CN112705157B - For removing Fe (CO) 5 And/or Ni (CO) 4 Purifying agent of (2), preparation method and application thereof - Google Patents
For removing Fe (CO) 5 And/or Ni (CO) 4 Purifying agent of (2), preparation method and application thereofDownload PDFInfo
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Abstract
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for removing Fe (CO)5 And/or Ni (CO)4 A preparation method and application thereof.
Background
Metal carbonyls are a special class of coordination compounds formed by transition metals and carbon monoxide ligands, also known as carbonyl complexes, which are formed primarily because gas mixtures with high CO partial pressures are susceptible to reaction with pipeline surface components. In the industry starting from synthesis gas, fe (CO)5 And Ni (CO)4 The greatest hazard to the reaction process is that these metal carbonyls decompose and deposit on the catalyst, cover the catalyst surface, block catalyst channels and provide unwanted active sites, produce other by-products, and make separation of subsequent products difficult. Therefore, the method can effectively remove the metal carbonyl compound in the raw material gas, prolong the service activity and service life of the catalyst, and has important strategic significance and good development prospect.
Patent document CN 102814160a relates to a purifying agent for removing carbonyl iron and nickel in synthesis gas, and preparation and application thereof. The general formula of the purifying agent is CuZnAl (0) -carrier, has high removal precision, and can reduce the total content of carbonyl iron and carbonyl nickel in raw material gas from 180ppm to 0.008ppm.
Patent document CN1344672A discloses a Cu-Zn-Cr system purifying agent prepared by adopting a coprecipitation and mechanical mixing method, which not only can effectively remove Fe (CO) in synthesis gas5 And Ni (CO)4 But also plays a role in removing S.
Patent document CN1422692a discloses a protective agent for a supported methanol synthesis catalyst. The protective agent is prepared from Al2 O3 As a carrier, selecting one or more metal oxides from Mo, cu and Cr as a first metal component; at least one group IIA metalThe oxide is used as a metal auxiliary component, and the content of metal carbonyl in the synthesis gas can be reduced to below 0.1 ppm.
Aiming at the problem of low precision of removing metal carbonyl compounds by the existing purifying agent, the purifying agent with low cost, no toxicity, environmental protection and good stability is developed, and has important strategic significance for preparing low-carbon olefin, aromatic hydrocarbon and oxygen-containing compounds from synthetic gas by the purifying agent with high removal efficiency.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for removing Fe (CO)5 And/or Ni (CO)4 The purifying agent provided by the invention has the function of removing Fe (CO) by matching a carrier with a special structure with a specific main active component5 And Ni (CO)4 The purifying agent has the advantages of high efficiency and large capacity of adsorbing Fe and Ni, does not contain toxic heavy metal Cr element, has no pollution, and has the advantages of low-cost and easily obtained raw materials and simple preparation process. The invention mainly solves the problems that the catalyst in the one-step preparation of olefin, aromatic hydrocarbon and oxygen-containing compound from the synthesis gas is easy to be poisoned and deactivated by metal carbonyl compound, other byproducts are generated and the selectivity of target products is reduced.
In one aspect, the present invention provides a method for removing Fe (CO)5 And/or Ni (CO)4 Comprises: gamma-Al2 O3 A modified carrier, a primary active ingredient and optionally a co-active ingredient;
wherein the main active component is copper and/or copper oxide;
the auxiliary active component is selected from at least one of Zn, zr, la, alkali metal and respective oxides, preferably at least one of Zn, zr, K and respective oxides;
the gamma-Al2 O3 The modified carrier comprises a platy hydrotalcite-like compound Mg2 Al(OH)7 。
According to the invention, by reacting gamma-Al2 O3 X-ray diffraction analysis (XRD analysis) of the modified support was performed to determine gamma-Al2 O3 The modified support comprisesSheet hydrotalcite-like compound Mg2 Al(OH)7 。
In some preferred embodiments of the invention, the gamma-Al is2 O3 The total mass of the modified carrier is calculated as the reference, the content of the main active component is 1 to 10 weight percent, preferably 1 to 6 weight percent, and the content of the auxiliary active component is 0 to 5 weight percent, preferably 0.5 to 3 weight percent
In some preferred embodiments of the invention, the gamma-Al2 O3 The preparation method of the modified carrier comprises the following steps:
a) gamma-Al using an impregnating solution containing a magnesium source2 O3 Carrying out dipping treatment;
b) For gamma-Al after dipping treatment2 O3 Drying; and
c) For gamma-Al after drying treatment2 O3 Performing first roasting treatment to obtain the gamma-Al2 O3 And (3) modifying the carrier.
In some preferred embodiments of the present invention, the magnesium source is used in an amount of Mg element, the magnesium source and the γ -Al2 O3 The mass ratio of (1) to (5) to (8) is 100, preferably (1) to (5) is 100.
According to the present invention, the magnesium source is selected from at least one of magnesium chloride, magnesium nitrate and magnesium sulfate.
In some preferred embodiments of the present invention,
the conditions of the impregnation treatment include: the temperature of the dipping treatment is 40-80 ℃, and the time of the dipping treatment is 10-20 hours; and/or
The conditions of the drying treatment include: the vacuum degree is 0.1 kPa-50 kPa, the drying treatment temperature is 60-100 ℃, and the drying treatment time is 6-24 hours; and/or
The conditions of the first firing treatment include: the temperature of the first roasting treatment is 350-550 ℃, and the time of the first roasting treatment is 3-5 h.
In still another aspect, the present invention provides a method for preparing the above-mentioned purifying agent, including:
i) At the same timeAdding a precursor solution of the main active component and optionally a co-active component and a precipitant to the mixture containing the gamma-Al2 O3 Preparing a purifying agent precursor in an aqueous solution of the modified carrier;
ii) aging the purifying agent precursor, and performing second roasting treatment after aging treatment to obtain the purifying agent.
According to the invention, the precursor solution of the main active component and optionally the co-active component is a solution formed by a soluble salt of copper and optionally a soluble salt of at least one of Zn, zr, la, alkali metals.
According to the invention, the soluble salt of copper is selected from at least one of copper chloride, copper nitrate, copper sulphate, copper acetate and copper citrate.
According to the invention, the precipitant is a sodium carbonate solution, preferably the concentration of the precipitant is 0.1mol/L to 10mol/L.
According to the present invention, the aged scavenger precursor may be washed, preferably with deionized water, several times, and dried at 80-120 ℃ before the second calcination treatment.
In some preferred embodiments of the invention, step i) is carried out at a stirring speed of 100r/min to 350r/min and/or at a temperature of 50℃to 80 ℃.
In some preferred embodiments of the present invention, the temperature of the aging treatment is 50 ℃ to 80 ℃ and the time of the aging treatment is 2 hours to 3 hours; and/or
The temperature of the second roasting treatment is 450-550 ℃, and the time of the second roasting treatment is 1-3 h.
In a further aspect, the present invention provides a purifying agent as defined above or a purifying agent prepared according to the above preparation method for removing Fe (CO)5 And/or Ni (CO)4 Application in the field.
In yet another aspect of the invention, a method for removing Fe (CO) is provided5 And/or Ni (CO)4 Comprises the following steps: to contain Fe (CO)5 And/or Ni (CO)4 With the above-mentioned purifying agent or according to the above-mentioned preparation methodThe prepared purifying agent is contacted, so that Fe (CO) in the material is removed5 And Ni (CO)4 。
In some preferred embodiments of the invention, the feedstock may be synthesis gas or a carbon dioxide/carbon monoxide/hydrogen mixture.
According to the present invention, the carbon dioxide/carbon monoxide/hydrogen mixed gas refers to a mixed gas including carbon dioxide, carbon monoxide and hydrogen at the same time.
In some preferred embodiments of the invention, the contacting occurs in a fixed bed reactor; preferably, the contacting conditions include: the temperature is 50-300 ℃, preferably 100-200 ℃, and/or the pressure is 0-10 MPa, preferably 2-8 MPa, and/or the volume space velocity of the material is 25h-1 ～350h-1 Preferably 60h-1 ～280h-1 。
In some preferred embodiments of the invention, the scavenger is subjected to an activation treatment prior to the contacting, the activation treatment conditions comprising: at a temperature of 100-200 ℃ and/or a pressure of 0-10 MPa and/or an activating atmosphere of H2 Or synthesis gas.
Compared with the prior art, the technical scheme of the invention has the following advantages: mg modified gamma-Al2 O3 Wherein the Mg (Al) O phase is formed, and the interaction between Cu and Mg (Al) O is more than that between Cu and gamma-Al2 O3 The interaction is strong, and the stronger interaction is beneficial to the transfer of electrons. Meanwhile, the purifying agent has the advantages of large specific surface area, good dispersibility of active components and stable structure, and is Fe (CO) in synthesis gas or carbon dioxide/carbon monoxide/hydrogen mixed gas5 And Ni (CO)4 The removal efficiency is high, the adsorption capacity is large, and the synthesis gas does not generate catalytic synthesis and hydrogenation reaction on the surface of the purifying agent. The preparation method of the purifying agent is simple to operate and environment-friendly, the used raw materials are cheap and easy to obtain, the purifying agent can be used for preparing olefin, aromatic hydrocarbon and oxygen-containing compound in industrial production by a one-step method of synthesis gas, and has good application prospect.
Drawings
FIG. 1 shows the gamma-Al obtained in example 12 O3 Modified carrierXRD pattern of the body.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present invention, a Bruker D8 type diffractometer was used for the X-ray diffraction experiment. The instrument operating conditions were as follows: the X-ray source is Cu-K alpha line with wavelength of
The accelerating voltage is 40kV, the detector current is 100mA, the scanning range is 5-80 degrees, the scanning step length is 0.01 degrees, and the scanning speed is 4 degrees/min.
In the following embodiment, copper nitrate is Cu (NO3 )2 ·3H2 O; the sodium carbonate is anhydrous sodium carbonate; cupric citrate is C6 H4 Cu2 O7 ·2.5H2 O。
Example 1
1、γ-Al2 O3 Preparation of modified support
According to the mass of magnesium in magnesium nitrate and gamma-Al2 O3 The mass ratio of (3) to (100) is that of gamma-Al2 O3 Soaking in magnesium nitrate solution at 50deg.C for 12 hr, drying at 100deg.C under vacuum (vacuum degree of 0.5 kPa) for 12 hr, and calcining at 500deg.C in air for 3 hr to obtain gamma-Al2 O3 Modified supports (i.e. Mg-gamma-Al2 O3 )。
For the prepared gamma-Al2 O3 Carrying out X-ray diffraction analysis on the modified carrier to obtain gamma-Al2 O3 XRD pattern of the modified support (as shown in figure 1). As can be seen from FIG. 1, the modified gamma-Al2 O3 The weak flaky hydrotalcite-like compound Mg appears2 Al(OH)7 Is a diffraction peak of (2).
2. Preparation of purifying agent
1.13g of copper nitrate (Cu (NO)3 )2 ·3H2 O) dissolving in 9mL deionized water to form uniform copper nitrate solution, then dissolving 0.49g sodium carbonate in 9mL deionized water to form precipitant, and dripping the two solutions into a solution containing 10.0g Mg-gamma-Al under vigorous stirring (with the rotating speed of 300 r/min) and 70 ℃ in parallel flow2 O3 In the beaker of (2), aging for 2 hours, filtering, washing for several times, drying at 100 ℃, and roasting at 500 ℃ for 3 hours to obtain the purifying agent 1.
In the purifying agent 1, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The content of copper oxide was 3.74% by weight based on the total mass of (C).
Example 2
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 And (3) modifying the carrier.
2. Preparation of purifying agent
2.26g of copper nitrate is dissolved in 9mL of deionized water to form a uniform copper nitrate solution, then 0.98g of sodium carbonate is dissolved in 9mL of deionized water to form a precipitator, and the two solutions are dropwise added in parallel flow with 10.0g of Mg-gamma-Al under vigorous stirring (the rotating speed is 300 r/min) and 70 DEG C2 O3 In the beaker of (2), aging for 2 hours, filtering, washing for several times, drying at 100 ℃, and roasting at 500 ℃ for 3 hours to obtain the purifying agent 2.
In the purifying agent 2, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The copper oxide content was 7.48wt% based on the total mass of (C).
Example 3
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 And (3) modifying the carrier.
2. Preparation of purifying agent
Dissolving 0.378g copper nitrate in 9mL deionized water to form a uniform copper nitrate solution, then dissolving 0.49g sodium carbonate in 9mL deionized water to form a precipitant, and dissolving the twoThe solution was added dropwise to a solution containing 10.0g of Mg-gamma-Al in parallel flow under vigorous stirring (rotation speed: 300 r/min) at 70 ℃2 O3 In the beaker of (2), aging for 2 hours, filtering, washing for several times, drying at 100 ℃, and roasting at 500 ℃ for 3 hours to obtain the purifying agent 3.
In the purifying agent 3, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The content of copper oxide was 1.25wt% based on the total mass of the catalyst.
Example 4
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 And (3) modifying the carrier.
2. Preparation of purifying agent
1.13g of copper nitrate and 0.47g of zirconium nitrate (Zr (NO)3 )4 ·5H2 O) dissolving in 9mL deionized water to form a uniform solution, then dissolving 1.41g sodium carbonate in 9mL deionized water to form a precipitant, and dripping the two solutions into a solution containing 10.0g Mg-gamma-Al under vigorous stirring (with the rotating speed of 300 r/min) and 70 ℃ in parallel flow2 O3 In the beaker of (2), aging for 2 hours, filtering, washing for several times, drying at 100 ℃, and roasting at 500 ℃ for 3 hours to obtain the purifying agent 4.
In the purifying agent 4, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The content of copper oxide was 3.74% by weight and the content of zirconium oxide was 1% by weight based on the total mass of (a) and (b).
Example 5
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 The modified carrier is different only in that the quality of magnesium in magnesium nitrate and gamma-Al are adjusted2 O3 The mass ratio of (2) is 0.5:100.
2. Preparation of purifying agent
1.13g of copper nitrate was dissolved in 9mL of deionized water to form a homogeneous copper nitrate solution, then 0.49g of sodium carbonate was dissolved in 9mL of deionized water to form a precipitant, and the two solutions were stirred vigorously (at 250 r/min) and at 70℃andDrop-wise adding 10.0g of Mg-gamma-Al2 O3 In the beaker of (2), aging for 2 hours, filtering, washing for several times, drying at 100 ℃, and roasting at 500 ℃ for 3 hours to obtain the purifying agent 5.
In the purifying agent 5, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The content of copper oxide was 3.74% by weight based on the total mass of (C).
Example 6
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 The modified carrier is different only in that the quality of magnesium in magnesium nitrate and gamma-Al are adjusted2 O3 The mass ratio of (2) is 5:100.
2. Preparation of purifying agent
1.13g of copper nitrate is dissolved in 9mL of deionized water to form a uniform copper nitrate solution, then 0.49g of sodium carbonate is dissolved in 9mL of deionized water to form a precipitator, and the two solutions are dropwise added in parallel flow with 10.0g of Mg-gamma-Al under vigorous stirring (the rotating speed is 300 r/min) and 70 DEG C2 O3 In the beaker of (2), aging for 2 hours, filtering, washing for several times, drying at 100 ℃, and roasting at 500 ℃ for 3 hours to obtain the purifying agent 6.
In the purifying agent 6, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The content of copper oxide was 3.74% by weight based on the total mass of (C).
Example 7
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 And (3) modifying the carrier.
2. Preparation of purifying agent
Scavenger 7 was prepared in the same manner as in example 1, except that copper citrate was used as the copper source. In the purifying agent 7, the main active component is copper oxide, and Mg-gamma-Al is used as the main active component2 O3 The content of copper oxide was 3.74% by weight based on the total mass of (C).
Comparative example 1
The scavenger 8 was synthesized according to patent document CN102218295 a. In particular, the method comprises the steps of,
19.1g of magnesium nitrate and 7.4g of copper nitrate are weighed and dissolved in 45.0g of deionized water, and 5.0g of gamma-Al is added after the mixture is uniformly mixed2 O3 Soaking for 2h, drying at 80 ℃ for 36h in an oven, and finally roasting at 500 ℃ for 4h to obtain the purifying agent 8.
The main active component is copper oxide, gamma-Al2 O3 The content of copper oxide was 48.9wt% based on the total mass of (C).
Comparative example 2
1、γ-Al2 O3 Preparation of modified support
Preparation of gamma-Al as in example 12 O3 And (3) modifying the carrier.
2. Preparation of purifying agent
A scavenger 9 was prepared in the same manner as in example 1 except that chromium nitrate was used instead of copper nitrate in example 1, so that the main active component of the prepared scavenger 9 was chromium oxide as Mg-gamma-Al2 O3 The content of chromium oxide was 3.74% by weight based on the total mass of the catalyst.
Application example 1
Fe (CO) in raw material gas is removed by using the purifying agents 1-9 respectively5 And Ni (CO)4 . The method comprises the following specific steps:
2.0g of a scavenger was charged into a reaction tube having an inner diameter of 6mm, and H was used2 After activation at 180℃for 10 hours, a mixed feed gas of hydrogen and carbon monoxide (nHydrogen gas :nCarbon monoxide =50:50) is introduced into a reaction tube, and enters a fixed bed for reaction, the reaction temperature is 180 ℃, the pressure of a reaction system is 2MPa, and the gas volume space velocity is 80h-1 Under the condition of Fe (CO)5 And Ni (CO)4 Is detected by gas chromatography with an electron capture detector. And compared to an empty reaction tube without the scavenger. The results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, fe (CO) in the raw material gas can be removed more thoroughly by using the purifying agent provided by the invention5 And Ni (CO)4 。
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (16)
1. For removing Fe (CO)5 And/or Ni (CO)4 Comprises: gamma-Al2 O3 A modified carrier, a primary active ingredient and optionally a co-active ingredient;
wherein the main active component is copper and/or copper oxide;
the auxiliary active component is selected from at least one of Zn, zr, la, alkali metals and respective oxides;
the gamma-Al2 O3 The modified carrier contains a platy hydrotalcite-like compound Mg2 Al(OH)7 ；
With said gamma-Al2 O3 The total mass of the modified carrier is calculated as a benchmark, the content of the main active component is 1-10wt%, and the content of the auxiliary active component is 0-5wt%;
the gamma-Al2 O3 The preparation method of the modified carrier comprises the following steps:
a) gamma-Al using an impregnating solution containing a magnesium source2 O3 Carrying out dipping treatment;
b) For gamma-Al after dipping treatment2 O3 Drying; and
c) For gamma-Al after drying treatment2 O3 Performing first roasting treatment to obtain the gamma-Al2 O3 Modifying the carrier;
the magnesium source and the gamma-Al2 O3 The mass ratio of (1) is (0.5-8): 100;
the conditions of the impregnation treatment include: the temperature of the dipping treatment is 40-80 ℃, and the time of the dipping treatment is 10-20 hours;
the conditions of the first firing treatment include: the temperature of the first roasting treatment is 350-550 ℃, and the time of the first roasting treatment is 3-5 hours;
the preparation method of the purifying agent comprises the following steps:
i) Simultaneously adding a precursor solution of the main active component and optionally a co-active component and a precipitant to the mixture containing the gamma-Al2 O3 Preparing a purifying agent precursor in an aqueous solution of the modified carrier;
ii) aging the purifying agent precursor, and performing second roasting treatment after aging treatment to obtain the purifying agent.
2. The scavenger according to claim 1, wherein the co-active component is selected from at least one of Zn, zr, K and the respective oxides.
3. The purifying agent according to claim 2, wherein the γ -Al is2 O3 The total mass of the modified carrier is calculated as a reference, and the content of the main active component is 1-6wt%.
4. The purifying agent according to claim 2, wherein the γ -Al is2 O3 The total mass of the modified carrier is calculated and based on the total mass, and the content of the auxiliary active component is 0.5-3 wt%.
5. The purifying agent according to claim 4, wherein the magnesium source is mixed with the γ -Al2 O3 The mass ratio of (1) to (5) is 100.
6. The purifying agent according to claim 5, wherein,
the conditions of the drying treatment include: the vacuum degree is 0.1kPa to 50kPa, the drying treatment temperature is 60 ℃ to 100 ℃, and the drying treatment time is 6 hours to 24 hours.
7. A process for the preparation of a catalyst as claimed in any one of claims 1 to 6 for the removal of Fe (CO)5 And/or Ni (CO)4 A method of purifying a chemical agent, comprising:
i) Simultaneously adding a precursor solution of the main active component and optionally a co-active component and a precipitant to the mixture containing the gamma-Al2 O3 Preparing a purifying agent precursor in an aqueous solution of the modified carrier;
ii) aging the purifying agent precursor, and performing second roasting treatment after aging treatment to obtain the purifying agent;
the gamma-Al2 O3 The preparation method of the modified carrier comprises the following steps:
a) gamma-Al using an impregnating solution containing a magnesium source2 O3 Carrying out dipping treatment;
b) For gamma-Al after dipping treatment2 O3 Drying; and
c) For gamma-Al after drying treatment2 O3 Performing first roasting treatment to obtain the gamma-Al2 O3 Modifying the carrier;
the magnesium source and the gamma-Al2 O3 The mass ratio of (1) is (0.5-8): 100;
the conditions of the impregnation treatment include: the temperature of the dipping treatment is 40-80 ℃, and the time of the dipping treatment is 10-20 hours;
the conditions of the first firing treatment include: the temperature of the first roasting treatment is 350-550 ℃, and the time of the first roasting treatment is 3-5 h.
8. The method according to claim 7, wherein step i) is performed at a stirring speed of 100r/min to 350r/min and/or a temperature of 50 ℃ to 80 ℃.
9. The preparation method according to claim 7 or 8, wherein the aging treatment is performed at 50 ℃ to 80 ℃ for 2 hours to 3 hours; and/or
The temperature of the second roasting treatment is 450-550 ℃, and the time of the second roasting treatment is 1-3 hours.
10. Purification agent according to any one of claims 1 to 6 or prepared according to the preparation method of any one of claims 7 to 9 for Fe (CO) removal5 And/or Ni (CO)4 Application in the field.
11. Fe (CO) removal5 And/or Ni (CO)4 Comprises the following steps: to contain Fe (CO)5 And/or Ni (CO)4 Contacting the material of any one of claims 1 to 6 or produced according to the production method of any one of claims 7 to 9, thereby removing Fe (CO) from the material5 And/or Ni (CO)4 。
12. The Fe (CO) removal of claim 115 And/or Ni (CO)4 Characterized in that the conditions of said contacting include: the temperature is 50-300 ℃, and/or the pressure is 0-10 MPa, and/or the volume airspeed of the material is 25h-1 ~350h-1 。
13. The Fe (CO) removal of claim 125 And/or Ni (CO)4 Characterized in that the conditions of said contacting include: the temperature is 100-200 ℃.
14. The Fe (CO) removal of claim 125 And/or Ni (CO)4 Is characterized in that the contact condition packageThe method comprises the following steps: the pressure is 2-8 MPa.
15. The Fe (CO) removal of claim 125 And/or Ni (CO)4 Characterized in that the conditions of said contacting include: the volume airspeed of the material is 60h-1 ~280h-1 。
16. The method according to any one of claims 11 to 15, wherein the scavenger is subjected to an activation treatment prior to the contacting, the activation treatment conditions comprising: the temperature is 100-200 ℃, and/or the pressure is 0-10 MPa, and/or the activation atmosphere is H2 Or synthesis gas.
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