 parts of lanthanum oxide, and the balance of H-ZMS-5 type molecular sieve. Wherein the preparation process of the H-ZMS-5 type molecular sieve is the same as that of example 1. The catalyst number is YCSY-05;
the catalyst performance evaluation was carried out in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 6
The catalyst used in this example comprises, in terms of weight fraction after calcination, 10 parts of nickel oxide, 1 part of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-11 type molecular sieve. Wherein, the H-ZMS-11 type molecular sieve is prepared by a 550 ℃ roasting method. The catalyst is numbered YCSY-06;
the procedure for evaluating the catalyst performance was the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 7
The catalyst used in the example comprises 8 parts of nickel oxide, 2 parts of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide and the balance of H-ZMS-11 type molecular sieve by weight fraction after calcination. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. Catalyst number YCSY-07;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 8
The catalyst used in the example comprises 6 parts of nickel oxide, 2 parts of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide and the balance of H-ZMS-11 type molecular sieve by weight fraction after calcination. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-08;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 9
The catalyst used in the example comprises 10 parts of nickel oxide, 1 part of ruthenium, 2 parts of iron carbide, 2 parts of lanthanum oxide and the balance of H-ZMS-11 type molecular sieve by weight fraction after calcination. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-09;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 10
The catalyst used in this example comprises, in terms of weight fraction after calcination, 5 parts of nickel oxide, 2 parts of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-11 type molecular sieve. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-10;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 11
The catalyst used in the example comprises 2 parts of nickel oxide, 2 parts of ruthenium, 1 part of iron carbide, 2 parts of lanthanum oxide and the balance of H-ZMS-11 type molecular sieve by weight fraction after calcination. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-11;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 12
The catalyst used in this example comprises, in terms of weight fraction after calcination, 9 parts of nickel oxide, 1 part of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-11 type molecular sieve. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-12;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 13
The catalyst used in the example comprises 8 parts of nickel oxide, 1 part of ruthenium, 2 parts of iron carbide, 1 part of lanthanum oxide and the balance of H-ZMS-11 type molecular sieve by weight fraction after calcination. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-13;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
Example 14
The catalyst used in this example comprises, in terms of weight fraction after calcination, 7 parts of nickel oxide, 1 part of ruthenium, 1 part of iron carbide, 1 part of lanthanum oxide, and the balance of H-ZMS-11 type molecular sieve. Wherein the preparation process of the H-ZMS-11 type molecular sieve is the same as that of example 6. The catalyst number is YCSY-14;
the catalyst evaluation conditions were the same as in example 1, and the reaction conditions and results are shown in Table 1.
TABLE 1
Claims (6)
1. A catalyst for preparing methyl acrylate from methyl formate and acetylene is characterized in that: the catalyst comprises 0-10 parts of nickel oxide, 3238 parts of ruthenium, 3238 parts of zxft, 0-10 parts of iron carbide and 3262 parts of lanthanum oxide, wherein the weight parts of nickel oxide, ruthenium, iron carbide and lanthanum oxide are not 0; the balance of H-ZMS-5 type molecular sieve or H-ZMS-11 type molecular sieve or the mixture of H-ZMS-5 type molecular sieve and H-ZMS-11 type molecular sieve.
2. The catalyst for preparing methyl acrylate from methyl formate and acetylene according to claim 1, wherein: the preparation process of the H-ZMS-5 type molecular sieve comprises the following steps: roasting the ZSM-5 molecular sieve at 500-550 ℃ for 3-5H to burn out the template agent, exchanging the template agent with 0.6-0.8 mol/L ammonium nitrate solution at 60-80 ℃, drying, and roasting at 500-550 ℃ for 3-5H to prepare the H-ZMS-5 type molecular sieve.
3. The catalyst for preparing methyl acrylate from methyl formate and acetylene according to claim 1, wherein: the preparation process of the H-ZMS-11 type molecular sieve comprises the following steps: roasting the ZSM-11 molecular sieve at 500-550 ℃ for 3-5H to burn out the template agent, exchanging the template agent with 0.6-0.8 mol/L ammonium nitrate solution at 60-80 ℃, drying, and roasting at 500-550 ℃ for 3-5H to prepare the H-ZMS-11 type molecular sieve.
4. The catalyst for preparing methyl acrylate from methyl formate and acetylene according to claim 1 or 2, wherein: the preparation method of the catalyst comprises the following steps: the main catalyst and the molecular sieve are prepared by a mechanical mixing method.
5. A method for preparing methyl acrylate from methyl formate and acetylene is characterized by comprising the following steps: in a fixed bed reaction, filling a catalyst bed layer formed by the catalyst of claim 1, taking methyl formate and acetylene as raw materials, and reacting the methyl formate and the acetylene at the temperature of 120-150 ℃, the reaction pressure of 0.1-2 MPa and the weight space velocity of 1-3 hours -1 Under the condition of passing through a fixed bed reactor filled with a catalyst bed layer, methyl formate and acetylene are generated in the fixed bed reactorAnd (3) preparing methyl acrylate through coupling addition reaction.
6. The process for preparing methyl acrylate from methyl formate and acetylene according to claim 5, wherein: the molar ratio of methyl formate to acetylene is 1:1.
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