CN109759085B - Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof - Google Patents
Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof Download PDFInfo
- Publication number
- CN109759085B CN109759085B CN201711094531.1A CN201711094531A CN109759085B CN 109759085 B CN109759085 B CN 109759085B CN 201711094531 A CN201711094531 A CN 201711094531A CN 109759085 B CN109759085 B CN 109759085B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- activated carbon
- iron
- sulfide
- carbon
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An active carbon loaded iron sulfide based catalyst for preparing methyl acetate by methanol gas phase carbonylation, a preparation method and an application thereof. The catalyst consists of a main catalyst and a carrier, wherein the active component of the main catalyst is one or two or more of ferric sulfide, ferrous sulfide or ferrous disulfide, and the carrier is one or two of coconut shell activated carbon or apricot shell activated carbon. The invention provides an active carbon loaded iron sulfide based catalyst for preparing methyl acetate by methanol gas phase carbonylation, which is composed of one or two or more of ferric sulfide, ferrous sulfide or ferrous disulfide as main active ingredients and one or two of coconut shell active carbon or apricot shell active carbon as carriers. 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 iron sulfide-based catalyst, and preparation and application thereof, which are used for a reaction for preparing methyl acetate by methanol gas-phase carbonylation. The catalyst is used in a fixed bed reactor, methyl iodide is used as a cocatalyst, and CH is added under the action of the catalyst at certain temperature and pressure3OH and CO can be converted into methyl acetate with high activity and high selectivity.
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 traditional method is to esterify acetic acid and methanol by using concentrated sulfuric acid as a catalyst, dehydrate the acetic acid and the methanol by using calcium chloride, neutralize the acetic acid and the methanol by using sodium carbonate, and fractionate the acetic acid and the methanol to obtain a methyl acetate finished product, but the process is complex and the concentrated sulfuric acid is required to be used. The second method is to use the technology of methanol carbonylation to prepare acetic acid, and to obtain methyl acetate with high activity, high selectivity and high stability in a fixed bed at one time by modulating the composition and process of the catalyst, but all require the use of noble metal catalyst iridium or rhodium. Therefore, the exploration of the non-noble metal catalyst with high activity and high selectivity has epoch-making significance for preparing methyl acetate by methanol carbonylation, and also attracts the attention of a plurality of scientific researchers.
In recent years, it has been reported that activated carbon-supported molybdenum sulfide-based catalyst is used for catalyzing methanol gas phase carbonylation with high selectivity in a non-noble metal non-iodine system, but the activated carbon-supported molybdenum sulfide-based catalyst has low activity, quick inactivation and instability; the synthesis of methyl acetate by the carbonylation of dimethyl ether on an H-MOR molecular sieve catalyst also draws attention of people, but the molecular sieve is easy to be deactivated by carbon deposition and has low space-time yield. Furthermore, the scholars reported that the activated carbon supported Ni-based catalyst also showed good activity for methanol vapor phase carbonylation, but the pain point was still that the catalyst was unstable.
Therefore, based on the development trend of synthesizing methyl acetate by methanol carbonylation at present and combining the characteristics and advantages of the traditional methanol carbonylation, the invention provides the supported catalyst for preparing the methyl acetate by the gas-phase carbonylation of the iron sulfide-based methanol, which takes the activated carbon-supported iron sulfide-based catalyst as the main catalyst and the methyl iodide as the cocatalyst. The catalyst has good activity and strong stability.
Disclosure of Invention
The invention aims to provide an iron sulfide-based catalyst taking one or two of iron sulfide, ferrous sulfide or ferrous disulfide as main components, which is used for the reaction of preparing methyl acetate by methanol gas-phase carbonylation. The catalyst is used in a fixed bed reactor, methyl iodide is used as a cocatalyst, and CH is added under the action of the catalyst at certain temperature and pressure3OH and CO can be converted into methyl acetate with high activity and high selectivity.
The technical scheme of the invention is as follows:
an iron sulfide-based catalyst containing a cocatalyst and used for preparing methyl acetate by methanol through gas-phase carbonylation, a preparation method and an application thereof.
The precursor of the iron is one or more than two of soluble iron-containing compounds 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 sulfur source 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, and the content and the mole number of iron are 0.5-4.
The carrier active carbon is coconut shell active carbon or apricot shell active carbon, wherein the specific surface area of the coconut shell active 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.
The iron-based sulfide catalyst needs to be prepared with active carbon-loaded iron-based catalyst and then subjected to gas-phase or liquid-phase vulcanization. The gas-phase vulcanization needs to be carried out for 2 hours at 200-500 ℃ before the sulfur source is switched for vulcanization or reduction and vulcanization are carried out simultaneously, or direct liquid-phase vulcanization is carried out.
The iron sulfide-based catalyst for preparing methyl acetate by gas-phase carbonylation of methanol, according to claim 1, before use, the prepared catalyst needs to be treated in situ with synthesis gas or hydrogen in a reactor at 200-450 ℃ for 1-4 h, then reactants such as CO and pumped methanol enter a fixed bed reactor filled with the granular catalyst of the invention to carry out methanol carbonylation, the main product is methyl acetate, and a trace or small amount of acetic acid byproduct is generated.
The temperature of the carbonylation reaction is 180-300 ℃, 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.
A catalyst for preparing methyl acetate from methanol by carbonylation is used for the reaction of converting methanol/CO as raw material to methyl acetate and the reaction gas contains H2，H2And the volume ratio of the carbon dioxide to the CO is 0.01-2.
The invention has the beneficial effects that:
compared with the prior art, the active carbon-supported iron sulfide-based catalyst for preparing methyl acetate by methanol gas-phase carbonylation and the preparation and application thereof are disclosed. The catalyst has high activity and good stability, does not use noble metal, and has great progress and epoch-making significance compared with the traditional Rh-based and Ir-based catalysts.
Secondly, the product separation is relatively simple, meanwhile, in the reaction liquid phase product, the reaction by-products only comprise process water and a small amount or trace amount of acetic acid, the water content is lower, and a large amount of unreacted methanol and noncorrosive methyl acetate are also contained, so that the product has lower corrosivity, the core part of the reaction device only needs hastelloy to be made of materials, and the method has the advantage of low investment. Meanwhile, the conversion rate of the methanol and the selectivity of the methyl acetate are both high, the reaction pressure is low, and the operation cost of the device is low.
Detailed Description
The following examples illustrate but do not limit the invention claimed, and the activation and evaluation conditions of the catalyst are described below.
Example 1
0.55g of FeCl was taken2.4H2O, dissolved in 7.5ml of H22.5ml of concentrated hydrochloric acid was added to the O aqueous solution to make FeCl2Completely dissolving, adding 5g of coconut shell activated carbon into the precursor solution, drying in a drying oven at 90 ℃ for 6h, transferring to a tube-making furnace, roasting with Ar at 30 ℃ for 2h, and cooling to obtain activated carbon-loaded FeCl2Is an iron source, non-sulfided iron-based catalyst.
Example 2
0.85g of ammonium molybdate was taken and dissolved in 7.5H2Dissolving ammonium molybdate completely in water solution O, adding 5g of coconut shell activated carbon into the precursor solution,then placing the mixture in a drying oven at 90 ℃ for drying for 6H, transferring the mixture in a tube-making furnace, roasting the mixture at 300 ℃ by using inert gas, and then using 10% H by volume fraction2S/H2And (4) vulcanizing at 400 ℃ for 6h and cooling to obtain the activated carbon loaded gas-phase vulcanized Mo-based catalyst.
Example 3
0.55g of FeCl was taken2.4H2O, dissolved in 7.5ml of H22.5ml of concentrated hydrochloric acid was added to the O aqueous solution to make FeCl2Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 deg.C oven for 6H, transferring to a tube-making furnace, and adding 10% H at 320 deg.C2S/H2Cooling after 6h of vulcanization to obtain FeCl loaded by active carbon2Is a source of iron, H2S is a sulfureted iron-based catalyst with sulfur source directly sulfurized in gas phase.
Example 4
0.55g of FeCl was taken2.4H2O, dissolved in 7.5ml of H22.5ml of concentrated hydrochloric acid was added to the O aqueous solution to make FeCl2Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 ℃ oven for 6H, transferring to a tube-making furnace, roasting at 300 ℃ under the protection of Ar gas for 2H, and then using 10% H2Vulcanizing at S/Ar 320 ℃ for 6h, and cooling to obtain activated carbon-loaded FeCl2Is a source of iron, H2S is a sulfur source and is directly gas-phase vulcanized by the reduction.
Example 5
0.55g of FeCl was taken2.4H2O, dissolved in 7.5ml of H22.5ml of concentrated hydrochloric acid was added to the O aqueous solution to make FeCl2Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 deg.C oven for 6h, transferring to a tube-making furnace, roasting at 300 deg.C under Ar gas protection for 2h, and adding 7.5ml of 8% (NH)4)2Impregnating with S solution, drying at 90 ℃, and roasting at 300 ℃ for 2h under Ar gas to obtain activated carbon-loaded FeCl2Is iron source, (NH)4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 6
0.55g of FeCl was taken2.4H2O, dissolved in 7.5ml of H22.5ml of concentrated hydrochloric acid was added to the O aqueous solution to make FeCl2Completely dissolving, adding 5g of coconut shell activated carbon into the precursor solution, then placing the precursor solution in a drying oven at 90 ℃ for drying for 6h, weighing 1.24g of thiourea to dissolve in 7.5ml of water solution, then placing the prepared activated carbon-supported catalyst into the solution for soaking, after 6h of curing, transferring the solution into the drying oven at 90 ℃ for drying, and roasting the solution at 300 ℃ under Ar gas for 2h to obtain activated carbon-supported FeCl2Is an iron source, thiourea is a sulfur source, and the liquid phase vulcanization is directly carried out on the iron sulfide-based catalyst.
Example 7
0.55g of FeCl was taken2.4H2O, dissolved in 7.5ml of H22.5ml of concentrated hydrochloric acid was added to the O aqueous solution to make FeCl2Completely dissolving, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 ℃ oven for 6h, and weighing 1.24g of thioacetamide C2H5NS is dissolved in 7.5ml of water solution, the prepared activated carbon supported catalyst is put into the solution for dipping, the solution is cooked for 6 hours and then is transferred into an oven at 90 ℃ for drying, and the dried solution is roasted for 2 hours at 300 ℃ under Ar gas to obtain activated carbon supported FeCl2Is iron source, thioacetamide is sulfur source, and is directly liquid-phase sulfurized iron-based catalyst.
Example 8
0.45g of FeCl was taken3Dissolved to 7.5ml of H2In an aqueous O solution, FeCl3Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 ℃ oven for 6H, transferring to a tube-making furnace, roasting at 300 ℃ under the protection of Ar gas for 2H, and then using 10% H2S/H2Vulcanizing at 320 ℃ for 6h, and cooling to obtain FeCl loaded with activated carbon3Is a source of iron, H2S is a sulfur source, and the sulfur source is directly gas-phase reduced and vulcanized.
Example 9
0.45g of FeCl was taken3Dissolved to 7.5ml of H2In an aqueous O solution, FeCl3Completely dissolved and thenAdding 5g of coconut shell activated carbon into the precursor solution, drying in an oven at 90 ℃ for 6h, and adding 7.5ml of 8% (NH)4)2Impregnating with S solution, drying at 90 ℃, and roasting at 300 ℃ for 2h under Ar gas to obtain activated carbon-loaded FeCl3Is iron source, (NH)4)2S is a sulfur source, and is a ferrous sulfide-based catalyst which is directly subjected to liquid phase reduction and vulcanization.
Example 10
1.17g of FeI are taken3Dissolved to 7.5ml of H2In an aqueous O solution, FeI3Dissolving completely, adding 5g of active carbon into the precursor solution, drying in a 90 ℃ oven for 6H, transferring to a tube-making furnace, roasting at 300 ℃ under the protection of Ar gas for 2H, and then using 10% H2S/H2Sulfurizing at 320 deg.C for 6h, and cooling to obtain FeI loaded with coconut shell activated carbon3Is a source of iron, H2S is a sulfur source, and the sulfur source is directly gas-phase reduced and vulcanized.
Example 11
1.17g of FeI are taken3Dissolved to 7.5ml of H2In an aqueous O solution, FeI3Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in an oven at 90 deg.C for 6 hr, adding 7.5ml of 8% (NH)4)2Impregnating with S solution, drying at 90 ℃, and roasting at 300 ℃ for 2h under Ar gas to obtain FeI loaded with activated carbon3Is iron source, (NH)4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 12
0.83g of FeI was taken2Dissolved to 7.5ml of H2In an aqueous O solution, FeI2Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 ℃ oven for 6H, transferring to a tube-making furnace, roasting at 300 ℃ under the protection of Ar gas for 2H, and then using 10% H2S/H2Vulcanizing at 320 ℃ for 6h, and cooling to obtain the FeI loaded with the activated carbon2Is a source of iron, H2S is a sulfur source, and the sulfur source is directly gas-phase reduced and vulcanized.
Example 13
0.83g of FeI was taken2Dissolved to 7.5ml of H2In an aqueous O solution, FeI2Dissolving completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in an oven at 90 deg.C for 6 hr, adding 7.5ml of 8% (NH)4)2Impregnating with S solution, drying at 90 ℃, and roasting at 300 ℃ for 2h under Ar gas to obtain FeI loaded with activated carbon2Is iron source, (NH)4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 14
0.4597g of ferrous nitrate Fe (NO) are taken3)2·6H2O, dissolved in 7.5ml of H2Dissolving ferrous nitrate in O water solution completely, adding 5g of coconut shell activated carbon into the precursor solution, drying in a 90 deg.C oven for 6 hr, adding 7.5ml of 8% (NH)4)2Soaking in S solution, drying at 90 deg.C, and roasting at 300 deg.C under Ar gas for 2 hr to obtain active carbon-supported Fe (NO)3)2Is iron source, (NH)4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 15
0.7106g of ferrous sulfate FeSO are taken4·7H2O, dissolved in 7.5ml of H2Dissolving ferrous sulfate in O water solution completely, adding 5g of activated carbon into the precursor solution, drying in a 90 deg.C oven for 6 hr, and adding 7.5ml of 8% (NH)4)2Impregnating with S solution, drying at 90 ℃, and roasting at 300 ℃ for 2h under Ar gas to obtain FeSO loaded with activated carbon4Is iron source, (NH)4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 16
0.4880g of iron acetate C were taken4H7FeO5Dissolved to 7.5ml of H2Dissolving ferric acetate in O water solution completely, adding 5g of activated carbon into the precursor solution, drying in a 90 deg.C oven for 6 hr, adding 7.5ml of 8% (NH)4)2Impregnating with S solution, drying at 90 ℃, and roasting at 300 ℃ for 2h under Ar gas to obtain the activated carbon loadThe iron acetate is an iron source, (NH)4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 17
0.6260g of ferric citrate hydrate FeC are taken6H5O7Dissolved to 7.5ml of H2Dissolving ferric citrate in O water solution completely, adding 5g of activated carbon into the precursor solution, drying in a 90 deg.C oven for 6h, transferring to a tube-making furnace, roasting at 300 deg.C under protection of Ar gas for 2h, and adding 7.5ml of 8% (NH)4)2Soaking in S solution, drying at 90 deg.C, and roasting at 300 deg.C under Ar gas for 2 hr to obtain active carbon loaded ferric citrate (NH) as iron source4)2S is a sulfur source and is directly used as a liquid phase vulcanized iron-based catalyst.
Example 18
The nickel sulfide-based catalyst of the embodiment 3 is used, the reaction temperature is 260 ℃, under the same conditions of other reactions and/or activation,
2.5Mpa，CH3OH/CO/H210/10/1 (mole ratio), LHSV of methanol is 6h-1。
Example 19
Using the nickel sulfide based catalyst of example 3, the reaction temperature was 260 ℃ and CO/H24 under other conditions, 2.5MPa, CH3OH/CO/H210/10/1 (mole ratio), LHSV of methanol is 6h-1。
Example 20
The nickel sulfide-based catalyst of example 3 was used under the reaction pressure of 1.7MPa and under the other conditions,
240℃，CH3OH/CO/H210/10/1 (mole ratio), LHSV of methanol is 6h-1。
Example 21
Using the nickel sulfide-based catalyst of example 3, methanol LHSV was 8h-1Under other conditions, at 240 deg.C and 2.5MPa, CH3OH/CO/H210/10/1 (molar ratio).
Example 22
Using the nickel sulfide-based catalyst of example 3, the pre-reaction activation temperature was 260 deg.CUnder other conditions, at 240 deg.C and 2.5MPa, CH3OH/CO/H210/10/1 (mole ratio), LHSV of methanol is 6h-1。
Example 23
Using the nickel sulfide-based catalyst of example 3, the pre-reaction activation temperature was 280 ℃ under the same conditions as those of 240 ℃, 2.5MPa, CH3OH/CO/H210/10/1 (mole ratio), LHSV of methanol is 6h-1。
The application cases 1-17 are applications of the prepared catalyst in a reaction for preparing methyl acetate by taking methanol and CO as raw materials, wherein the activation of the catalyst and the methanol fixed bed carbonylation reaction conditions in the application cases 1-17 are as follows, the reaction temperature and pressure and the catalyst activation conditions in the application cases 18-23 are slightly adjusted and changed, and the change conditions are mainly the change in the implementation cases.
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 for 1h, and the conditions are as follows: 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 iron sulfide-based catalyst.
The carbonylation reaction conditions were: 240 ℃, 2.5Mpa, CH3OH/CO/H210/10/1 (mole ratio), LHSV of methanol is 6h-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 iron sulfide-based catalysts prepared in examples 1 to 17, methyl acetate was prepared according to the above procedure, 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 (10)
1. The application of an activated carbon-supported iron sulfide-based catalyst in the preparation of one or a mixture of two of acetic acid and methyl acetate by methanol gas-phase carbonylation is characterized in that: the catalyst comprises a main catalyst and a carrier, wherein the main catalyst comprises:
the main catalyst comprises one or more of ferric sulfide, ferrous sulfide or ferrous disulfide;
the carrier is one or two of coconut shell carbon or apricot shell carbon;
the iron accounts for 0.5-10.0 wt% of the total mass of the catalyst, and the atomic ratio of the sulfur to the iron is 0.5-6: 1.
2. Use according to claim 1, characterized in that:
the iron accounts for 1-8 wt% of the total mass of the catalyst.
3. Use according to claim 1, characterized in that:
the iron accounts for 1-5 wt% of the total mass of the catalyst.
4. Use according to claim 1, characterized in that:
the carrier is one 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.
5. Use according to claim 1, characterized in that:
the carrier is one of coconut shell activated carbon or apricot shell activated carbon, and the specific surface area of the coconut shell activated carbon is 550-900 m2The average pore diameter of the coconut shell carbon is 1-100 nm;
apricot shell charcoalThe specific surface area of the polymer is 650 to 1000m2The average pore diameter of the apricot shell carbon is 1-100 nm.
6. Use according to claim 1, characterized in that:
firstly preparing an active carbon-loaded Fe catalyst, and then vulcanizing by using a sulfur source;
the preparation process of the Fe-Fe catalyst loaded by the active carbon comprises the following steps: dissolving an iron source in one or two solvents of water, ethanol or acetone to obtain an iron precursor solution, soaking the iron precursor solution on carrier activated carbon for 2-4 h, drying at 60-120 ℃, roasting for 1-6 h at 250-500 ℃ under the protection of inert gases such as nitrogen or argon, and then performing gas-phase or liquid-phase vulcanization at 200-400 ℃ for 1-6 h, wherein the atomic ratio of sulfur to iron is 0.5-6: 1;
one of the ways of vulcanization is gas phase vulcanization:
firstly preparing an active carbon-supported Fe-based catalyst in advance, and then using H in a tubular furnace2Restore first, then switch H2S sulfurization, or direct use of H in a tube furnace2And H2Reducing and vulcanizing the mixed gas of S; h2The volume content of S is 1-20%; the temperature of reduction and vulcanization is 200-600 ℃, and the time is 1-12 h;
or, the second mode of vulcanization is liquid phase vulcanization:
firstly, preparing a precursor solution containing a sulfur source, wherein the sulfur source is one or more than two of hydrogen sulfide, ammonium sulfide, sodium sulfide, potassium sulfide, thiourea or thioacetamide, and the mass fraction of sulfur in the precursor solution is 1-15%; and soaking the prepared activated carbon-supported Fe-based catalyst in the solution for vulcanization, standing at room temperature for 1-6 h, drying at 80-120 ℃, and then drying and roasting at 200-600 ℃ for 1-6 h.
7. Use according to claim 1, characterized in that:
the catalyst needs to be activated before use, in the presence of CO and H2Synthesis gas or pure H of2The medium activation temperature is 200-450 ℃, the time is 1-4 h, and the synthesis gasIn the formula of CO and H2The molar ratio is 1-20.
8. Use according to claim 1, characterized in that:
the reaction temperature is 180-280 ℃, and the reaction pressure is 0.5-6.5 MPa; the hourly space velocity of the reaction liquid is 0.1-15 h-1The molar ratio of CO to methanol is 0.25-4; the reaction process requires the use of H2，H2And CO in a volume ratio of 0.01-2, wherein in the reaction product, methyl acetate is a required main product, and the selectivity is more than 80 percent.
9. Use according to claim 1, characterized in that:
a cocatalyst methyl iodide needs to be added into the reactor, and the addition amount of the methyl iodide is 5-50.0 wt% of methanol.
10. Use according to claim 1, characterized in that:
the main reactor is made of hastelloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711094531.1A CN109759085B (en) | 2017-11-09 | 2017-11-09 | Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711094531.1A CN109759085B (en) | 2017-11-09 | 2017-11-09 | Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109759085A CN109759085A (en) | 2019-05-17 |
| CN109759085B true CN109759085B (en) | 2021-11-30 |
Family
ID=66448760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711094531.1A Active CN109759085B (en) | 2017-11-09 | 2017-11-09 | Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109759085B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852430B (en) * | 2021-01-07 | 2022-04-08 | 中南大学 | Passivator for repairing mercury contaminated soil and preparation method and application thereof |
| CN113582457B (en) * | 2021-08-10 | 2024-04-05 | 山东理工大学 | Semi-coke wastewater treatment method and semi-coke wastewater treatment system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334789A (en) * | 1999-02-16 | 2002-02-06 | 伊斯曼化学公司 | Method for carbonylation of lower aliphatic alcohols |
| CN1422178A (en) * | 2000-04-05 | 2003-06-04 | 伊斯曼化学公司 | Carbonylation catalyst supported on a carbonized polysulfonated divinylbenzene-styrene copolymer |
| CN104437552A (en) * | 2014-11-21 | 2015-03-25 | 江苏长三角精细化工有限公司 | Toluene chlorination catalyst using activated carbon as carrier |
| CN106140156A (en) * | 2015-04-20 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of activated carbon supported rhodium base catalyst and its preparation method and application |
| CN106179421A (en) * | 2016-07-19 | 2016-12-07 | 天津大学 | The preparation of sulfide catalyst and the application in lignin conversion thereof |
-
2017
- 2017-11-09 CN CN201711094531.1A patent/CN109759085B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334789A (en) * | 1999-02-16 | 2002-02-06 | 伊斯曼化学公司 | Method for carbonylation of lower aliphatic alcohols |
| CN1422178A (en) * | 2000-04-05 | 2003-06-04 | 伊斯曼化学公司 | Carbonylation catalyst supported on a carbonized polysulfonated divinylbenzene-styrene copolymer |
| CN104437552A (en) * | 2014-11-21 | 2015-03-25 | 江苏长三角精细化工有限公司 | Toluene chlorination catalyst using activated carbon as carrier |
| CN106140156A (en) * | 2015-04-20 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of activated carbon supported rhodium base catalyst and its preparation method and application |
| CN106179421A (en) * | 2016-07-19 | 2016-12-07 | 天津大学 | The preparation of sulfide catalyst and the application in lignin conversion thereof |
Non-Patent Citations (2)
| Title |
|---|
| Promotion effect of Fe in mordenite zeolite on carbonylation of dimethyl ether to methyl acetate;Hui Zhou等;《Catalysis Science &Technology》;20150107;第5卷;第1961-1968页 * |
| Reaction of Potassium TetracarbonyIhydridoferrate with Aryl Halides: Mechanistic Study and Extension to the Catalytic Carbonylation of Iodobenzene by a Bimetallic Fe(CO)5-Co2(CO)8 System;Jean-Jacques Brunet;《Organometallics》;19910101;第10卷(第1期);第341-346页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109759085A (en) | 2019-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4918218A (en) | Preparation of acetic acid and methyl acetate | |
| CN106866349B (en) | Method for preparing vinyl chloride by low-temperature hydrochlorination of acetylene | |
| WO2021073123A1 (en) | Hydrogenation catalyst modified with solid phase modifier and use thereof | |
| CN102441383A (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN109759085B (en) | Activated carbon-loaded iron sulfide-based catalyst and preparation and application thereof | |
| CN109046430A (en) | Nitrogen-dopped activated carbon supported palladium-iron catalyst and its application for benzophenone catalytic hydrogenation synthesis benzhydrol | |
| CN109384750B (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CA2823676A1 (en) | Hydrogenation catalyst comprising nickel on carbon | |
| CN101940958A (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN113145130A (en) | Supported copper-containing high-entropy alloy activated carbon catalyst for acetylene hydrochlorination reaction and preparation method and application thereof | |
| CN109485621A (en) | A method of producing gamma valerolactone | |
| CN109759084B (en) | Catalyst for preparing methyl acetate by methanol gas-phase carbonylation and preparation and application thereof | |
| CN115709072B (en) | Catalyst for preparing acetic acid by catalyzing methanol carbonylation and preparation method and application thereof | |
| Panwar et al. | Zinc grafted to magnetic nanostarch for cyclic carbonate synthesis from propargylic alcohols and CO2 at room temperature | |
| CN109759055B (en) | Activated carbon-supported sulfur-containing iridium-based catalyst and preparation and application thereof | |
| CN109759090B (en) | Active carbon-loaded iridium-based catalyst containing nickel iron sulfide, and preparation and application thereof | |
| CN109759086B (en) | Activated carbon loaded iron sulfide based catalyst containing auxiliary agent and preparation and application thereof | |
| Novakova et al. | Palladium-catalyzed liquid-phase hydrogenation/hydrogenolysis of disulfides | |
| CN103539718B (en) | The production method of indoles | |
| CN108067222B (en) | Activated carbon carrier-supported sulfur-promoted iridium-based catalyst and preparation and application thereof | |
| CN106622325B (en) | A kind of rhenium catalyst and its method for catalyzing and synthesizing 2- methyl-1,4-naphthaquinone | |
| CN107952439B (en) | Catalyst for catalyzing methanol carbonylation, preparation method thereof, and method for preparing acetic acid and methyl acetate by methanol carbonylation | |
| CN102441384B (en) | Method for preparing low-carbon olefin catalyst by high-activity-stability carrier-type iron-based synthetic gas | |
| JPH05995A (en) | Production of acetic acid | |
| CN104549496B (en) | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
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 |