CN111266131B - Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof - Google Patents

Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof Download PDF

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CN111266131B
CN111266131B CN202010133981.2A CN202010133981A CN111266131B CN 111266131 B CN111266131 B CN 111266131B CN 202010133981 A CN202010133981 A CN 202010133981A CN 111266131 B CN111266131 B CN 111266131B
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catalyst
reaction
molecular sieve
metal oxide
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CN111266131A (en
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李文双
魏晓娜
刘志强
姜叶葳
王闯
袁龙
陈诗通
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Chia Tai Energy Materials Dalian Co ltd
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
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    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention discloses a catalyst for preparing low-carbon olefin from synthesis gas, a preparation method and a use method thereof, wherein the catalyst consists of metal oxide with Fischer-Tropsch synthesis performance and a molecular sieve with catalytic cracking performance; wherein the metal oxide comprises Fe 2 O 3 、CuO、ZrO 2 (ii) a The catalyst comprises the following components in parts by weight: fe 2 O 3 20～60%、CuO 1～10%、ZrO 2 3-15% of molecular sieve; the molecular sieve is selected from one or a mixture of more of USY type, REUSY type and REHY type. The synthesis gas can simultaneously carry out Fischer-Tropsch synthesis reaction and cracking reaction under the action of the catalyst, and the teeter-totter phenomenon of the trade-off between the conversion rate of the synthesis gas and the selectivity of the low-carbon olefin in the prior art can be well solved.

Description

Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof
Technical Field
The invention relates to a catalyst, in particular to a catalyst for preparing low-carbon olefin from synthesis gas, a preparation method and a use method thereof, and belongs to the technical field of chemical industry.
Background
The lower olefin is an olefin having 4 or less carbon atoms. Low-carbon olefins represented by ethylene and propylene are very important basic organic chemical raw materials and occupy very important positions in national economy. The methods for preparing low-carbon olefins can be generally divided into two main categories: one is a petroleum route and the other is a non-petroleum route. Compared with the petroleum resources which are gradually deficient, the coal and natural gas resources are relatively rich, and the non-petroleum route which directly or indirectly prepares the low-carbon olefin by taking the coal-based or natural gas-based synthetic gas as the raw material has great attraction. The synthesis gas is used for directly preparing the low-carbon olefin by a one-step method, and the process flow is simpler and more economical than that of an indirect method.
The technology for preparing the low-carbon olefin by the synthesis gas one-step method originates from the traditional Fischer-Tropsch synthesis reaction, the carbon number distribution of the traditional Fischer-Tropsch synthesis product conforms to ASF (anaerobic-specific-Filter) distribution, namely, each hydrocarbon has the maximum theoretical selectivity, such as C 2 -C 4 The maximum selectivity of the fraction is 57%, the gasoline fraction (C) 5 -C 11 ) The selectivity of (a) is at most 48%. The ASF distribution of the Fischer-Tropsch synthesis product limits the selectivity of synthesizing low-carbon olefin.
Chinese patent CN101757925A provides a molten iron catalyst for producing low-carbon olefin from synthesis gas, which is composed of iron oxide and cocatalyst alumina, calcium oxide, potassium oxide, etc., the catalyst has high Fischer-Tropsch synthesis activity and selectivity, the conversion per pass reaches more than 95%, the methane selectivity is less than 10%, and the low-carbon olefin content is 35%.
In chinese patent CN1083415A, a group IIA alkali metal oxide such as MgO, or an iron-manganese catalyst system supported by a high-silicon zeolite molecular sieve (or a phospho-aluminum zeolite), is used, and strong base K or Cs ions are used as an auxiliary agent, and higher activity (90% of CO conversion) and selectivity (66% of low-carbon olefin selectivity) can be obtained at a reaction temperature of 300-400 ℃ and a reaction pressure of 1.0-5.0 MPa for preparing low-carbon olefin from synthesis gas. The catalyst is a load type Fischer-Tropsch synthesis catalyst, and the Silicalite-2 carrier of the catalyst plays a role in improving the dispersion degree of metal active components and the stability of the catalyst. The preparation process of the catalyst is complex, and particularly, the preparation and forming process of the carrier zeolite molecular sieve has high cost and is not beneficial to industrial production.
In 2016, sunrichh research institute and Chongqing researchers at Shanghai high research institute reported that a cobalt-based catalyst with preferential exposure to [101] and [020] manganese-assisted carbide realizes the selectivity of low-carbon olefin of 60.8% and the selectivity of methane of 5% under the CO conversion rate of 31.8%.
Alumina-loaded ZnCr was reported by the institute of encyclopedia of chemico-physical research, the institute of academia and Panxilian, academy of sciences 2 O 4 The oxide and the multi-stage pore SAPO-34 molecular sieve composite bifunctional catalyst (Jiao et al, science 351 (2016) 1065-1068) realizes the selectivity of 80% of low-carbon olefin when the CO conversion rate is 17%, and when the conversion rate is increased to 35%, the selectivity of the low-carbon olefin is 69%.
The prior art has the following defects: although the Fischer-Tropsch synthesis reaction can obtain higher CO conversion rate, high low-carbon olefin selectivity is difficult to obtain, and the low-carbon olefin catalyst prepared from the bifunctional synthesis gas in which the methanol synthesis catalyst and the methanol-to-olefin catalyst are coupled together can obtain higher low-carbon olefin selectivity but is difficult to obtain high CO conversion rate at the same time. The conversion rate of CO and the selectivity of the low-carbon olefin are in a trade-off state, and a seesaw effect exists.
Therefore, how to achieve high conversion rate and simultaneously obtain high selectivity of the low-carbon olefin is still a big difficulty in the field.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a catalyst for preparing low-carbon olefin by directly converting synthesis gas and a using method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, a catalyst for preparing low-carbon olefin from synthesis gas is provided, wherein the catalyst consists of a metal oxide with Fischer-Tropsch synthesis performance and a molecular sieve with catalytic cracking performance; wherein the metal oxide comprises Fe 2 O 3 、CuO、ZrO 2 ；
The catalyst comprises the following components in parts by weight: fe 2 O 3 20～60％、CuO 1～10％、ZrO 2 3 to 15 percent of the total weight of the composition, and the balance of the total weight of the compositionSieving; the molecular sieve is selected from one or a mixture of more of USY type, REUSY type and REHY type.
In some embodiments, the catalyst component comprises by weight: fe 2 O 3 35～45％、CuO 3～6％、ZrO 2 5 to 10 percent, and the balance being molecular sieve.
In some embodiments, the molecular sieve has a silica to alumina ratio to SiO 2 /Al 2 O 3 The molar ratio of (a) is 4-13, and the specific surface area is more than or equal to 700m 2 /g，Na 2 O≤1％。
In some embodiments, the molecular sieve is REUSY type, RE in REHY type 2 O 3 The content is more than or equal to 2.5wt percent.
In a second aspect, a method for preparing the catalyst is provided, which comprises: mixing the metal oxide and the molecular sieve according to the proportion to obtain the catalyst.
In some embodiments, the metal oxide is prepared by coprecipitation of a corresponding metal nitrate solution and a sodium carbonate solution.
In some embodiments, the method for preparing the catalyst comprises mixing the metal oxide and the molecular sieve in the following manner:
mixing metal oxide powder and molecular sieve powder, grinding, tabletting, molding, crushing and sieving to obtain the final catalyst;
or, the metal oxide and the molecular sieve are respectively ground, tabletted and molded, and then mechanically mixed after being ground and sieved to obtain the catalyst;
or, in the process of preparing the precipitate of the metal oxide, adding the molecular sieve into a reaction kettle to be mixed with the precipitate, washing, drying, roasting, grinding, tabletting, molding, crushing and sieving the obtained mixture to obtain the catalyst.
In some embodiments, a method of preparing the metal oxide comprises:
s1, converting the weight of corresponding metal nitrate according to the weight ratio of metal oxide, weighing ferric nitrate, cupric nitrate and zirconium nitrate according to the measurement, adding deionized water, and preparing into a solution A with a certain concentration;
s2, according to the chemicalFormula (I) calculating Na required to completely precipitate the metal salt 2 CO 3 Amount of (1), and weighing Na 2 CO 3 Adding deionized water to prepare a certain solution B;
s3, dropwise adding the solution A and the solution B into the reaction kettle in a parallel flow manner, stirring and reacting;
s4, keeping the temperature for continuously stirring after the reaction is finished, and standing and aging at a certain temperature to obtain a reaction precipitate;
s5, centrifugally separating, washing and filtering the precipitate to obtain a filter cake;
s6, drying the filter cake to obtain an intermediate product;
s7, roasting the intermediate product to obtain powder C, namely the metal oxide.
Further, the mass concentration of the solution A in the step S1 is 15-30%;
in the step S2, the mass concentration of the solution B is 15-30%;
the dropping speed in the step S3 is 100-300 ml/h, and the reaction temperature is 50-80 ℃;
the stirring time in the step S4 is 30-60 min, the standing and aging temperature is 60-80 ℃, and the time is 3-5 h;
the drying temperature in the step S6 is 80-120 ℃, and the time is 12-24 h;
the roasting temperature in the step S7 is 350-650 ℃, and the time is 3-6 h.
In a third aspect, a method for using the catalyst for preparing low carbon olefin from synthesis gas is provided, wherein the catalyst is used for fischer-tropsch synthesis-cracking reaction, and the reaction conditions comprise:
the Fischer-Tropsch synthesis-cracking reaction is carried out in a fixed bed tubular reactor, and the reaction temperature is 300-500 ℃, preferably 350-450 ℃; the reaction pressure is 0.5-4MPa, preferably 0.5-2MPa;
the total volume space velocity of the raw material gas is 1500-9000h -1 Preferably 3000-6000h -1 ；H 2 And CO in a volume ratio of (0.5-5) to 1, preferably (1-3) to 1. The reaction products were analyzed on-line by gas chromatography.
In some embodiments, the catalyst for preparing low-carbon olefins from synthesis gas is used in a method that hydrogen is introduced to reduce and activate the catalyst at 300-450 ℃ and 0.5-2MPa for 4-6h before the Fischer-Tropsch synthesis-cracking reaction.
In the invention, in order to improve the selectivity of directly preparing the low-carbon olefin from the synthesis gas, the Fischer-Tropsch synthesis catalyst is physically and chemically modified, for example, the proper pore channel structure of a molecular sieve is utilized, so that the low-carbon olefin can be conveniently diffused away from a metal active center in time, and the secondary reaction of the low-carbon olefin is inhibited; the metal ion dispersibility is improved, and the olefin selectivity is better; the selectivity of the low-carbon olefin can also be improved by changing the interaction between the metal and the carrier; the addition of proper transition metal can strengthen the bond energy between the active component and carbon, inhibit methane generation and raise the selectivity of low carbon olefin.
The invention has the advantages that: compared with the existing catalyst, the catalyst prepared by the invention has the advantages that: the combination of the metal oxide with the Fischer-Tropsch synthesis function and the molecular sieve with the cracking function can further crack and convert heavy hydrocarbon generated by Fischer-Tropsch synthesis into low-carbon olefin, thereby improving the selectivity of the low-carbon olefin while keeping higher conversion rate of synthesis gas. The selected molecular sieve is favorable for mass transfer and diffusion of heavy hydrocarbon. The synthesis gas can simultaneously carry out Fischer-Tropsch synthesis reaction and cracking reaction under the action of the catalyst, and the teeter-totter phenomenon of the trade-off between the conversion rate of the synthesis gas and the selectivity of the low-carbon olefin in the prior art can be well solved.
Detailed Description
The present invention will be described in detail with reference to the following examples.
A catalyst for preparing low-carbon olefin from synthetic gas comprises metal oxide with Fischer-Tropsch synthesis performance and a molecular sieve with catalytic cracking performance; wherein, the components of the catalyst are as follows by weight: fe 2 O 3 20～60％、CuO 1～10％、ZrO 2 3-15% of molecular sieve and the balance of molecular sieve;
the molecular sieve is selected from at least one of USY type, REUSY type and REHY type, and the ratio of silicon to aluminum in the molecular sieve is SiO 2 /Al 2 O 3 In a molar ratio of 413, specific surface area is more than or equal to 700m 2 /g，Na 2 O is less than or equal to 1 percent; among them, REUSY type, RE in REHY type 2 O 3 The content is more than or equal to 2.5wt percent.
The metal oxide is prepared from a corresponding metal nitrate solution and a sodium carbonate solution by adopting a coprecipitation method, and the preparation method comprises the following steps:
s1, converting the weight of corresponding metal nitrate according to the weight ratio of metal oxide, weighing ferric nitrate, cupric nitrate and zirconium nitrate according to the measurement, adding deionized water, and preparing into a solution A with the concentration of 15-30%;
s2, calculating Na required for completely precipitating metal salt according to a chemical formula 2 CO 3 In an amount of 115% by weight of Na 2 CO 3 Adding deionized water to prepare a solution B with the concentration of 15-30 percent;
s3, dropwise adding the solution A and the solution B into the reaction kettle in a cocurrent flow manner, wherein the dropwise adding speed is 100-300 ml/h, stirring, and reacting at 50-80 ℃;
s4, keeping the temperature after the reaction is finished, continuously stirring for 30-60 min, and then standing and aging for 3-5 h at the temperature of 60-80 ℃ to obtain reaction precipitate;
s5, centrifugally separating, washing and filtering the precipitate to obtain a filter cake;
s6, drying the filter cake for 12-24 h at 80-120 ℃ to obtain an intermediate product;
s7, roasting the intermediate product at 350-650 ℃ for 3-6 h to obtain powder C, namely the metal oxide.
The metal oxide may be mixed with the molecular sieve by any of the following:
a1, mixing powdery metal oxide with a molecular sieve, grinding, tabletting, crushing and sieving to obtain a catalyst;
a2, respectively grinding, tabletting and forming the metal oxide and the molecular sieve, and mechanically mixing after grinding and sieving to obtain a catalyst;
and A3, in the precipitation process of preparing the metal oxide, adding the molecular sieve into a reaction kettle to be mixed with the precipitate, and then washing, drying, roasting, grinding, tabletting, crushing and sieving the obtained mixture to obtain the catalyst.
The catalyst is used for the reaction conditions of the Fischer-Tropsch synthesis-cracking reaction, and comprises the following components: a fixed bed reactor is adopted, and before reaction, hydrogen is firstly introduced to activate the catalyst for 4-6h at the temperature of 300-450 ℃ and under the pressure of 0.5-2 MPa. The reaction conditions are as follows: h 2 And CO in a volume ratio of 0.5-5, preferably 1-3, at a reaction temperature of 300-500 ℃, preferably 350-450 ℃; the reaction pressure is 0.5-4MPa, preferably 0.5-2MPa; the total volume space velocity of the raw material gas is 1500-9000h -1 Preferably 3000-6000h -1 . The reaction product was analyzed on-line by gas chromatography.
Example 1
M1, preparation of a catalyst:
40.4g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、4.83g Cu(NO 3 ) 2 ·3H 2 O、8.59gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
25.6g of Na were weighed 2 CO 3 150g of deionized water is added to prepare a solution B.
And under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, keeping the temperature and stirring for 1h after 30min of dropwise adding, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing precipitates, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Weighing the powder C and the USY molecular sieve, grinding and mixing according to the weight ratio of 1 2 O 3 40％、CuO 4％、ZrO 2 6% and USY 50%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 2
M1, preparation of a catalyst:
40.4g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、4.83g Cu(NO 3 ) 2 ·3H 2 O、8.59gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
25.6g of Na were weighed 2 CO 3 And adding 150g of deionized water to prepare a solution B.
And under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, keeping the temperature and stirring for 1h after 30min of dropwise adding, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing precipitates, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Weighing the powder C and the REUSY molecular sieve, grinding and mixing according to the weight ratio of 1 2 O 3 40％、CuO4％、ZrO 2 6% and REUSY 50%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of phi 8mm, introducing hydrogen into the fixed bed reactor, reducing the catalyst for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas into the fixed bed reactor to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 3
M1, preparation of a catalyst:
40.4g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、4.83g Cu(NO 3 ) 2 ·3H 2 O、8.59gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
25.6g of Na were weighed 2 CO 3 Adding 150g of deionized water to prepareAnd (4) solution B.
Under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, keeping the temperature and stirring for 1h after 30min of dropwise adding is finished, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing the precipitate, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Weighing powder C and REHY molecular sieve, grinding and mixing according to the weight ratio of 1 2 O 3 40％、CuO4％、ZrO 2 6% and REHY 50%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 4
M1, preparation of a catalyst:
40.4g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、4.83g Cu(NO 3 ) 2 ·3H 2 O、8.59gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
25.6g of Na are weighed 2 CO 3 And adding 150g of deionized water to prepare a solution B.
And under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, and finishing dropwise adding for 30 min.
Weighing 20.02g of REUSY, adding into a reaction kettle, mixing with the precipitate, keeping the temperature and stirring for 1h, stopping stirring, keeping the temperature, standing and aging for 3h, centrifugally washing the precipitate, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain a mixture D. Tabletting the mixture D, pulverizing, sieving, and collecting 40-60 mesh granules to obtain Fe 2 O 3 40％、CuO 4％、ZrO 2 6% and REUSY 50%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of phi 8mm, introducing hydrogen into the fixed bed reactor, reducing the catalyst for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas into the fixed bed reactor to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 5
M1, preparation of a catalyst:
40.4g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、4.83g Cu(NO 3 ) 2 ·3H 2 O、8.59gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
25.6g of Na were weighed 2 CO 3 150g of deionized water is added to prepare a solution B.
Under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, keeping the temperature and stirring for 1h after 30min of dropwise adding is finished, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing the precipitate, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Respectively tabletting the powder C and a REUSY molecular sieve, crushing and sieving, and mixing 40-60-mesh particles according to the proportion of 1 2 O 3 40％、CuO 4％、ZrO 2 6% and REUSY 50%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: the volume ratio of the raw materials H2 and CO is 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 6
M1, preparation of a catalyst:
45.54g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、6.07g Cu(NO 3 ) 2 ·3H 2 O、13.92gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
31.07g of Na were weighed 2 CO 3 And adding 150g of deionized water to prepare a solution B.
And under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, keeping the temperature and stirring for 1h after 30min of dropwise adding, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing precipitates, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Weighing the powder C and the REUSY molecular sieve, grinding and mixing according to the weight ratio of 1.5 2 O 3 45％、CuO 5％、ZrO 2 10% and REUSY 40%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 7
M1, preparation of a catalyst:
35.42g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、7.29g Cu(NO 3 ) 2 ·3H 2 O、5.57gZr(NO 3 ) 4 ·9H 2 O, adding 150g of deionized water to prepare a solution A.
31.07g of Na were weighed 2 CO 3 150g of deionized water is added to prepare a solution B.
Under the condition of stirring, keeping the temperature in the reaction kettle at 70 ℃, dropwise adding the solution A and the solution B in a parallel flow manner into the reaction kettle, keeping the temperature and stirring for 1h after 30min of dropwise adding is finished, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing the precipitate, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Weighing the powder C and the REUSY molecular sieve, grinding and mixing according to the weight ratio of 0.82 2 O 3 35％、CuO 6％、ZrO 2 4% and REUSY 55%.
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of phi 8mm, introducing hydrogen into the fixed bed reactor, reducing the catalyst for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas into the fixed bed reactor to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 8
M1, preparation of a catalyst: the same as in example 2.
M2, evaluation of catalyst: taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 The volume ratio of the CO to the raw material gas is 1.5, the reaction temperature is 350 ℃, the reaction pressure is 1.0MPa, and the total volume space velocity of the raw material gas is 6000h -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 9
M1, preparation of a catalyst: the same as in example 2.
M2, evaluation of catalyst: taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of phi 8mm, introducing hydrogen into the fixed bed reactor, reducing the catalyst for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas into the fixed bed reactor to react, wherein the reaction conditions are as follows:starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 10
M1, preparation of a catalyst: the same as in example 2.
M2, evaluation of catalyst: taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 11
M1, preparation of a catalyst: the same as in example 2.
M2, evaluation of catalyst: taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Example 12
M1, preparation of a catalyst: the same as in example 2.
M2, evaluation of catalyst: taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 1
M1, preparation of a catalyst:
40.4g Fe (NO) are weighed out 3 ) 3 ·9H 2 O、4.83g Cu(NO 3 ) 2 ·3H 2 O、8.59gZr(NO 3 ) 4 ·9H 2 And O, adding 150g of deionized water to prepare a solution A.
25.6g of Na are weighed 2 CO 3 And adding 150g of deionized water to prepare a solution B.
Under the condition of stirring, dropwise adding the solution A and the solution B in a parallel flow manner into a reaction kettle, keeping the temperature in the reaction kettle at 70 ℃, keeping the temperature for 30min, continuing to keep the temperature and stirring for 1h, stopping stirring, keeping the temperature and standing for aging for 3h, centrifugally washing the precipitate, drying at 110 ℃ for 6h, and roasting at 450 ℃ for 4h to obtain powder C.
Tabletting the powder C, pulverizing, sieving, and collecting 40-60 mesh granules to obtain Fe powder with weight composition 2 O 3 80％、CuO 8％、ZrO 2 12% of the synthesis gas is used to prepare the low-carbon olefin catalyst (the catalyst does not contain molecular sieve).
M2, evaluation of catalyst:
taking 2ml of catalyst, filling the catalyst into a fixed bed reactor with the diameter of 8mm, introducing hydrogen to reduce for 4 hours at the temperature of 450 ℃ and under the pressure of 1MPa, and then introducing feed gas to react, wherein the reaction conditions are as follows: starting material H 2 And CO in a volume ratio of 2 -1 。
The reaction product was analyzed on-line by gas chromatography, and the reaction results are shown in Table 1.
TABLE 1 evaluation results of catalyst performance for olefin production from synthesis gas
Figure BDA0002396638300000161
As shown in table 1 above:
compared with comparative example 1, different molecular sieves and the same oxide combination are respectively selected in example 1, example 2 and example 3, and the combination has good promotion effect on the improvement of the selectivity of the low-carbon olefin, wherein the REUSY effect is better.
Examples 2, 4 and 5 show the effect of different mixing modes of the oxide and the molecular sieve on the reaction result.
Examples 2, 6 and 7 show the effect of the ratios of different oxide compositions on the reaction results.
Examples 8, 9, 10, 11 and 12 show different H 2 The reaction process conditions such as/CO, space velocity, temperature, pressure, etc., have an influence on the reaction result.
The above examples demonstrate that: compared with the existing catalyst, the catalyst prepared by the invention has the advantages that: the combination of the metal oxide with the Fischer-Tropsch synthesis function and the molecular sieve with the cracking function can further crack and convert heavy hydrocarbon generated by Fischer-Tropsch synthesis into low-carbon olefin, thereby improving the selectivity of the low-carbon olefin while keeping higher conversion rate of synthesis gas. The selected molecular sieve is favorable for mass transfer and diffusion of heavy hydrocarbon. The synthesis gas can simultaneously carry out Fischer-Tropsch synthesis reaction and cracking reaction under the action of the catalyst, and the teeter-totter phenomenon of the trade-off between the conversion rate of the synthesis gas and the selectivity of the low-carbon olefin in the prior art can be well solved.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalents or equivalent changes fall within the protection scope of the present invention.

Claims (7)

1. The catalyst is used for preparing low-carbon olefin from synthesis gas, and is characterized by consisting of a metal oxide with Fischer-Tropsch synthesis performance and a molecular sieve with catalytic cracking performance; wherein the metal oxide comprises Fe 2 O 3 、CuO、ZrO 2 ；
The catalyst comprises the following components in parts by weight: fe 2 O 3 35～45%、CuO 3～6%、ZrO 2 5-10% of molecular sieve and the balance of molecular sieve; the molecular sieveOne or more of USY type, REUSY type and REHY type; in the molecular sieve, siO is the ratio of silicon to aluminum 2 /Al 2 O 3 The molar ratio of (a) is 4-13, and the specific surface area is more than or equal to 700m 2 /g，Na 2 O≤1%；
The metal oxide is prepared from a corresponding metal nitrate solution and a sodium carbonate solution by adopting a coprecipitation method, and the preparation method of the metal oxide comprises the following steps:
s1, converting the weight of corresponding metal nitrate according to the weight ratio of metal oxide, weighing ferric nitrate, cupric nitrate and zirconium nitrate according to the measurement, and adding deionized water to prepare a solution A;
s2, calculating Na required for completely precipitating metal salt according to a chemical formula 2 CO 3 Amount of (1), and weighing Na 2 CO 3 Adding deionized water to prepare a solution B;
s3, enabling the solution A and the solution B to flow in parallel and be dripped into a reaction kettle, stirring and reacting;
s4, keeping the temperature for continuous stirring after the reaction is finished, and standing and aging to obtain a reaction precipitate;
s5, centrifugally separating, washing and filtering the precipitate to obtain a filter cake;
s6, drying the filter cake to obtain an intermediate product;
s7, roasting the intermediate product to obtain powder C, namely the metal oxide.
2. The catalyst for preparing low-carbon olefin by using synthesis gas as claimed in claim 1, wherein RE in REUSY type and REHY type in the molecular sieve 2 O 3 The content is more than or equal to 2.5wt percent.
3. A method for preparing the catalyst according to any one of claims 1 to 2, comprising: mixing the metal oxide and the molecular sieve according to the proportion to obtain the catalyst.
4. The method of claim 3, wherein the metal oxide and the molecular sieve are mixed by:
mixing metal oxide powder and molecular sieve powder, grinding, tabletting and forming, crushing and sieving to obtain the final catalyst;
or, the metal oxide and the molecular sieve are respectively ground, tabletted and molded, and then are mechanically mixed after being crushed and sieved to obtain the catalyst;
or, in the process of preparing the metal oxide precipitate, adding the molecular sieve into a reaction kettle to be mixed with the precipitate, washing, drying, roasting, grinding, tabletting, molding, crushing and sieving the obtained mixture to obtain the catalyst.
5. The use of the catalyst for the synthesis gas preparation of lower olefins according to any of claims 1-2, wherein the catalyst is used in fischer-tropsch synthesis-cracking reaction under reaction conditions comprising:
the Fischer-Tropsch synthesis-cracking reaction is carried out in a fixed bed tubular reactor, the reaction temperature is 300-500 ℃, and the reaction pressure is 0.5-4MPa;
the total volume space velocity of the raw material gas is 1500-9000h -1 ；H 2 And CO in a volume ratio of (0.5-5) to 1.
6. The use method of the catalyst for preparing low carbon olefin hydrocarbon from synthesis gas as claimed in claim 5, wherein the reaction temperature of the Fischer-Tropsch synthesis-cracking reaction is 350-450 ℃ and the reaction pressure is 0.5-2MPa;
the total volume space velocity of the feed gas is 3000-6000h -1 ；H 2 And the volume ratio of CO is (1-3) to 1.
7. The use method of the catalyst for preparing low carbon olefin hydrocarbon from synthesis gas as claimed in claim 5, wherein hydrogen is introduced to the catalyst for reduction activation at 300-450 ℃ and 0.5-2MPa for 4-6h before the Fischer-Tropsch synthesis-cracking reaction.
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