Catalyst for wide-range compression of methanol from synthesis gas and preparation method thereof

Abstract

The invention relates to a catalyst for wide pressure of methanol from synthesis gas and a preparation method thereof. The catalyst comprises the following components: a catalyst active component, the catalyst active component comprises a mixed oxide of Cu, Zn, Sm and Al or consists of the mixed oxide of Cu, Zn, Sm and Al, and the molar ratio of Cu to Zn to Sm to Al is (10-75): (20-60): (0.5-7): (1-10); the binder is selected from one or more of gamma-Al2O3, silicon dioxide, a silicon-aluminum molecular sieve, activated carbon, a titanium-silicon molecular sieve, hydrotalcite, aluminum silicate, magnesium aluminate spinel, titanium dioxide, bentonite, diatomite, magnesium phosphate, calcium aluminate and calcium silicate. The catalyst provided by the invention can be used for synthesizing methanol from CO and / or CO2 and H2, the reaction can be carried out at low temperature and under wide pressure, and the catalyst shows high activity and good thermal stability.

Description

Technical Field

[0001] The present invention belongs to the field of chemical technology and catalysts, and specifically relates to a catalyst for synthesizing methanol from synthesis gas and a preparation method thereof, and more particularly to a catalyst for synthesizing methanol from the reaction of CO and / or CO2 and H2 and a preparation method thereof. Background Art

[0002] Methanol is an important basic organic chemical raw material. In recent years, with the rapid development of science and technology and the change of energy structure, more new uses of methanol have been opened up. The zinc-chromium catalyst successfully developed by BASF in Germany has low activity. In order to obtain higher catalytic activity and higher conversion rate, it needs to be operated under high temperature (317-319°C) and high pressure (25-35MPa) conditions. It is gradually being eliminated. The copper-based catalyst successfully developed by ICI in the UK and Lurgi in Germany is widely used because of its good activity, high selectivity, and it is a low-pressure (5-10MPa) catalyst. At present, the industrial methanol synthesis catalyst is mainly Cu-Zn-Al catalytic system, which generally requires higher pressure for reaction.

[0003] In order to overcome the high-pressure disadvantage of industrial methanol synthesis catalysts, in recent years, some domestic and foreign patents have reported a series of heat-resistant copper-based catalysts for synthesizing methanol.

[0004] Chinese patent application CN1173393A introduces a metal oxide catalyst of five components coexisting Cu / Zn / Al / M' / M" prepared by a mixed coprecipitation method. M' is selected from metals scandium (Se), yttrium (Y) or lanthanide rare earths of group IIIB, and M" is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Ne), tantalum (Ta), molybdenum (Mo), and tungsten (W) of group IVB, VB or VIB. The component ratio (atomic ratio) is Cu 20-80, Zn 25-70, Al 6-15, M' 0.1-10, and M" 0.1-10.

[0005] Chinese patent application CN1660493A introduces a new copper-based methanol synthesis catalyst and its preparation method. The catalyst is mainly composed of copper and zinc active matrix and a secondary component of thermally stable high-surface active carrier. Summary of the invention

[0006] The object of the present invention is to provide a copper-based catalyst with high activity and good thermal stability for synthesizing methanol by the wide-pressure reaction of CO and / or CO2 and H2 at low temperature and wide pressure, and a preparation method thereof.

[0007] According to one aspect of the present invention, there is provided a catalyst for wide compression of methanol from synthesis gas, comprising the following components, or consisting essentially of the following components:

[0008] A catalyst active component, the catalyst active component includes or consists of a mixed oxide of Cu, Zn, Sm, and Al, wherein the molar ratio of Cu, Zn, Sm, and Al is 10-75:20-60:0.5-7:1-10; a binder, the binder is one or more selected from γ-Al2O3, silica, silica-alumina molecular sieve, activated carbon, titanium silicon molecular sieve, hydrotalcite, aluminum silicate, magnesium aluminum spinel, titanium dioxide, bentonite, diatomaceous earth, magnesium phosphate, calcium aluminate, and calcium silicate.

[0009] In some embodiments, the molar ratio of the active component metals of the catalyst, Cu, Zn, Sm and Al, is 5-25:4-20:0.25-2.5:1.

[0010] In some embodiments, the binder is one or more selected from γ-Al2O3, 5A molecular sieve, ZSM-5, 3A molecular sieve, diatomaceous earth, MCM-41, Beta molecular sieve, and Y molecular sieve.

[0011] In some embodiments, the binder is used in an amount of 0.01 to 20 wt % based on the weight of the catalyst.

[0012] In some embodiments, the particle size of the binder is 20 nm to 275 um.

[0013] In some embodiments, the pore size of the binder is 0.2 nm to 80 nm.

[0014] According to the present invention, the oxides of Cu, Zn, Sm and Al are composed of halogen-free ions (such as Cl - ,Br - ) and no SO4 2- The oxide is obtained by calcining a salt thereof (e.g. a water-soluble salt). The salt, such as a water-soluble salt, is preferably selected from nitrates, acetates, formates, sulfates and hydrochlorides.

[0015] In some embodiments, the molar ratio of the active components of the catalyst, Cu, Zn, Sm and Al, is 10-75:20-40:0.5-7:1-5.

[0016] In some embodiments, the atomic ratio (molar ratio) of the active components of the catalyst, Cu, Zn, Sm and Al, is: 10-65:20-40:0.5-7:1.5-5.

[0017] In some embodiments, the atomic ratio (molar ratio) of the active components of the catalyst, Cu, Zn, Sm and Al, is 40-65:20-40:0.5-7:2-5.

[0018] According to another aspect of the present invention, there is provided a method for preparing a catalyst for wide compression of methanol from synthesis gas, the method comprising the following steps:

[0019] 1) preparing a mixed aqueous solution or an acid-base solution or an organic solution of each active component metal of the catalyst, Sm and a salt selected from one or more of Cu, Zn and Al;

[0020] 2) adding the solution of step 1) to the precipitant aqueous solution under stirring at 60-80° C. to obtain a precipitate, and controlling the end point pH to be 7.0-9.4;

[0021] 3) Wash the precipitate obtained in step 2) with deionized water until there is no halogen ion (such as Cl - Br - ) and / or SO4 2- ;

[0022] 4) adding a binder (20 nm to 275 μm), a solution or powder of one or more salts selected from Cu, Zn and Al remaining in step 1) (if any), and an optional strong electron-withdrawing CO or CO2 molecular activator or a solution thereof to the precipitate treated in step 3), stirring and mixing evenly, and allowing to stand;

[0023] 5) drying the mixture obtained in step 4) and, if necessary, separating the solid mixture obtained, at 70-160° C. and calcining at 300-400° C. for 2-4 h;

[0024] 6) grinding, shaping, and crushing the calcined product obtained in step 5) to obtain a catalyst, or

[0025] The calcined product obtained in step 5) is added to a solution of a strong electron-withdrawing CO or CO2 molecular activator, impregnated, dried, and crushed to obtain a catalyst.

[0026] Wherein, in the method, the molar ratio of each active component metal of the catalyst, Cu, Zn, Sm and Al is 10-75:20-60:0.5-7:1-10.

[0027] In some embodiments, the molar ratio of Cu, Zn, Sm and Al is 5-25: 4-20: 0.25-2.5: 1. In some embodiments, the molar ratio of the active metal components of the catalyst, Cu, Zn, Sm and Al, is 10-75: 20-40: 0.5-7: 1-5.

[0028] In some embodiments, the ratio of each active component metal of the catalyst, Cu, Zn, Sm and Al, is measured by atomic ratio (molar ratio): Cu is 10-65, Zn is 20-40, Sm is 0.5-7, and Al is 1.5-5.

[0029] In some embodiments, the ratio of each active component of the catalyst, Cu, Zn, Sm and Al, is measured by atomic ratio (molar ratio): Cu is 40-65, Zn is 20-40, Sm is 0.5-7, and Al is 2-5.

[0030] According to the present invention, when each raw material is in a powder state or is added, its particle size can range from tens of nanometers to hundreds of micrometers, for example, 20nm to 275um.

[0031] In some embodiments, in step 1), the salt of Sm and Cu, Zn and Al is one or more selected from nitrate, acetate, formates, sulfates, hydrochlorides, perchlorates, oxalates, acetylacetonates, metallocene derivative salts and stearates.

[0032] In some embodiments, in step 1), the acid-base solution can be a hydrochloric acid solution, an oxalic acid solution, a nitric acid solution, a sulfuric acid solution, an acetic acid solution, a formic acid solution, a phosphoric acid solution, a benzoic acid solution, etc.

[0033] In some embodiments, in step 1), the organic solution can be ethanol solution, isopropanol solution, ethyl acetate solution, ether solution, tetrahydrofuran solution, dichloromethane solution, hexane solution, etc.

[0034] In some embodiments, in step 2), the adding is performed under stirring at 65-70°C.

[0035] In some embodiments, in step 2), the precipitant is one or more selected from Na2CO3, NaHCO3, K2CO3, KHCO3, Cs2CO3, Na2HPO3, K2HPO3, and sodium acetate, calcium acetate, lithium diisopropylamide, triethylamine, and pyridine.

[0036] In some embodiments, in step 2), the precipitant is 98.5% Cl - ≤0.1%.

[0037] In some embodiments, in step 2), the end point pH is controlled to be 7.0-8.0.

[0038] In some embodiments, in step 4), the binder is one or more selected from γ-Al2O3, silica, silica-alumina molecular sieve, activated carbon, titanium silicate molecular sieve, hydrotalcite, aluminum silicate, magnesium aluminum spinel, titanium dioxide, bentonite, diatomaceous earth, magnesium phosphate, calcium aluminate, and calcium silicate.

[0039] In some embodiments, in step 4), the binder is one or more selected from γ-Al2O3, 5A molecular sieve, ZSM-5, 3A molecular sieve, diatomaceous earth, MCM-41, Beta molecular sieve, and Y molecular sieve.

[0040] In some embodiments, in step 4), the amount of the binder is 0.01 to 20 wt % based on the weight of the catalyst.

[0041] In some embodiments, in step 4), the particle size of the binder can be, for example, 20 nm to 275 um. According to the present invention, the strong electron-withdrawing CO or CO2 molecular activator includes, but is not limited to, organic reagents and metal elements, and the metal elements include, for example, Zr and aluminum. In addition, the strong electron-withdrawing CO or CO2 molecular activator can be added alone or introduced in the form of a salt.

[0042] In some embodiments, in step 4), the strong electron-withdrawing CO or CO2 molecular activator is selected from one or more of oxalic acid, oxalate, acetylacetonate, metallocene derivative salt, nitrilotriacetic acid, nitrilotriacetate, formic acid, formate, acetic acid, acetate, p-toluenesulfonic acid, p-toluenesulfonate, tetramethylpiperidinol oxide, acetonitrile, adiponitrile, and 1,2-dichloroethane, preferably one or more of oxalic acid, oxalate, nitrilotriacetic acid, nitrilotriacetate, formic acid, formate, acetic acid, acetate, p-toluenesulfonic acid, p-toluenesulfonate, and tetramethylpiperidinol oxide.

[0043] According to the present invention, a strong electron-withdrawing CO or CO2 molecule activator is added. When CO or CO2 is adsorbed on the catalyst surface, the strong electron-withdrawing agent activates the CO or CO2 molecule at low temperature and low pressure by reducing the electron cloud density of the CO or CO2 molecule, making it easy to react with H2.

[0044] In some embodiments, in step 4), the amount of strongly electron-withdrawing CO or CO2 molecular activator is 0.5% to 40% of the total metal molar amount of the catalyst active ingredients, preferably 10% to 30%, for example 1%, 2%, 3%, 5%, 8%, 10%, 12%, 15%, 17%, 19%, 20%, 22%, 28%, etc.

[0045] In some embodiments, in step 4), the amount of the strong electron-withdrawing CO or CO2 molecular activator is more than 20% of the molar amount of the Cu component metal, for example, 30%, 35% or 40%. In some embodiments, it is less than 60% of the molar amount of the Cu component metal.

[0046] In some embodiments, in step 4), the solution of the strong electron-withdrawing CO or CO2 molecular activator can be an aqueous solution, an ammonia solution, an ethanol solution, an acetone solution, an ether solution, a tetrahydrofuran solution, a pyridine solution, a triethylamine solution, etc.

[0047] In some embodiments, in step 4), the mixing is stirred for 0.5 to 4 hours.

[0048] In some embodiments, in step 5), drying is performed at 100-120° C. for 2-5 hours.

[0049] In some embodiments, in step 5), calcination is performed at 300-400° C. for 2-3 h.

[0050] In some embodiments, in step 6), the particle size of the catalyst is 20-40 mesh.

[0051] The catalyst according to the present invention needs to be activated before use, and can be activated (reduced) in a fixed bed reactor, using low H2 (H2 / N2=3 / 97) for reduction for 16 to 20 hours at a reduction temperature of 190 to 280° C. When the temperature is higher than 280° C., copper particles are easily sintered.

[0052] According to another aspect of the present invention, there is provided a method for synthesizing methanol, the method comprising:

[0053] The catalyst is activated by reducing the catalyst with a mixture of H2 / N2 of 3 / 97 for 16 to 20 hours at a reduction temperature of 190 to 280°C;

[0054] The activated catalyst is loaded into the reactor and the raw gas CO, H2, CO2, N2 is introduced at a space velocity of 1000-15000h -1 , the reaction pressure is 0.5-10 MPa (for example, 0.5, 1.5, 2.5, 3.5, 4.5, 5.5, 6.5, 7.5, 8.5 MPa), and the reaction temperature is 190-280°C.

[0055] The raw gas composition is CO:H2:CO2:N2=10~20:50~90:2~8:2~8.

[0056] The activity evaluation of the catalyst was carried out by heating reduction and activity evaluation in a gas phase fixed bed reactor. The catalyst loading was 3g, the raw gas composition was CO:H2:CO2:N2=15:70:5:5, the reaction pressure could be as low as 0.5MPa, and the space velocity was 3000h -1 The evaluation temperature is 220℃, and the result is called initial activity. Then the catalyst is heat treated at 400℃ for 6h in a synthesis gas atmosphere, and then cooled to 220℃. The result is called activity after heat treatment. The product is analyzed by gas chromatography, and the catalyst activity is expressed as methanol space-time yield (gg -1 cat.h -1The catalyst of the present invention has the characteristics of high catalytic activity under low gas pressure, and after heat treatment at 400° C., the CO conversion rate is high, the by-products are small, and the selectivity of methanol is stable.

[0057] CO + 2H2 = CH3OH

[0058] CO2+3H2=CH3OH+H2O.

[0059] The catalyst of the present invention is used to synthesize methanol from CO and / or CO2 and H2. The reaction can be carried out at low temperature and wide pressure, and the catalyst exhibits high activity and good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is the pore distribution diagram of the catalyst obtained using Beta molecular sieve as a binder in Example 8;

[0061] Figure 2 This is the pore distribution diagram of the catalyst obtained using silica sol as a binder in Example 12. DETAILED DESCRIPTION

[0062] The following examples are only listed as examples of embodiments of the present invention and do not constitute any limitation to the present invention. It can be understood by those skilled in the art that modifications within the scope of the essence and concept of the present invention fall within the scope of protection of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are all commercially available products.

[0063] The binder raw materials are as follows:

[0064]

[0065]

[0066] Example 1

[0067] 1) Take 65 ml of 1M-Cu(CH3COO)2 ethanol solution, 7 ml of 1M-SmCl2 dilute hydrochloric acid aqueous solution and 5 ml of 1M-Al(NO3)3 aqueous solution, place them in a 400 ml beaker and stir to mix.

[0068] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0069] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - .

[0070] 4) Add 1.0 g of γ-Al2O3 (200-300 mesh) and 1 M-ZnC2O4 and 37.5 ml of 0.6 M oxalic acid aqueous solution to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0071] 5) Filter, dry the filter cake at 110℃ for 4h, crush, and calcine at 300℃ for 3h.

[0072] 6) Finally, the mixed oxide obtained in step 5 is ground, tableted, crushed, sieved, and collected into a 20-40 mesh catalyst for later use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 65: 37.5: 7: 5 (atomic ratio).

[0073] The catalyst was activated (reduced) in a fixed bed reactor before use, and reduced with low H2 (H2 / N2=3 / 97) for 16 h at a reduction temperature of 240°C.

[0074] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=15:70:5:5, the reaction pressure is 2.0 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.74 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The activity after heat treatment was 1.54 g / min. -1 cat.h -1 .

[0075] Comparative Example 1

[0076] The steps and conditions are the same as those in Example 1, except that 37.5 ml of a 1M aqueous solution of ZnCl2 is added in step 1), and no oxalic acid or oxalate solution is added in step 4). The initial activity of the catalyst is 1.30 gg-1 cat.h-1, and the activity after heat treatment is 1.00 gg-1 cat.h-1.

[0077] Embodiment 2-3

[0078] According to the amount of materials in Table 1, the type of strong electron-withdrawing activator was changed. The other conditions and preparation method were the same as those in Example 1. The activity measurement results are shown in Table 1.

[0079] Example 4

[0080] 1) Take 65 ml of 1M Cu(NO3)2 aqueous solution, 20 ml of 1M Zn(NO3)2 aqueous solution, 7 ml of 1M SmCl2 dilute hydrochloric acid aqueous solution and 5 ml of 1M Al(NO3)3 aqueous solution, place them in a 400 ml beaker and stir to mix.

[0081] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0082] 3) Wash the precipitate prepared in step 2 with 60° C. deionized water until there is no Cl-.

[0083] 4) Add 2.0 g of 3A molecular sieve and 25 ml of 0.9 M tetramethylpiperidinyl oxide ethanol solution to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0084] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 350°C for 3 h.

[0085] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 65: 20: 7: 5 (atomic ratio).

[0086] The catalyst was activated (reduced) in a fixed bed reactor before use, and reduced with low H2 (H2 / N2=3 / 97) for 19 h at a reduction temperature of 200°C.

[0087] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=15:70:5:5, the reaction pressure is 8.5 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.84 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.60 g / min. -1 cat.h -1 .

[0088] Example 5

[0089] 1) Take 65 ml of 1M Cu(NO3)2 aqueous solution, 35 ml of 1M ZnCl2 aqueous solution, 6 ml of 1M Sm(CH3COO)2 dilute hydrochloric acid aqueous solution, and 4 ml of 1M Al(NO3)2 aqueous solution in a 400 ml beaker and stir to mix.

[0090] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0091] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - .

[0092] 4) Add 1.0 g of titanium silicate molecular sieve to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0093] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 330°C for 3 h.

[0094] 6) Finally, the mixed oxide obtained in step 5 was pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst precursors. 40 ml of 0.5 M tetramethylpiperidinyl oxide ethanol solution was added and immersed for 16 hours, and dried at 120° C. for 4 hours to obtain a catalyst. The distribution ratio of the active components of the obtained catalyst was Cu: Zn: Sm: Al = 65: 35: 6: 4 (atomic ratio).

[0095] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 18 h at a reduction temperature of 210°C.

[0096] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=15:70:5:5, the reaction pressure is 8.0 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.75 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.52 g / min. -1 cat.h -1 .

[0097] Example 6

[0098] 1) Take 65 ml of 1M Cu(NO3)2 aqueous solution, 7 ml of 1M SmCl2 dilute hydrochloric acid aqueous solution and 5 ml of 1M Al(NO3)3 aqueous solution, place them in a 400 ml beaker and stir to mix.

[0099] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0100] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - .

[0101] 4) Add 1.0 g of 5A molecular sieve and 1 M-ZnC2O4 and 37.5 ml of 0.56 M oxalic acid solution to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0102] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 300°C for 3 h.

[0103] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 65: 37.5: 7: 5 (atomic ratio).

[0104] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 16 h at a reduction temperature of 240°C.

[0105] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor for temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg-1cat.h-1). The catalyst loading was 3g, the raw gas composition was CO:H2:CO2:N2=15:70:5:5, the reaction pressure was 0.5MPa, and the space velocity was 3000h -1 The evaluation temperature was 210°C and the initial activity was 1.70 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.52 g / min. -1 cat.h -1 .

[0106] Example 7

[0107] 1) Take 40 ml of 1M CuCl2 aqueous solution, 40 ml of 1M ZnSO4 aqueous solution, 5 ml of 1M SmCl2 dilute hydrochloric acid aqueous solution and 2 ml of 1M Al(NO3)3 aqueous solution, place in a 400 ml beaker and stir to mix.

[0108] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0109] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - and SO4 2- .

[0110] 4) Add 2.0 g of 3A molecular sieve and 24 mmol of nitrilotriacetic acid to the precipitate, add water and stir for 0.5 h, and let stand for 10 min.

[0111] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 320°C for 3 h.

[0112] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The distribution ratio of the active components of the obtained catalyst is Cu: Zn: Sm: Al = 40: 40: 5: 2 (atomic ratio).

[0113] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 20 h at a reduction temperature of 220°C.

[0114] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=13:71:6:5, the reaction pressure is 4.5 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.63 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.40 g / min. -1 cat.h -1 .

[0115] Example 8

[0116] 1) Take 50 ml of 1M CuSO4 aqueous solution, 22 ml of 1M Zn(CH3COO)2 aqueous solution, 0.5 ml of 1M Sm(CH3COO)2 dilute hydrochloric acid aqueous solution and 2 ml of 1M Al(NO3)3 aqueous solution, place them in a 400 ml beaker and stir to mix.

[0117] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0118] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - .

[0119] 4) Add 1.0 g of Beta molecular sieve and 100 ml of 0.3 M adiponitrile ethanol solution to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0120] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 380°C for 3 h.

[0121] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 50: 22: 0.5: 2 (atomic ratio).

[0122] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 17 h at a reduction temperature of 210°C.

[0123] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor for temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg-1cat.h-1). The catalyst loading was 3g, the raw gas composition was CO:H2:CO2:N2=11:70:7:7, the reaction pressure was 5.5MPa, and the space velocity was 3000h -1 The evaluation temperature was 210°C and the initial activity was 1.30 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.14 g / min. -1 cat.h -1 .

[0124] Example 9

[0125] 1) Take 55 ml of 1M CuBr2 aqueous solution, 30 ml of 1M Zn(CH3COO)2 aqueous solution, and 2 ml of 1M Sm(CH3COO)2 dilute hydrochloric acid aqueous solution, place them in a 400 ml beaker and stir to mix.

[0126] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0127] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - and no Br - .

[0128] 4) Add 1.0 g of aluminum silicate (3Al2O3·2SiO2), 3 mmol of aluminum stearate powder and 30 ml of an aqueous solution containing 0.6 M acetonitrile to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0129] 5) Filter, dry the filter cake at 110℃ for 4h, crush, and calcine at 400℃ for 3h.

[0130] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 55: 30: 2: 3.

[0131] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 18 h at a reduction temperature of 190°C.

[0132] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=20:65:5:5, the reaction pressure is 3.0 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.37 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.21 g / min. -1 cat.h -1 .

[0133] Example 10

[0134] 1) Place 30 ml of 1M Zn(CH3COO)2 aqueous solution, 2 ml of 1M Sm(CH3COO)2 dilute hydrochloric acid aqueous solution, and 3 ml of 1M Al(NO3)2 aqueous solution in a 400 ml beaker and stir to mix.

[0135] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0136] 3) Wash the precipitate prepared in step 2 with 60° C. deionized water until there is no Cl-.

[0137] 4) Add 1.0 g of titanium dioxide, 55 ml of 1 M copper oxalate ammonia solution and 23 mmol of 1,2-dichloroethane to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0138] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 340°C for 3 h.

[0139] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 55: 30: 2: 3.

[0140] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 20 h at a reduction temperature of 280°C.

[0141] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=19:68:5:5, the reaction pressure is 3.5 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.40 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.28 g / min. -1 cat.h -1 .

[0142] Embodiment 11

[0143] 1) Place 45 ml of 1M Cu(NO3)2 aqueous solution, 35 ml of 1M ZnCl2 aqueous solution, 6 ml of 1M Sm(CH3COO)2 dilute hydrochloric acid aqueous solution, and 3 ml of 1M Al(NO3)2 aqueous solution in a 400 ml beaker and stir to mix.

[0144] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0145] 3) Wash the precipitate prepared in step 2 with 60°C deionized water until there is no Cl - .

[0146] 4) Add 1.0 g of titanium silicalite and 35 ml of 0.5 M zirconium acetate ethanol solution to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0147] 5) Filter, dry the filter cake at 110℃ for 4h, crush, and calcine at 365℃ for 3h.

[0148] 6) Finally, the mixed oxide obtained in step 5 is tableted, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 45: 35: 6: 3 (atomic ratio).

[0149] The catalyst was activated (reduced) in a fixed bed reactor before use and reduced with low H2 (H2 / N2=3 / 97) for 20 h at a reduction temperature of 230°C.

[0150] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=15:70:5:5, the reaction pressure is 4.0 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.70 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.46 g / min. -1 cat.h -1 .

[0151] Example 12

[0152] 1) Take 65 ml of 1M Cu(NO3)2 aqueous solution, 20 ml of 1M Zn(NO3)2 aqueous solution, 7 ml of 1M SmCl2 dilute hydrochloric acid aqueous solution and 5 ml of 1M Al(NO3)3 aqueous solution, place them in a 400 ml beaker and stir to mix.

[0153] 2) Take 150ml of 1M-Na2CO3 aqueous solution and place it in a 1000ml beaker, heat it to 70℃, and add the mixed solution obtained in step 1 to the Na2CO3 aqueous solution at a rate of 20ml / min while stirring until a precipitate is precipitated. After aging for 2h, stop heating and stirring. At this time, the pH of the mixed solution is 7.5.

[0154] 3) Wash the precipitate prepared in step 2 with 60° C. deionized water until there is no Cl-.

[0155] 4) Add 5.0 g of hydrogen form silica sol (content 30%) and 25 ml of 0.9 M tetramethylpiperidinyl oxide ethanol solution to the precipitate, stir for 0.5 h, and let stand for 10 min.

[0156] 5) Filter, dry the filter cake at 110°C for 4 h, crush it, and calcine it at 350°C for 3 h.

[0157] 6) Finally, the mixed oxide obtained in step 5 is pressed into tablets, crushed and sieved to collect 20-40 mesh catalyst for use. The active component distribution ratio of the obtained catalyst is Cu: Zn: Sm: Al = 65: 20: 7: 5 (atomic ratio).

[0158] The catalyst was activated (reduced) in a fixed bed reactor before use, and reduced with low H2 (H2 / N2=3 / 97) for 19 h at a reduction temperature of 200°C.

[0159] The activity of the catalyst was evaluated by using a gas phase fixed bed reactor to carry out temperature reduction and activity evaluation. The product was analyzed by gas chromatography, and the activity of the catalyst was expressed as space-time yield (gg -1 cat.h -1 ) The catalyst loading is 3 g, the raw gas composition is CO:H2:CO2:N2=15:70:5:5, the reaction pressure is 8.5 MPa, and the space velocity is 3000 h -1 The evaluation temperature was 210°C and the initial activity was 1.85 gg -1 cat.h -1 The catalyst was then heat treated at 400°C for 5 h in a syngas atmosphere and then cooled to 210°C. The results showed that the activity after heat treatment was 1.67 g / min. -1 cat.h -1 .

[0160] Table 1. Catalyst preparation and catalytic reaction results

[0161]

[0162] Compared with the prior art, the present invention provides a catalyst capable of synthesizing methanol from CO and / or CO2 and H2 at low temperature and wide pressure, and the catalyst has high activity and excellent thermal stability.

[0163] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A catalyst for preparing methanol from synthesis gas, comprising or essentially consisting of the following components: A catalyst active component, the catalyst active component comprises or consists of a mixed oxide of Cu, Zn, Sm and Al, wherein the molar ratio of Cu, Zn, Sm and Al is 10-75:20-60:0.5-7:1-10; for example, 40-65:20-40:0.5-7:2-5; The binder is one or more selected from γ-Al2O3, silica, silica-alumina molecular sieve, activated carbon, titanium silicate molecular sieve, hydrotalcite, aluminum silicate, magnesium aluminum spinel, titanium dioxide, bentonite, diatomaceous earth, magnesium phosphate, calcium aluminate, and calcium silicate, and is particularly selected from one or more selected from γ-Al2O3, 5A molecular sieve, ZSM-5 molecular sieve, 3A molecular sieve, diatomaceous earth, MCM-41, Beta molecular sieve, and Y molecular sieve.

2. The catalyst according to claim 1, wherein The molar ratio of the active components of the catalyst, namely, Cu, Zn, Sm and Al, is 5-25:4-20:0.25-2.5:1; and / or The amount of the binder is 0.01 to 20 wt % based on the weight of the catalyst; and / or The particle size of the binder is 20nm to 275um, and / or The basic pore diameter of the binder is 0.2nm to 80nm.

3. A method for preparing a catalyst for producing methanol from synthesis gas, the method comprising the following steps: 1) preparing a mixed aqueous solution or an acid-base solution or an organic solution of each active component metal of the catalyst, Sm and a salt selected from one or more of Cu, Zn and Al; 2) adding the solution of step 1) to the precipitant aqueous solution under stirring at 60-80° C. to obtain a precipitate, and controlling the end point pH to be 7.0-9.4; 3) Wash the precipitate obtained in step 2) with deionized water until there is no halogen ion (such as Cl - Br - ) and / or SO4 2- ; 4) adding a binder, a solution or powder of one or more salts of Cu, Zn and Al that are not selected in step 1), if any, and an optional strong electron-withdrawing CO or CO2 molecular activator or a solution thereof to the precipitate treated in step 3), stirring and mixing evenly, and allowing to stand; 5) drying the mixture obtained in step 4) and, if necessary, separating the solid mixture obtained, at 70-160° C. and calcining at 300-400° C. for 2-4 h; 6) grinding, shaping, and crushing the calcined product obtained in step 5) to obtain a catalyst, or The calcined product obtained in step 5) is added to a solution of a strong electron-withdrawing CO or CO2 molecular activator, impregnated, dried, and crushed to obtain a catalyst. in, In the method, the molar ratio of the active component metals of the catalyst, Cu, Zn, Sm and Al, is 10-75:20-60:0.5-7:1-10; for example, 40-65:20-40:0.5-7:2-5.

4. The preparation method according to claim 3, wherein In step 1), The salt of Sm, Cu, Zn and Al is one or more selected from nitrate, acetate, format, sulfate, hydrochloride, perchlorate, oxalate, acetylacetonate, metallocene derivative salt and stearate; The acid-base solution is a hydrochloric acid solution, an oxalic acid solution, a nitric acid solution, a sulfuric acid solution, an acetic acid solution, a formic acid solution, a phosphoric acid solution or a benzoic acid solution of a salt; The organic solvent is ethanol solution, isopropanol solution, ethyl acetate solution, ether solution, tetrahydrofuran solution, dichloromethane solution or hexane solution.

5. The preparation method according to claim 3, wherein: In step 2), Adding under stirring at 65-70°C; and / or The precipitant is one or more selected from Na2CO3, NaHCO3, K2CO3, KHCO3, Cs2CO3, Na2HPO3, K2HPO3, sodium acetate, calcium acetate, lithium diisopropylamide, triethylamine, and pyridine; and / or The precipitant is 98.5% Cl - ≤ 0.1%; and / or Control the end point pH = 7.0 ~ 8.

0.

6. The preparation method according to claim 3, wherein: In step 4), The binder is one or more selected from γ-Al2O3, silicon dioxide, silica-alumina molecular sieve, activated carbon, titanium-silica molecular sieve, hydrotalcite, aluminum silicate, magnesium aluminum spinel, titanium dioxide, bentonite, diatomaceous earth, magnesium phosphate, calcium aluminate, calcium silicate, in particular one or more selected from γ-Al2O3, 5A molecular sieve, ZSM-5 molecular sieve, 3A molecular sieve, diatomaceous earth, MCM-41, Beta molecular sieve, Y molecular sieve; and / or Based on the weight of the catalyst, the binder is used in an amount of 0.01 to 20 wt %; and / or The particle size of the binder is 20nm to 275um, and / or The basic pore diameter of the binder is 0.2nm to 80nm.

7. The preparation method according to claim 3, wherein: In step 4), The strong electron-withdrawing CO or CO2 molecular activator is one or more selected from oxalic acid, oxalate, acetylacetonate, metallocene derivative salt, nitrilotriacetic acid, nitrilotriacetate, formic acid, formate, acetic acid, acetate, p-toluenesulfonic acid and salt, tetramethylpiperidinoxide, acetonitrile, adiponitrile, 1,2-dichloroethane; and / or The amount of the strong electron-withdrawing CO or CO2 molecular activator is 0.5% to 40% of the total metal molar amount of the catalyst active component; and / or The solution of the strong electron-withdrawing CO or CO2 molecular activator is an aqueous solution, an ammonia solution, an ethanol solution, an acetone solution, an ether solution, a tetrahydrofuran solution, a pyridine solution, or a triethylamine solution; and / or Stir and mix for 0.5 to 4 hours.

8. The preparation method according to claim 3, wherein: In step 5), drying at 100-120° C. for 2-5 hours; and / or Calcinate at 300-400℃ for 2-3h.

9. The preparation method according to claim 3, wherein: The catalyst obtained in step 6) is reduced with H2 / N2=3 / 97 for 16 to 20 hours at a reduction temperature of 190 to 280°C.

10. A method for synthesizing methanol, the method comprising: The catalyst according to claim 1 or 2 or the catalyst prepared by the preparation method according to any one of claims 3 to 9 is loaded into a reactor, and raw gas CO, H2, CO2, N2 is introduced at a space velocity of 1000 to 15000 h -1 , the reaction pressure is 0.5~10MPa, and the reaction temperature is 190~280℃; In particular, the raw gas composition is: CO:H2:CO2:N2=10~20:50~90:2~8:2~8.

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