CN114797903B - Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof - Google Patents
Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract
本发明涉及催化剂领域，公开了合成气制低碳醇催化剂，该催化剂的制备方法，以及该催化剂在合成气制低碳醇中的应用。所述催化剂含有活性组分Co、Mo、K、S和助剂M，其中，M选自Mg、Ca和La中的至少一种元素；以所述催化剂的总量为基准，Co的含量为5.5‑17wt％，Mo的含量为33‑47wt％，K的含量为4‑9wt％，S的含量为30‑50wt％，M的含量为0.05‑0.9wt％，其中，M与Mo的摩尔比为0.005‑0.09：1。本发明的合成气制低碳醇催化剂用于合成气制低碳醇反应中，催化活性高，提高了产物中总醇的选择性和总醇的时空产率。
The invention relates to the field of catalysts, and discloses a catalyst for producing low-carbon alcohol from synthesis gas, a preparation method of the catalyst, and the application of the catalyst in producing low-carbon alcohol from synthesis gas. The catalyst contains active components Co, Mo, K, S and auxiliary agent M, wherein M is selected from at least one element among Mg, Ca and La; based on the total amount of the catalyst, the content of Co is 5.5-17wt%, the content of Mo is 33-47wt%, the content of K is 4-9wt%, the content of S is 30-50wt%, the content of M is 0.05-0.9wt%, where the molar ratio of M to Mo is 0.005‑0.09:1. The synthesis gas to lower alcohol alcohol catalyst of the present invention is used in the synthesis gas to lower alcohol alcohol reaction, has high catalytic activity, and improves the selectivity of the total alcohol in the product and the space-time yield of the total alcohol.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing low-carbon alcohol from synthesis gas, a preparation method of the catalyst and application of the catalyst in preparing low-carbon alcohol from synthesis gas.
Background
The energy is the basis of human survival and civilization evolution, but China is a country with oil deficiency, less gas and more coal, and has important strategic significance in developing modern coal chemical industry and developing coal clean and efficient conversion technology. While synthesis gas (CO+H) is produced by coal gasification 2 ) The synthesis gas is converted into the low-carbon alcohol by the catalytic conversion, so that the shortage of petroleum resources in China can be relievedAnd is one of the most practical and feasible ways for realizing the efficient and clean conversion of coal resources. The low-carbon mixed alcohol can be used as a gasoline additive, fuel and high-added value chemicals after separation.
The selectivity of target products is lower due to the complexity of the reaction process and the mechanism of the synthesis gas to prepare the low-carbon alcohol, and the selectivity of byproducts of methanol and hydrocarbons is higher. In the reaction process, CO is required to be dissociated and adsorbed to realize carbon chain growth, CO is required to be non-dissociated and adsorbed, the CO is inserted when the carbon chain is increased to a certain length, so that alcohol is generated, and the coordinated matching of the two reactions is realized, so that more target products C can be obtained 2 OH-C 6 OH, if the insertion capability of CO is weaker, more hydrocarbons are obtained after the carbon chain is lengthened, and if the carbon chain is weaker, CO is hydrogenated to generate more methanol, thereby leading to a target product C 2 + The alcohol selectivity is low, so the design and development of a catalyst with high selectivity and high activity and excellent stability is a key factor for the breakthrough of the technology.
MoS 2 The base catalyst has the advantages of unique sulfur resistance, higher activity, higher alcohol selectivity, long service life and the like, and is considered as one of the most promising catalyst systems for synthesizing low-carbon alcohol, but the current MoS 2 The base catalyst still has the problems of low catalytic activity, low total alcohol selectivity, low total alcohol space time yield and the like.
CN103459020a discloses a catalyst for converting synthesis gas into alcohol comprising nickel, molybdenum, at least one metal selected from palladium, ruthenium, chromium, gold, zirconium and aluminum, and a combination of at least one of alkali metals or alkaline earth metals as promoters, although the catalyst may enhance C 2 -C 4 Alcohol selectivity, but conversion is lower and total alcohol selectivity is lower.
US4882360 discloses a catalyst for preparing low-carbon alcohol from synthesis gas and a preparation method thereof. The catalyst comprises at least one of molybdenum and tungsten as a first component, at least one of Fe, co and Ni as a second component, an alkali metal or alkaline earth metal auxiliary agent as a third component, and other components and a carrier as a fourth component, wherein the catalyst is at a reaction temperatureAbout 300 ℃, the reaction pressure is 10MPa, and the airspeed is 1000-2000h -1 When the total alcohol selectivity in the product is more than 70%, CH 3 OH/C 2 + Alcohol (wt%)<0.5, but the space velocity used is lower, resulting in a lower space-time yield of the alcohol product.
Disclosure of Invention
The invention aims to overcome the MoS existing in the prior art 2 The base catalyst is used for preparing low-carbon alcohol from synthesis gas, has the problems of low total alcohol selectivity and low total alcohol space-time yield, and provides the catalyst for preparing low-carbon alcohol from synthesis gas, and the preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for preparing low carbon alcohol from synthesis gas, which contains an active component Co, mo, K, S and an auxiliary agent M, wherein M is at least one element selected from Mg, ca and La;
based on the total amount of the catalyst, the Co content is 5.5-17wt%, the Mo content is 33-47wt%, the K content is 4-9wt%, the S content is 30-50wt%, and the M content is 0.05-0.9wt%, wherein the molar ratio of M to Mo is 0.005-0.09:1.
the second aspect of the invention provides a preparation method of a catalyst for preparing low-carbon alcohol from synthesis gas, which comprises the following steps:
(1) Preparing an ammonium thiomolybdate solution and a mixed solution containing cobalt salt and M salt;
(2) Carrying out coprecipitation reaction on the ammonium thiomolybdate solution and the mixed solution in a base solution;
(3) Carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, and then washing, drying and roasting the obtained solid to obtain a precursor;
wherein the drying and the roasting are performed under the protection of inert gas;
(4) Mixing the precursor with potassium carbonate, grinding and tabletting to obtain the catalyst;
wherein M is at least one element selected from Mg, ca and La; the dosages of the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate are such that the catalyst obtained contains 5.5 to 17 weight percent of Co, 33 to 47 weight percent of Mo, 4 to 9 weight percent of K, 30 to 50 weight percent of S and 0.05 to 0.9 weight percent of M; the dosages of the ammonium thiomolybdate and the M salt are as follows: the molar ratio of M to Mo is 0.005-0.09:1.
in a third aspect, the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas, which is prepared by the preparation method.
In a fourth aspect, the invention provides the use of a catalyst for preparing low-carbon alcohol from synthesis gas as described above in preparing low-carbon alcohol from synthesis gas.
By the technical scheme, the catalyst for preparing the low-carbon alcohol from the synthetic gas is used in the reaction for preparing the low-carbon alcohol from the synthetic gas, has high catalytic activity, and improves the selectivity of the total alcohol in the product and the space-time yield of the total alcohol.
Drawings
FIG. 1 is an X-ray diffraction analysis (XRD) pattern of the catalysts prepared in examples 1-3 and comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a catalyst for preparing low-carbon alcohol from synthesis gas, which contains an active component Co, mo, K, S and an auxiliary agent M, wherein M is at least one element selected from Mg, ca and La;
based on the total amount of the catalyst, the Co content is 5.5-17wt%, the Mo content is 33-47wt%, the K content is 4-9wt%, the S content is 30-50wt%, and the M content is 0.05-0.9wt%, wherein the molar ratio of M to Mo is 0.005-0.09:1.
in some embodiments of the invention, the aforementioned catalyst composition achieves the objects of the invention, in order to further increase the activity of the catalyst and to further increase the selectivity of the total alcohols in the product and the space-time yield of the total alcohols, it is preferred that the content of Co is 6.5-16 wt.%, the content of Mo is 35-45 wt.%, the content of K is 4.5-7 wt.%, the content of S is 35-45 wt.%, and the content of M is 0.08-0.6 wt.%, based on the total amount of the catalyst.
In some embodiments of the invention, co, mo and the auxiliary M are present as sulfides and K is K in the catalyst for preparing low-carbon alcohol from synthetic gas 2 S 3 O 6 Is present in the form of (c). Co and Mo sulfides exist in a variety of forms, including complex metal sulfides (Co-MoS 2 ) And independent metal sulfides (MoS) 2 、CoS 2 And Co 9 S 8 ). Wherein in the presence of a separate metal sulfide phase (CoS 2 、Co 9 S 8 、MoS 2 ) On which CO dissociative adsorption, H occurs 2 Dissociation adsorption and CH x The formation of species occurs over a period of about 100 to 200 hours under reaction evaluation conditions, coS 2 Gradually change into Co more favorable for reaction 9 S 8 The method comprises the steps of carrying out a first treatment on the surface of the In a potassium promoted complex metal sulfide phase (Co-MoS 2 ) On which non-dissociative adsorption of CO, carbon chain growth and alcohol formation reactions occur.
In some embodiments of the invention, the synthesis gas to lower alcohol catalyst of the invention is subjected to phase analysis using an X-ray diffractometer (XRD) available from Rigaku corporation under the model D/max-2600/pc. In an X-ray diffraction analysis (XRD) diagram, characteristic peaks and K of the catalyst for preparing the low-carbon alcohol by using the synthetic gas appear at 2 theta = 19.0 degrees, 23.9 degrees, 24.7 degrees, 24.9 degrees, 26.5 degrees, 28.1 degrees and 31.1 degrees 2 S 3 O 6 The standard card PDF-75-1479 is consistent, which shows that K is formed in the catalyst for preparing low-carbon alcohol from the synthetic gas 2 S 3 O 6 A structure; k is not generated in the catalyst for preparing low-carbon alcohol from synthesis gas without adding the auxiliary agent M 2 S 3 O 6 Is not formed into K 2 S 3 O 6 Structure, described in MoS 2 The addition agent M is introduced in the preparation process of the base catalyst, so that the K on the catalyst can be promoted 2 S 3 O 6 Of a structureFormation, K 2 S 3 O 6 The structure can stabilize the intermediate product of the reaction and change the electronic structure of the catalyst, so that the activation of CO is easy, simultaneously the hydrogenation activity of alkyl species is reduced, and the addition of the auxiliary agent M is also beneficial to reducing Co-MoS 2 The size of the active sites increases the number of active sites per weight of the catalyst, thereby increasing the catalytic activity of the catalyst as well as the selectivity of the total alcohol in the product and the space-time yield of alcohol.
In some embodiments of the invention, if the molar ratio of the auxiliary M to Mo is greater than 0.09, not only does the effect of increasing the total alcohol selectivity and the total alcohol space-time yield, but the catalyst activity is reduced; if the molar ratio of the auxiliary M to Mo is less than 0.005, the content of M in the catalyst is too low to improve the total alcohol selectivity and the total alcohol space-time yield, so that only the molar ratio of the auxiliary M to Mo is controlled to be 0.005-0.09: within the range of 1, the effect of increasing the selectivity and space-time yield of the total alcohol can be achieved. In order to further increase the selectivity to total alcohol and the space-time yield of total alcohol, the molar ratio of auxiliary M to Mo is preferably from 0.008 to 0.06:1, more preferably 0.01 to 0.05:1.
in some embodiments of the invention, in order to ensure that the two active centers (Co-MoS 2 And MoS 2 、CoS 2 ) In order to increase the catalytic activity of the catalyst in the reaction of preparing low-carbon alcohol from synthesis gas and the selectivity of total alcohol in the product, preferably, the molar ratio of Co to Mo is 0.2-0.8:1, more preferably 0.3 to 0.7:1.
in some embodiments of the invention, to promote the formation of sulfides of Co, mo active metals, to increase the catalytic activity of the catalyst and the selectivity of the total alcohols in the product, the molar ratio of S to Mo is preferably from 2 to 4:1, more preferably 2.5-3.5:1.
the second aspect of the invention provides a preparation method of a catalyst for preparing low-carbon alcohol from synthesis gas, which comprises the following steps:
(1) Preparing an ammonium thiomolybdate solution and a mixed solution containing cobalt salt and M salt;
(2) Carrying out coprecipitation reaction on the ammonium thiomolybdate solution and the mixed solution in a base solution;
(3) Carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, and then washing, drying and roasting the obtained solid to obtain a precursor;
wherein the drying and the roasting are performed under the protection of inert gas;
(4) Mixing the precursor with potassium carbonate, grinding and tabletting to obtain the catalyst;
wherein M is at least one element selected from Mg, ca and La; the dosages of the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate are such that the catalyst obtained contains 5.5 to 17 weight percent of Co, 33 to 47 weight percent of Mo, 4 to 9 weight percent of K, 30 to 50 weight percent of S and 0.05 to 0.9 weight percent of M; the dosages of the ammonium thiomolybdate and the M salt are as follows: the molar ratio of M to Mo is 0.005-0.09:1.
in some embodiments of the present invention, the amounts of ammonium thiomolybdate, cobalt salt, M salt and potassium carbonate may be selected according to the content and molar ratio of the aforementioned components, and will not be described herein.
In some embodiments of the present invention, the cobalt salt may be a water-soluble cobalt salt commonly used in the art, selected from water-soluble cobalt salts, may be commercially available, and for example, may be at least one selected from cobalt acetate, cobalt nitrate, and cobalt sulfate.
In some embodiments of the present invention, the M salt may be a water-soluble M salt commonly used in the art, selected from water-soluble salts containing M element, may be commercially available, and for example, may be at least one selected from acetate, nitrate and sulfate containing M element.
In some embodiments of the present invention, in step (1), the ammonium thiomolybdate solution may be formulated according to a conventional method, for example, the step of formulating the ammonium thiomolybdate solution may specifically be: reacting ammonium molybdate and ammonium sulfide solution at 50-70 deg.c for 0.2-4 hr.
In some specific embodiments of the present invention, in the step (2), a catalyst precursor with a predetermined proportion can be obtained by using a base solution, and the precipitation reaction can be maintained to be performed within a pH range of 4-6, and in addition, the mixed solution of the ammonium thiomolybdate solution, the cobalt salt and the M salt can be ensured to be uniformly precipitated at a set temperature when the mixed solution is dropped into a precipitation flask. In order to further increase the selectivity of the total alcohols in the product and the space-time yield of the total alcohols, the base liquid is preferably an acetic acid solution with a mass concentration of 20 to 40 wt.%.
In some embodiments of the present invention, preferably, in step (2), the conditions of the coprecipitation reaction include: the aging temperature is 50-60 ℃ and the aging time is 0.5-12h.
In some embodiments of the present invention, in step (3), the solid-liquid separation may be performed by a conventional separation method to separate solids therein. For example, solid-liquid separation can be achieved by filtration.
In some embodiments of the present invention, the solid obtained by solid-liquid separation may be washed with deionized water, and then dried and baked under inert gas protection to obtain the precursor. In order to prevent the catalyst from being oxidized drastically and from structural change, the drying and the calcination are carried out in an inert atmosphere. The inert atmosphere may be an atmosphere formed of various gases which do not react with the reactants and products, for example, an atmosphere formed of nitrogen and/or helium and/or argon.
In some embodiments of the present invention, the drying conditions are not particularly limited as long as the solvent attached to the product can be removed, and for example, the drying conditions generally include: the drying temperature may be 40-120deg.C, preferably 70-110deg.C; the drying time may be 2 to 25 hours, preferably 4 to 20 hours.
In some embodiments of the present invention, the conditions for the calcination are not particularly limited as long as CoMoS can be caused 4 Decomposition into Co-MoS 2 The excess S may be distilled off in the form of an elemental S, and the conditions for calcination typically include, for example: the roasting temperature can be 300-500 ℃ and the roasting time can beCan be 0.3-6h. To avoid Co-MoS 2 The active center particles are larger and the activity is reduced, preferably the roasting temperature is 350-400 ℃, and the roasting time is 0.5-4h.
The third aspect of the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas, which is prepared by the preparation method. The catalyst contains an active component Co, mo, K, S and an auxiliary agent M, wherein M is at least one element selected from Mg, ca and La;
based on the total amount of the catalyst, the Co content is 5.5-17wt%, the Mo content is 33-47wt%, the K content is 4-9wt%, the S content is 30-50wt%, and the M content is 0.05-0.9wt%, wherein the molar ratio of M to Mo is 0.005-0.09:1.
in some embodiments of the present invention, preferably, co is present in an amount of 6.5 to 16wt%, mo is present in an amount of 35 to 45wt%, K is present in an amount of 4.5 to 7wt%, S is present in an amount of 35 to 45wt%, and M is present in an amount of 0.08 to 0.6wt%, based on the total amount of the catalyst.
In some embodiments of the invention, preferably, the molar ratio of M to Mo is 0.008 to 0.06:1, more preferably 0.01 to 0.05:1.
in some embodiments of the invention, preferably, the molar ratio of Co to Mo is 0.2 to 0.8:1, more preferably 0.3 to 0.7:1.
in some embodiments of the invention, the molar ratio of S to Mo is preferably from 2 to 4:1, more preferably 2.5-3.5:1.
in some embodiments of the invention, preferably, co, mo and M are present as sulfides, K is K 2 S 3 O 6 Is present in the form of (c).
In a fourth aspect, the invention provides the use of a catalyst for preparing low-carbon alcohol from synthesis gas as described above in preparing low-carbon alcohol from synthesis gas.
In some embodiments of the invention, a method for producing lower alcohols from synthesis gas using the catalyst of the invention may comprise: the catalyst of the invention is molded and put into a fixed bed reactor, the air in the reactor is replaced by inert gas, and thenAnd then heating the reactor, and introducing reaction gas into the reactor to react after the temperature and the pressure rise to the temperature and the pressure required by the reaction, thereby preparing the low-carbon alcohol. Wherein the reaction conditions include: the pressure is 7-10MPa, the temperature is 320-350 ℃, and the volume airspeed is 2000-4000 mL.g -1 ·h -1 Volume ratio H of reaction gas 2 Co=0.8-1.2: 1. wherein the synthesis gas to lower alcohols may be carried out in a fixed bed or a fluidized bed, preferably in a fixed bed.
In the invention, the pressure is gauge pressure.
The present invention will be described in detail by way of examples, but it should be understood that the scope of the present invention is not limited by the examples.
In the following examples and comparative examples, the raw materials used are commercially available.
The molar (or weight) composition of the prepared catalyst component for preparing the low-carbon alcohol from the synthetic gas is analyzed and determined by an X-ray fluorescence spectrometer (XRF) with the model number ZSX Primus II purchased from Rigaku company, a Upside Radiation X-ray generator, a 4kW Rh target is adopted, the category range of the test element is F-U, the diameter of the test area is 30mm, and the test method is a full-element semi-quantitative method;
x-ray diffraction analysis was performed on the produced synthesis gas-produced lower alcohol catalyst by X-ray diffractometer (XRD) available from Rigaku corporation under the model D/max-2600/pc;
the microscopic morphology of the catalyst for preparing the low-carbon alcohol from the synthesis gas is measured by a Scanning Electron Microscope (SEM) with the model of Nova Nano SEM 450 purchased from FEI company, the adopted accelerating voltage is 20kV-30kV, the resolution limit is about 1.2nm, and the magnification is 25-200K times.
The catalytic performance of the prepared catalyst for preparing low-carbon alcohol from synthetic gas was evaluated by a four-way reactor purchased from Altamira company.
The reaction conditions include: the pressure is 8MPa, the temperature is 345 ℃, and the volume airspeed is 3000mL g -1 ·h -1 Volume ratio H of reaction gas 2 /CO＝1/1。
The evaluation process comprises the following steps: tabletting and sieving the catalyst of the inventionObtaining particles with 20-40 meshes, fixing a catalyst on a constant temperature section of a reactor by quartz sand, wherein the loading amount of the catalyst is 1.5 g, after leakage inspection of the device, replacing air in the reactor with inert gas He gas for 3-5 times, then heating the reactor, and after the temperature and the pressure are raised to the temperature and the pressure required by the reaction (345 ℃,8 MPa), obtaining 37.5mL (standard condition) of H 2 And 37.5mL CO and 3.26mL N 2 And (3) introducing (internal standard gas) into a reactor to perform the reaction of preparing the low-carbon alcohol from the synthesis gas.
After the reacted gas tail gas enters a cold trap to carry out gas-liquid separation, adopting Agilent 7890 chromatography to carry out online analysis on the tail gas, wherein H 2 、CO、CH 4 、N 2 Analyzing by a TDX-01 carbon molecular sieve chromatographic column, taking He as carrier gas, and adopting TCD for detection; c (C) 1 -C 6 Hydrocarbons (olefins, alkanes) by modification of Al 2 O 3 And (3) filling chromatographic column analysis, wherein Ar is used as a carrier, and FID detection is adopted. The remaining product was analyzed by off-line chromatography Shimadzu GC-2010, and the liquid product was analyzed by two Porpak Q columns, TCD (water and methanol) and FID (C) 1 -C 5 Is detected by the detector.
CO conversion, total alcohol selectivity and C 2 + The alcohol selectivity is used as an evaluation index for the performance of the catalyst for preparing the low-carbon alcohol from the synthesis gas. CO conversion (χCO), product selectivityBased on the number of moles of carbon, carbon-based selectivity and total alcohol selectivity (S ROH Based on moles of carbon, carbon-based selectivity) is calculated from the following equations:
wherein χco represents CO conversion;indicating product selectivity; s is S ROH Indicating total alcohol selectivity; f represents the mole number of the substance, i represents the carbon atom number of the substance; />Represents the number of moles of inlet CO, +.>The number of moles of CO at the outlet is indicated.
Example 1
(1) 100g of ammonium molybdate solution with the concentration of 26.5 weight percent is heated to 60 ℃, 206.5g of ammonium sulfide solution with the concentration of 20 weight percent is added, and the mixture is reacted for 1 hour at 60 ℃ to obtain ammonium thiomolybdate solution; 13.2g of cobalt acetate and 0.42g of magnesium acetate are dissolved in 280mL of deionized water to prepare a mixed solution;
(2) Dropping the ammonium thiomolybdate solution and the mixed solution into a base solution (30 wt% acetic acid solution of the base solution) at the same speed at the temperature of 55 ℃ for coprecipitation reaction, and aging for 1h at the temperature of 55 ℃ to obtain a precipitate;
(3) Filtering and washing the precipitate, drying the precipitate for 12 hours at 90 ℃ under the protection of nitrogen atmosphere, and roasting the precipitate for 1 hour at 400 ℃ under the protection of nitrogen atmosphere to obtain a precursor;
(4) 9g of precursor and 1g of K 2 CO 3 Mixing, grinding and tabletting, and the prepared catalyst is denoted as S1.
Wherein, the mol ratio of Mg to Mo is 0.011:1, a step of; the molar ratio of Co to Mo is 0.35:1, a step of; the molar ratio of S to Mo is 2.7:1, the content of Mo is 42.43wt%, the content of Co is 9.12wt%, the content of Mg is 0.12wt%, the content of K is 5.66wt%, and the content of S is 38.33wt%.
Example 2
(1) Heating 100g of ammonium molybdate solution with the concentration of 26.5 weight percent to 60 ℃, then adding 340.5g of ammonium sulfide solution with the concentration of 20 weight percent, and reacting for 1h at 65 ℃ to obtain ammonium thiomolybdate solution; 30.5g of cobalt nitrate and 0.94g of lanthanum acetate are dissolved in 320mL of deionized water to prepare a mixed solution;
(2) Dropping the ammonium thiomolybdate solution and the mixed solution into a base solution (30 wt% acetic acid solution of the base solution) at the same speed at the temperature of 55 ℃ for coprecipitation reaction, and aging for 2 hours at the temperature of 55 ℃ to obtain a precipitate;
(3) Filtering and washing the precipitate, drying the precipitate for 12 hours at 90 ℃ under the protection of nitrogen atmosphere, and roasting the precipitate for 1.5 hours at 390 ℃ under the protection of nitrogen atmosphere to obtain a precursor;
(4) 9g of precursor and 1g of K 2 CO 3 Mixing, grinding and tabletting, and the prepared catalyst is denoted as S2.
Wherein, the mole ratio of La to Mo is 0.01:1, a step of; the molar ratio of Co to Mo was 0.7:1, a step of; the molar ratio of S to Mo is 3.4:1, 34.86wt% of Mo, 14.99wt% of Co, 0.50wt% of La, 5.66wt% of K and 39.65wt% of S.
Example 3
(1) 100g of ammonium molybdate solution with the concentration of 26.5 weight percent is heated to 55 ℃, 206.5g of ammonium sulfide solution with the concentration of 20 weight percent is added, and the mixture is reacted for 1 hour at the temperature of 55 ℃ to obtain ammonium thiomolybdate solution; 18.9g of cobalt acetate and 0.87g of calcium sulfate were dissolved in 280mL of deionized water to prepare a mixed solution;
(2) Dropping the ammonium thiomolybdate solution and the mixed solution into a base solution (30 wt% acetic acid solution of the base solution) at the same speed at the temperature of 55 ℃ for coprecipitation reaction, and aging for 1h at the temperature of 55 ℃ to obtain a precipitate;
(3) Filtering and washing the precipitate, drying at 100 ℃ for 8 hours under the protection of nitrogen atmosphere, and roasting at 360 ℃ for 4 hours under the protection of nitrogen atmosphere to obtain a precursor;
(4) 8.9g of precursor and 1.1g of K 2 CO 3 Mixing, grinding and tabletting, and the prepared catalyst is denoted as S3.
Wherein, the molar ratio of Ca to Mo is 0.03:1, a step of; the molar ratio of Co to Mo is 0.5:1, a step of; the molar ratio of S to Mo is 3:1, 38.32wt% of Mo, 11.75wt% of Co, 0.48wt% of Ca, 6.22wt% of K and 38.45wt% of S.
Example 4
The procedure of example 1 was followed except that in step (1), the amount of magnesium acetate added was 2.3g, and the catalyst obtained was designated as S4.
Wherein, the mol ratio of Mg to Mo is 0.06:1.
example 5
The procedure of example 1 was followed except that in step (1), the amount of magnesium acetate added was 3.4g, and the resultant catalyst was designated as S5.
Wherein the molar ratio of Mg to Mo is 0.09:1.
example 6
The procedure of example 1 was followed except that in step (1), the amount of cobalt acetate added was 30.2g, and the catalyst obtained was designated as S6.
Wherein, the mole ratio of Co to Mo is 0.8:1.
example 7
The procedure of example 1 was followed except that in step (1), the amount of cobalt acetate added was 5.7g, and the catalyst obtained was designated as S7.
Wherein the molar ratio of Co to Mo is 0.15:1.
example 8
The procedure of example 1 was followed except that in step (1), the amount of ammonium sulfide solution added was 175.9g, and the resultant catalyst was designated as S8.
Wherein, the mol ratio of S to Mo is 2.3:1.
example 9
The procedure of example 1 was followed except that in step (1), the amount of ammonium sulfide solution added was 321.2g, and the resultant catalyst was designated as S9.
Wherein, the mol ratio of S to Mo is 4.2:1.
example 10
The procedure of example 1 was followed except that in step (1), the amount of magnesium acetate added was 3.5g, and the resultant catalyst was designated as S10.
Wherein the content of Mg is 0.9wt%.
Example 11
The procedure of example 1 was followed except that in step (4), the amount of potassium carbonate added was 1.70g, and the resultant catalyst was designated as S11.
Wherein the content of K is 9wt%.
Example 12
In the same manner as in example 1 except that in step (1), 13.2g of cobalt acetate, 0.22g of magnesium acetate and 0.12g of lanthanum acetate were dissolved in 280mL of deionized water to prepare a mixed solution, the obtained catalyst was designated as S12.
Wherein the content of Mg is 0.06wt% and the content of La is 0.06wt%.
Example 13
In the same manner as in example 1 except that in step (1), 13.2g of cobalt acetate, 0.13g of calcium acetate and 0.12g of lanthanum acetate were dissolved in 280mL of deionized water to prepare a mixed solution, the obtained catalyst was designated as S13.
Wherein the content of Ca is 0.06wt% and the content of La is 0.06wt%.
Example 14
In the same manner as in example 1 except that in step (1), 13.2g of cobalt acetate and 0.22g of magnesium acetate, 0.13g of calcium acetate and 0.12g of lanthanum acetate were dissolved in 280mL of deionized water to prepare a mixed solution, the catalyst was designated as S14.
Wherein the content of Mg is 0.06wt%, the content of Ca is 0.06wt%, and the content of La is 0.06wt%.
Comparative example 1
The procedure of example 1 was followed except that the mixed solution of step (1) was free of magnesium acetate, and the resultant catalyst was designated as D1.
Comparative example 2
The procedure of example 1 was followed except that in step (1), the amount of magnesium acetate added was 3.7g, and the resultant catalyst was designated as D2. Wherein the content of Mg is 1wt%.
Comparative example 3
The procedure of example 2 was followed except that lanthanum acetate was added in an amount of 2.3g in step (1), and the resultant catalyst was designated as D3. Wherein the La content was 1.2wt%.
Comparative example 4
The procedure of example 1 was followed except that in step (1), the amount of magnesium acetate added was 0.11g, and the resultant catalyst was designated as D4. Wherein, the mol ratio of Mg to Mo is 0.003:1.
the lower alcohol catalysts prepared from the synthesis gas prepared in examples 1 to 3 and comparative example 1 were subjected to X-ray diffraction analysis (XRD), and the results are shown in fig. 1.
In FIG. 1, S1 is the X-ray diffraction curve of the catalyst for producing lower alcohols from synthesis gas obtained in example 1, S2 is the X-ray diffraction curve of the catalyst for producing lower alcohols from synthesis gas obtained in example 2, S3 is the X-ray diffraction curve of the catalyst for producing lower alcohols from synthesis gas obtained in example 3, and D1 is the X-ray diffraction curve of the catalyst for producing lower alcohols from synthesis gas obtained in comparative example 1. As can be seen from FIG. 1, the low-carbon alcohol catalyst (corresponding to curves S1, S2 and S3 in the figures) prepared in examples 1-3 has characteristic peaks 2θ=19.0 °, 23.9 °, 24.7 °, 24.9 °, 26.5 °, 28.1 °, 31.1 ° and K respectively 2 S 3 O 6 The standard card PDF-75-1479 is consistent, which shows that K is formed in the catalyst for preparing low-carbon alcohol from the synthetic gas 2 S 3 O 6 A structure; in contrast, K was not present in the catalyst for producing lower alcohols from synthesis gas prepared in comparative example 1 (corresponding curve D1) 2 S 3 O 6 Is not formed into K 2 S 3 O 6 The structure shows that the addition of the auxiliary agent M can promote the K on the catalyst 2 S 3 O 6 Formation of structure, K 2 S 3 O 6 The structure can stabilize the intermediate of the reaction and change the electronic structure of the catalyst, so that the activation of CO is easy and the hydrogenation activity of alkyl species is reduced, thereby improving the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol. The remaining examples are similar and the results are not shown.
The catalyst performance of the synthesis gas-to-lower alcohol catalysts prepared in examples 1 to 14 and comparative examples 1 to 4 was evaluated, and the results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the catalyst containing adjuvant M has better catalytic activity, selectivity for total alcohol in the product and space-time yield for total alcohol than the catalyst without adjuvant M.
In particular, as can be seen from comparing the evaluation results of examples 1 to 5, the molar ratio of the control aid M to Mo is within the preferred range of the present invention, and the activity, the total alcohol selectivity and the total alcohol space time yield of the prepared catalyst are further improved;
comparing the results of the evaluations of example 1 and examples 6 to 7, it can be seen that controlling the molar ratio of Co to Mo within the preferred range of the present invention can further improve the catalytic activity of the catalyst, the selectivity of the total alcohols in the product and the space-time yield of the total alcohols;
comparing the results of the evaluations of example 1 and examples 8 to 9, it can be seen that controlling the molar ratio of S to Mo within the preferred range of the present invention can further improve the catalytic activity of the catalyst, the selectivity of the total alcohols in the product and the space-time yield of the total alcohols;
comparing the results of the evaluation of example 1 and example 10, it can be seen that the content of the auxiliary M is within the preferred range of the present invention, which can further improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol;
comparing the results of the evaluation of example 1 and example 11, it can be seen that the content of K is within the preferred range of the present invention, which can further improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol;
comparing the results of the evaluations of examples 1 to 3 and examples 12 to 14, it can be seen that the activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol can be further improved also when the auxiliary M is two or three of Mg, ca and La.
As can be seen from comparing the results of the evaluation of example 1 and comparative example 1, the catalyst without the auxiliary M failed to improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol.
As can be seen from comparing the results of the evaluation of example 1 and comparative examples 2 to 3, the content of the auxiliary M in the catalyst is within the range defined by the present invention, so that the catalytic activity of the catalyst can be improved, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol can be improved, and the content of the auxiliary M is too high to improve the catalytic performance, but also the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol can be reduced.
As can be seen from comparing the results of the evaluation of example 1 and comparative example 4, the catalyst in which the molar ratio of the auxiliary M to Mo is not within the range defined by the present invention is not significant in the effect of improving the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (28)
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| CN101428229A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof |
| CN108325548A (en) * | 2018-03-15 | 2018-07-27 | 内蒙古大学 | A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | A kind of preparation method and application of synthesis gas to lower alcohol catalyst |
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| CN101428229A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof |
| CN108325548A (en) * | 2018-03-15 | 2018-07-27 | 内蒙古大学 | A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | A kind of preparation method and application of synthesis gas to lower alcohol catalyst |
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