CN109759090B - Active carbon-loaded iridium-based catalyst containing nickel iron sulfide, and preparation and application thereof - Google Patents
Active carbon-loaded iridium-based catalyst containing nickel iron sulfide, and preparation and application thereof Download PDFInfo
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Abstract
An iridium-based catalyst loaded by active carbon and containing nickel iron sulfide, and preparation and application thereof. The catalyst consists of three parts, namely a main catalyst, an auxiliary catalyst and a carrier, wherein the active component of the main catalyst is a soluble compound of iridium, the auxiliary catalyst is one or more than two of sulfides containing iron, nickel and the like, and the carrier is one or two of coconut shell activated carbon or apricot shell activated carbon. An iridium-based catalyst containing nickel iron sulphide for the gas-phase carbonylation of methanol to produce methyl acetate. The catalyst is used for preparing CH in a fixed bed reactor under certain temperature and pressure and the action of the catalyst3OH and CO can be converted into methyl acetate with high activity and high selectivity.
Description
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to an active carbon-loaded iridium-based catalyst containing nickel iron sulfide, and preparation and application thereof.
Background
Methyl acetate is increasingly replacing acetone, butanone, ethyl acetate, cyclopentane, etc. internationally. Because it does not limit the discharge of organic pollutants, it can reach the new environmental standard of paint, printing ink, resin and adhesive factories. The synthesis of ethanol by methyl acetate hydrogenation is also one of the main ways for preparing ethanol by coal at present. The preparation method mainly comprises (1) directly carrying out esterification reaction on acetic acid and methanol by taking sulfuric acid as a catalyst to generate a methyl acetate crude product, then dehydrating by using calcium chloride, neutralizing by using sodium carbonate, and fractionating to obtain a methyl acetate finished product. (2) Dimethyl ether is synthesized by carbonylation on an H-MOR molecular sieve catalyst, but the molecular sieve is easy to be deactivated by carbon deposition, and the space-time yield is very low. (3) When the methanol is carbonylated to prepare the acetic acid, the methyl acetate exists as a byproduct, but the selectivity is low and the separation cost is high. The vast majority of the current commercially viable methyl acetate synthesis routes go through the intermediate step of acetic acid.
Currently, the methanol carbonylation process dominates in the industrial production of acetic acid, and the production capacity of the current acetic acid production device adopting the process accounts for 94 percent of the total production capacity of acetic acid. The industrial process for the carbonylation of methanol to produce acetic acid has gone through roughly three stages of development over the past 50 years:
the first stage is as follows: the BSAF company first achieved the commercial production of acetic acid by the methanol carbonylation process using a cobalt catalyst at relatively high reaction temperatures and pressures (250 ℃, 60MPa) in 1960. The acetic acid produced by the method has low purity, the main byproducts are higher alcohol, higher aldehyde and higher carboxylic acid, and the product separation cost is higher. And a second stage: the company Monsanto developed rhodium-iodides (RhI) with higher activity and selectivity3) A catalytic system. The reaction temperature and pressure were also relatively low (about 175 ℃ C., 3.0MPa), and the selectivity of acetic acid based on methanol was 99% or more, and the selectivity based on CO was also 90% or more. The corrosion resistance of the device is very high, and a full zirconium alloy reaction kettle is needed. And a third stage: the industrialization of Ir catalysts is the methanol carbonylation process for the production of acetic acid. The process greatly improves the stability of the catalyst, the reaction is carried out under the condition of lower water content, the generation of liquid by-products is reduced, and the conversion rate of CO is improved. The Celanese chemical company improves the stability of the Rh catalyst by adding high-concentration inorganic iodide (mainly lithium iodide), and after adding the lithium iodide and methyl iodide auxiliary agent, the water content in the reactor can be obviously reduced (about 4-5 percent), and simultaneously, higher carbonylation rate can be maintained, and the separation cost of the new process is obviously reduced.
The company Chiyoda, japan, and UOP jointly developed the acitica process based on a heterogeneous Rh catalyst in which an active Rh complex is chemically immobilized on a polyvinylpyridine resin. The strong and weak coordinate bond chelating polymer catalyst which is formed by researching and combining the Yuan-national Cynanchum Paniculatum of the chemical research institute of Chinese academy of sciences also forms an independent intellectual property system, and the catalyst system has the characteristics of high stability, high activity and the like and can improve the selectivity of CO utilization.
Although homogeneous Rh-based and Ir-based catalytic systems have achieved good industrial applications, considerable catalytic activity and selectivity have been achieved, with selectivity to acetic acid being greater than 99%. However, since the emergence of the homogeneous catalyst system, certain disadvantages are presented, such as easy loss of the noble metal catalyst, difficult separation of the product from the catalyst, complex catalyst circulation and recovery, etc.
In view of the above-mentioned shortcomings of homogeneous reaction catalytic systems, some researchers have focused on supported heterogeneous catalytic systems. Compared with homogeneous catalysis systems, heterogeneous catalysis systems have natural advantages, for example, the catalyst and the product are convenient to separate, the concentration of the catalyst is not limited by solubility, and the productivity can be improved by increasing the concentration of the catalyst. The load type heterogeneous catalysis system can be roughly divided into a polymer carrier, an activated carbon carrier, an inorganic oxide carrier and other systems according to different carriers, but the load type catalyst system has the problems of lower activity than that of the homogeneous catalysis system, easy removal of active ingredients, higher requirement on the carrier, insufficient stability of the catalyst and the like.
Thus, the current methanol carbonylation to synthesize acetic acid has limited potential for mining. Methyl acetate is prepared by carbonylation of methanol at high selectivity, so that an acetic acid synthesis route is directly skipped, expensive zirconium materials are not used, the esterification process is reduced, and the mass production cost is saved.
Disclosure of Invention
The invention aims to provide a sulfur-containing iridium-based catalyst which takes sulfur-containing iridium as a main active component, takes one or two of other sulfur compounds such as iron, nickel and the like as a cocatalyst, takes one or two of coconut shell activated carbon or apricot shell activated carbon as a carrier, and is used for preparing methyl acetate through methanol gas-phase carbonylation. The catalyst is used for preparing CH in a fixed bed reactor under certain temperature and pressure and the action of the catalyst3OH and CO may be highly reactiveAnd the methyl acetate is converted with high selectivity. The technical scheme of the invention is as follows:
a sulfur-containing iridium-based catalyst for preparing methyl acetate from methanol by gas-phase carbonylation and with the help of iron and nickel sulfide is characterized by comprising a main catalyst, sulfur, a cocatalyst and a carrier. The active component of the main catalyst is iridium, one or more of other iron, nickel and other sulfides are taken as an auxiliary agent, the carrier is coconut shell activated carbon, and the specific surface area of the coconut shell activated carbon is 500-1000 m2(ii) the average pore diameter is 1-200 nm, and the specific surface area of the apricot shell carbon is 600-1200 m2(ii)/g, the average pore diameter is 1 to 200 nm.
The main catalyst is a soluble compound of iridium, preferably chloride and chloroiridic acid, wherein the content of the main active component iridium is 0.1-5.0% of the weight of the catalyst.
The catalyst contains sulfur, and the atomic ratio of the sulfur to an active component Ir of the main catalyst is 0.5-6: 1.
the catalyst is characterized in that the catalyst needs to be sulfurized, and sulfur is one or more than two of soluble sulfur-containing compounds such as hydrogen sulfide, ammonium sulfide, sodium sulfide, potassium sulfide, thiourea and thioacetamide (preferably one or two of ammonium sulfide, thiourea, hydrogen sulfide and thioacetamide).
The catalyst promoter is one or two of iron sulfide, ferrous disulfide, nickel sulfide and other sulfur-containing compounds; the carrier is one or more than two of coconut shell carbon or apricot shell carbon; the atomic ratio of sulfur to iron or nickel is 0.5-6.
The activated carbon is coconut shell activated carbon or apricot shell activated carbon, wherein the specific surface area of the coconut shell activated carbon is 550-900 m2The average pore diameter is 5-100 nm optimally; the specific surface area of the apricot shell carbon is 650-1000 m2The average pore diameter is preferably 5 to 100 nm.
IrCl is added3Or H2IrCl6And a precursor mixed solution of an oxide or chloride of a cocatalyst, dipping the mixed solution on activated carbon for 2-4 h, evaporating the solvent in a water bath at 60-80 ℃, and drying the solvent in an oven at 100-120 DEG CDrying for 8 hours, roasting for 4 hours at 250-400 ℃ under the protection of nitrogen, and then carrying out liquid phase or gas phase vulcanization treatment, wherein the vulcanization temperature is 200-450 ℃, the vulcanization time is 1-6 hours, and the preferable vulcanization time is 1-2 hours.
The CO and pumped reactants such as methanol and the like enter a fixed bed reactor filled with the granular catalyst to carry out methanol carbonylation reaction, the main product is methyl acetate, and a trace or small amount of acetic acid by-product is generated.
The temperature of the carbonylation reaction is 180-280 ℃, the pressure is 0.5-3.5 MPa, and the liquid volume space velocity is 0.1-15 h-1。
The cocatalyst reactant also comprises methyl iodide which accounts for 5-35.0% of the weight of the methanol.
The main reactor is made of hastelloy.
The catalyst for preparing methyl acetate by carbonylation of methanol is used for the reaction of converting methanol/CO as raw materials into methyl acetate, and a certain amount of H is required to be added into reaction gas2，H2And the volume ratio of the CO to the carbon dioxide is 0.01-2: 1.
The invention has the beneficial effects that:
compared with the prior art, the heterogeneous catalyst is relatively simple in product separation, and meanwhile, in a reaction liquid-phase product, reaction byproducts only comprise process water and a small amount or trace amount of acetic acid, the water content is low, and a large amount of unreacted methanol and noncorrosive methyl acetate are also contained, so that the product is low in corrosivity, and the core part of a reaction device only needs Hastelloy in material, so that the heterogeneous catalyst has the advantage of low investment. Meanwhile, the catalyst contains sulfur, so that the stability and the activity of the catalyst are greatly improved, the conversion rate of methanol and the selectivity of methyl acetate are both high, the reaction pressure is low, and the running cost of the device is low.
Detailed Description
The following examples illustrate but do not limit the invention claimed.
Example 1
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal AC. Evaporating in 80 deg.C water bathAnd drying the solvent in a 120 ℃ oven for 8h, and roasting at 300 ℃ for 2h under the protection of nitrogen to obtain the active carbon-loaded sulfur-free Ir/AC catalyst.
Example 2
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal AC. Evaporating solvent in 80 deg.C water bath, oven drying at 120 deg.C for 8 hr, roasting at 300 deg.C under nitrogen protection for 2 hr, and adding 10% H2S/H2Vulcanizing the gas at 300 ℃ for 6H, and cooling to obtain H2S gas phase sulfided activated carbon supported sulfur-containing Ir-S/AC catalyst.
Example 3
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3And 0.54g FeCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating solvent in 80 deg.C water bath, oven drying at 120 deg.C for 8 hr, roasting at 300 deg.C under nitrogen protection for 4 hr, and adding 10% H2S/H2And vulcanizing the gas at 320 ℃ for 6h, and cooling to obtain the active carbon-loaded sulfur-containing iridium-based catalyst Ir-Fe-S/AC.
Example 4
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3And 0.65g of NiCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating solvent in 80 deg.C water bath, oven drying at 120 deg.C for 8 hr, roasting at 300 deg.C under nitrogen protection for 4 hr, and adding 10% H2S/H2And vulcanizing the gas at 320 ℃ for 6h, and cooling to obtain the active carbon-loaded sulfur-containing iridium-based catalyst Ir-Ni-S/AC.
Example 5
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3And 0.54g FeCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating solvent in 80 deg.C water bath, oven drying at 120 deg.C for 8 hr, roasting at 300 deg.C under nitrogen protection for 4 hr, and adding 8% (NH)4)2And dropwise adding the S aqueous solution in the same volume, standing and curing for 6h, and drying at 120 ℃ for 12h to obtain the active carbon-loaded sulfur-containing iridium-based catalyst Ir-Fe-S/AC-2.
Example 6
Measuring and measuring5mL of concentrated HCl was added to 10mL of deionized water, and 0.24g of IrCl was weighed3And 0.54g FeCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating the solvent in a water bath at 80 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, dropwise adding an aqueous solution in which 2.47g of thiourea is dissolved in the aqueous solution at the same volume, standing and curing for 6h, and drying at 120 ℃ for 12h to obtain the active carbon-supported sulfur-containing iridium-based catalyst Ir-Fe-S/AC-3.
Example 7
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3And 0.54g FeCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating the solvent in a water bath at 80 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, dripping an aqueous solution in which 2.46g of thioacetamide is dissolved into the solution in an equal volume, standing and curing the solution for 6h, and drying at 120 ℃ for 12h to obtain the active carbon-supported sulfur-containing iridium-based catalyst Ir-Fe-S/AC-4.
Example 8
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3、0.65gNiCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating solvent in 80 deg.C water bath, oven drying at 120 deg.C for 8 hr, roasting at 300 deg.C under nitrogen protection for 4 hr, and adding 8% (NH)4)2And dropwise adding the S aqueous solution in the same volume, then standing and curing for 6h, and drying at 120 ℃ for 12h to obtain the active carbon-loaded sulfur-containing iridium-based catalyst Ir-Ni-S/AC-2.
Example 9
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3、0.65gNiCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating the solvent in a water bath at 80 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, dropwise adding an aqueous solution in which 2.47g of thiourea is dissolved in the aqueous solution at the same volume, standing and curing for 6h, and drying at 120 ℃ for 12h to obtain the active carbon-supported sulfur-containing iridium-based catalyst Ir-Ni-S/AC-3.
Example 10
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3、0.65gNiCl2In the above 15mL of hydrochloric acidDissolved in the solution, and then impregnated with 10.0g of coconut shell charcoal. Evaporating the solvent in a water bath at 80 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, dripping an aqueous solution in which 2.46g of thioacetamide is dissolved into the solution in an equal volume, standing and curing the solution for 6h, and drying at 120 ℃ for 12h to obtain the active carbon-supported sulfur-containing iridium-based catalyst Ir-Ni-S/AC-4.
Example 11
5mL of concentrated HCl was weighed into 10mL of deionized water, and 0.24g of IrCl was weighed3、0.54gFeCl2、0.15gNiCl2Dissolved in the above 15mL of hydrochloric acid solution, and then impregnated with 10.0g of coconut charcoal. Evaporating solvent in 80 deg.C water bath, oven drying at 120 deg.C for 8 hr, roasting at 300 deg.C under nitrogen protection for 4 hr, and adding 10% H2S/H2And vulcanizing the gas at 320 ℃ for 6h, and cooling to obtain the active carbon-loaded sulfur-containing iridium-based catalyst Ir-Fe-Ni-S/AC.
The application case is the application of the prepared catalyst in the reaction for preparing methyl acetate by taking methanol and CO as raw materials
Activation of the catalyst: before the catalyst is used, CO/H is in the reactor2＝3，GHSV＝7500h-1In-situ reduction activation is carried out under the conditions that: raising the temperature from room temperature to 240 ℃ at the speed of 5 ℃/min under normal pressure, and keeping the temperature for 1 hour to obtain the activated iridium-based catalyst.
The carbonylation reaction conditions were: 240 ℃, 2.5Mpa, CH3OH/CO/H24/4/1 (mole ratio), LHSV of methanol is 8h-1. After the reaction tail gas is cooled by a cold trap, the gas product is analyzed on line, and a chromatographic instrument is an Agilent 7890B GC, a PQ packed column and a TCD detector. Off-line analysis of liquid phase product, FFAP capillary chromatographic column, FID detector. And (4) performing internal standard analysis, wherein isobutanol is used as an internal standard substance.
Using the iridium-based catalysts prepared in examples 1 to 11, methyl acetate was prepared according to the above-described procedures, and the conversion of methanol and the selectivity of methyl acetate are shown in Table 1.
TABLE 1
Other products are mainly acetic acid, calculated on converted methanol.
Claims (8)
1. The application of an iridium-based catalyst loaded by activated carbon and containing nickel iron sulfide in preparing methyl acetate by methanol gas-phase carbonylation is characterized in that:
the reaction conditions are as follows: the reaction temperature is 180-280 ℃, and the reaction pressure is 0.5-6.5 MPa; the volume space velocity of the reaction liquid is 0.1-15 h-1The molar ratio of CO to methanol is 0.25-2, and H2And CO in a volume ratio of 0.01-2, wherein methyl acetate is a required main product; a cocatalyst methyl iodide needs to be added into the reactor, and the addition amount of the methyl iodide is 5-35% of that of the methanol;
the catalyst comprises a main catalyst, sulfur, a cocatalyst and a carrier:
the main catalyst is one or more than two of iridium sulfides,
the cocatalyst is one or more of iron sulfide, ferrous disulfide and nickel sulfide;
the carrier is one or more than two of coconut shell carbon or apricot shell carbon;
the iridium accounts for 0.5-5.0 wt% of the total mass of the catalyst; the catalyst promoter Fe and/or Ni accounts for 0.1-5.0 wt% of the total mass of the catalyst, the atomic ratio of sulfur in the iridium sulfide to iridium is 0.5-6: 1, and the atomic ratio of sulfur in the catalyst promoter to Fe and/or Ni is 0.5-6: 1;
before use, the vulcanized catalyst needs to be subjected to reduction activation, the activation temperature in the synthesis gas is 200-450 ℃, the activation time is 1-4H, and the synthesis gas is CO and H2The molar ratio is 1-20: 1.
2. Use according to claim 1, characterized in that:
the carrier is one or two of coconut shell activated carbon or apricot shell activated carbon, and the specific surface area of the coconut shell activated carbon is 500-1100 m2The average pore diameter of the coconut shell carbon is 1-200 nm; the specific surface area of the apricot shell carbon is 600-1200 m2The average pore diameter of the apricot shell carbon is 1-200 nm.
3. Use according to claim 2, characterized in that:
the specific surface area of the coconut shell carbon is 550-900 m2The average pore diameter of the coconut shell carbon is 1-100 nm; the specific surface area of the apricot shell carbon is 650-1000 m2The average pore diameter of the apricot shell carbon is 1-100 nm.
4. Use according to claim 1, characterized in that: the preparation method of the catalyst comprises the following steps of,
firstly, preparing an iridium-based catalyst loaded by activated carbon and containing iron and nickel, and then vulcanizing by using a sulfur source;
the preparation method of the iridium-based catalyst loaded by the activated carbon and containing iron and nickel comprises the following steps: under the action of acid, dissolving an iridium precursor and a precursor of an iron-nickel catalyst promoter in one or two solvents of water, ethanol or acetone; then dipping the obtained precursor mixed solution on a carrier for 2-4 h, evaporating the solvent in a water bath at 60-100 ℃, drying at 100-120 ℃ in an oven, roasting at 250-400 ℃ for 1-4 h under the protection of nitrogen or argon, and finally performing liquid phase or gas phase vulcanization at 200-500 ℃ for 1-6 h;
the acid is hydrochloric acid, nitric acid or sulfuric acid;
the precursor of the iridium is Ir2O3、IrO2、Ir(OH)3、Ir(OH)4、IrCl3、IrCl4、H2IrCl6、[Ir(CO)2I2]-One or more than two of them;
the precursor of the cocatalyst Fe is an iron-containing compound: one or more of ferric nitrate, ferric acetate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric oxalate, ferrous oxalate, ferric gluconate, ferric citrate, ferric phosphate, ferric stearate, ferric benzoate, ferric bromide, ferrous oxalate, ferric iodide and ferrous iodide;
the precursor of Ni of the cocatalyst is a soluble nickel compound: one or more of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, nickel oxalate, nickel gluconate, nickel citrate, nickel phosphate, nickel stearate, nickel benzoate, nickel bromide and nickel iodide.
5. Use according to claim 4, characterized in that: the vulcanization time is 1-2 h;
the acid is any one of concentrated hydrochloric acid with the molar concentration of 12mol/L, 14.4mol/L concentrated nitric acid or 18mol/L concentrated sulfuric acid;
the precursor of the iridium is IrCl3And H2IrCl6One or two of them.
6. Use according to claim 4, characterized in that:
one mode of sulfidation of the catalyst is H2S gas phase vulcanization, H2S gas is vulcanized through a catalyst bed layer, the vulcanizing temperature is 250-400 ℃, and the time is 1-6 hours;
another sulfidation mode for the catalyst is liquid phase sulfidation: the preparation method comprises the steps of dipping a soluble sulfide precursor solution into a liquid phase for vulcanization, dipping a precursor mixed solution of iridium, iron, nickel and other auxiliaries on activated carbon, drying at 60-120 ℃, preparing an Ir-based catalyst loaded on the activated carbon, dipping the Ir-based catalyst into a precursor solution in which one or two of ammonium sulfide, sodium sulfide, potassium sulfide, thiourea or thioacetamide is dissolved, vulcanizing, curing for 1-6 hours, and drying and roasting.
7. Use according to claim 1, characterized in that:
the synthesis gas is CO and H2The molar ratio is 1-10: 1.
8. Use according to claim 1, characterized in that:
the main reactor is made of hastelloy.
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