CN112705256A - Catalyst unit and method for directly preparing olefin from synthesis gas - Google Patents
Catalyst unit and method for directly preparing olefin from synthesis gas Download PDFInfo
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- CN112705256A CN112705256A CN201911025112.1A CN201911025112A CN112705256A CN 112705256 A CN112705256 A CN 112705256A CN 201911025112 A CN201911025112 A CN 201911025112A CN 112705256 A CN112705256 A CN 112705256A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 34
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims description 12
- 229910017119 AlPO Inorganic materials 0.000 claims description 2
- 241000269350 Anura Species 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- -1 carbon hydrocarbon Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst unit for directly preparing olefin from synthesis gas, which comprises at least one catalyst subunit, wherein the catalyst subunit comprises a first catalyst section and a second catalyst section; the first catalyst is a mixed catalyst of an oxide and a molecular sieve, and the second catalyst is a molecular sieve catalyst. Preferably, the first catalyst sections and the second catalyst sections of the different catalyst units are arranged alternately. Also discloses a method for directly preparing olefin by using the synthesis gas, which comprises the step of enabling the synthesis gas to pass through the catalyst unit and react to obtain the olefin. The catalyst and the method for directly preparing the olefin from the synthesis gas reduce the selectivity of oxygen-containing compounds such as methanol generated by reaction and improve the selectivity of C2-C4 olefin on the premise of not reducing the CO conversion rate. The selectivity of the oxygen-containing compound such as methanol can be greatly reduced and can reach below 0.2 percent and even be reduced to 0.
Description
Technical Field
The invention relates to a catalyst for directly preparing olefin from synthesis gas and a method for directly preparing olefin by using the catalyst, belonging to the technical field of chemical engineering.
Background
The energy characteristics of China are 'rich coal, lack of oil and little gas'. The dependence of petroleum consumption on the outside is high, the economic development is severely restricted, and clean and efficient utilization of coal, natural gas, biomass and the like is always an important issue of sustainable development. In principle, coal, natural gas and biomass are directly converted into chemicals with a poor industrialization prospect, so that the selection of a proper conversion medium as a platform for coal chemical industry and natural gas chemical industry to realize chemical synthesis is particularly necessary. In recent years, with the increasing maturity of coal gasification, natural gas reforming, and biomass gasification technologies, syngas chemistry has been considered the most feasible alternative to petroleum-based production of oil and bulk chemicals.
The low-carbon olefin, which is C2-C4 olefin, is a very important chemical raw material. Ethylene production is a measure of the state of the chemical industry. At present, the outstanding problems in the production of ethylene and propylene in China are low consumption self-sufficiency and outstanding supply-demand contradiction. The conventional process for producing ethylene mainly by steam cracking technology is completely dependent on and consumes a large amount of non-renewable petroleum resources. The development of the low-carbon hydrocarbon synthesis technology of a non-petroleum route can not only supplement the existing production technology, but also provide reference for the utilization of new energy in the future.
At present, the research on the technology of preparing low carbon hydrocarbon from synthesis gas is still in the research and development stage of the laboratory, mainly focuses on the research and development of catalysts, and the research on the process is relatively deficient. The catalyst is mainly divided into two systems, one is a modified catalyst based on a Fischer-Tropsch synthesis catalyst, and the other is a supported catalyst mainly taking iron and cobalt as active centers, the catalyst generally has high CO conversion rate, the hydrocarbon product distribution generally meets the ASF carbon number distribution rule, and the selectivity of the C2-C4 hydrocarbon product is difficult to break through 60%. Another concept is to use a dual function coupled catalyst process. I.e., coupling the oxide and the molecular sieve. science (2016) has published that ZnCrOx in combination with MSAPO molecular sieves achieves C2-C4 hydrocarbon selectivity over 90% (excluding CO 2). German Korea (2016) also discloses a process using a ZnZr oxide and SAPO34 combined catalyst, and the C2-C4 hydrocarbon selectivity of the catalyst is over 90% (excluding CO 2).
Disclosure of Invention
The invention aims to solve the problems of the prior art and provides a catalyst unit for direct synthesis gas-to-olefin production, which comprises at least one catalyst subunit, wherein the catalyst subunit comprises a first catalyst section and a second catalyst section; the first catalyst is a mixed catalyst of an oxide and a molecular sieve, and the second catalyst is a molecular sieve catalyst.
According to a preferred embodiment of the invention, the first catalyst sections and the second catalyst sections of the different catalyst units are arranged alternately. That is, if there are a plurality of catalyst units, the second catalyst section of the previous catalyst unit is adjacent to the first catalyst section of the next catalyst unit. The first catalyst sections of different catalyst units or the second catalyst sections of different catalyst units are not adjacent.
According to a preferred embodiment of the invention, the weight ratio of the first catalyst section to the second catalyst section is (10-50): 1.
according to a preferred embodiment of the present invention, the weight ratio of the oxides to the molecular sieve in the first catalyst section is from (1: 6) to (6: 1); preferably (1: 4) to (4: 1).
According to a preferred embodiment of the present invention, the oxide is an oxide having CO conversion activity, preferably including at least one of oxides of Zn, Cr, In, Zr, Al, Ga, and composite oxides thereof.
According to a preferred embodiment of the present invention, the molecular sieve in the first catalyst section and the molecular sieve in the second catalyst section may be the same or different, each being independently selected from the group consisting of AlPO and SAPO molecular sieves; preferably selected from the group consisting of AlPO-18, AlPO-17, AlPO-34, AlPO-14, AlPO-11, AlPO-5, SAPO-18, SAPO-17, SAPO-11, and SAPO-5.
According to some embodiments of the present invention, the first catalyst may be a mixture of oxide particles and molecular sieve particles, or may be particles of a mixed powder of oxide and molecular sieve.
In the prior art, a catalyst is mainly loaded into a solid bed reactor in a mode of physically mixing an oxide and a molecular sieve, synthesis gas firstly generates methanol on the oxide catalyst and then diffuses on the molecular sieve to generate low-carbon olefin, and due to the limitation of the mixing mode, part of methanol can not be converted into olefin, so that a certain methanol selectivity in a final product is about 2%, and the economic benefit of the whole system is limited to a certain extent. The sectional catalyst of the invention can overcome the defects of the catalyst in the prior art, convert part of methanol products generated in the first section into target products, namely low-carbon olefin, improve the selectivity of the target products and improve the economy.
According to another aspect of the present invention, there is provided a method for directly preparing olefins from synthesis gas, comprising passing the synthesis gas through the above catalyst unit, and reacting to obtain olefins.
According to a preferred embodiment of the invention, synthesis gas is passed from the first catalyst section through the catalyst unit. That is, the syngas is passed through the first catalyst section before the second catalyst section.
According to a preferred embodiment of the invention, the synthesis gas comprises hydrogen and carbon monoxide in a molar ratio of 0.5 to 3.
According to a preferred embodiment of the present invention, the reaction temperature is 340-460 ℃; and/or the reaction pressure is 0.5-8 MPa; and/or the volume space velocity is 800--1。
According to a further aspect of the present invention, there is provided a fixed bed reactor for direct synthesis gas to olefins, packed with a catalyst unit as described above.
According to a preferred embodiment of the invention, the first catalyst section of the catalyst unit is located above the second catalyst section.
According to another aspect of the present invention, there is provided a method for directly producing olefins from synthesis gas, comprising feeding the synthesis gas into the above fixed bed reactor, and reacting the synthesis gas with the catalyst unit filled therein to obtain olefins.
According to a preferred embodiment of the invention, the synthesis gas is fed into the fixed bed reactor from above.
According to a preferred embodiment of the invention, the synthesis gas comprises hydrogen and carbon monoxide in a molar ratio of 0.5 to 3.
According to a preferred embodiment of the present invention, the reaction temperature of the fixed bed reactor is 340-; and/or the reaction pressure is 0.5-8 MPa; and/or the volume space velocity is 800--1。
The catalyst and the method for directly preparing the olefin from the synthesis gas reduce the selectivity of oxygen-containing compounds such as methanol generated by reaction and improve the selectivity of C2-C4 olefin on the premise of not reducing the CO conversion rate. The selectivity of the oxygen-containing compound such as methanol can be greatly reduced and can reach below 0.2 percent and even be reduced to 0. The method is simple and easy for industrialization.
Drawings
FIG. 1 shows a schematic diagram of a catalyst unit according to an embodiment of the invention.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
FIG. 1 illustrates a catalyst unit according to some embodiments of the invention comprising one catalyst sub-unit comprising a first catalyst section and a second catalyst section in a weight ratio of 30:1, the first catalyst section being a mixed catalyst section of an oxide and a molecular sieve and the second catalyst section being a molecular sieve section.
[ example 1 ]
The method for directly preparing olefin by using synthesis gas comprises the steps of filling a catalyst in a fixed bed by adopting two-section filling, wherein the upper section is a mixed catalyst of an oxide and a molecular sieve, the mixing ratio is 1:1 (mass ratio), the oxide is a ZnCr composite oxide, and the molecular sieve is an SAPO-34 molecular sieve; the lower section is SAPO-34 molecular sieve catalyst, the total mass of the upper section catalyst is 1.5g, and the loading of the lower section catalyst is 0.05g, as shown in FIG. 1. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), H in the synthesis gas2The molar ratio of CO is 1:1, the reaction is carried out for 100 hours, the reaction product is monitored on line by adopting gas chromatography, and the reaction result is shown in Table 1.
[ example 2 ]
The catalyst filling method for directly preparing olefin from synthesis gas adopts two-section filling for filling the catalyst in a fixed bed, wherein the upper section is a mixed catalyst of oxide and a molecular sieve, the mixing ratio is 1:1 (mass ratio), the oxide is ZnCr composite oxide, and the molecular sieve is SAPO-34 molecular sieve; the lower section is SAPO-34 molecular sieve catalyst, the total mass of the upper section catalyst is 1.5g, and the loading of the lower section catalyst is 0.03g, as shown in FIG. 1. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
[ example 3 ]
Catalyst filling for directly preparing olefin from synthesis gasThe method comprises the steps of filling a catalyst in a fixed bed by adopting two-section filling, wherein the upper section is a mixed catalyst of an oxide and a molecular sieve, the mixing ratio is 1:1 (mass ratio), the oxide is a ZnAl composite oxide, and the molecular sieve is an SAPO-34 molecular sieve; the lower section is SAPO-34 molecular sieve catalyst, the total mass of the upper section catalyst is 1.5g, and the loading of the lower section catalyst is 0.05g, as shown in FIG. 1. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
[ example 4 ]
The catalyst filling method for directly preparing olefin from synthesis gas adopts two-section filling for filling the catalyst in a fixed bed, wherein the upper section is a mixed catalyst of oxide and a molecular sieve, the mixing ratio is 1:1 (mass ratio), the oxide is ZnZr composite oxide, and the molecular sieve is SAPO-34 molecular sieve; the lower section is SAPO-34 molecular sieve catalyst, the total mass of the upper section catalyst is 1.5g, and the loading of the lower section catalyst is 0.05g, as shown in FIG. 1. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
[ example 5 ]
The catalyst filling method for directly preparing olefin from synthesis gas adopts two-section filling for filling the catalyst in a fixed bed, wherein the upper section is a mixed catalyst of oxide and a molecular sieve, the mixing ratio is 1:1 (mass ratio), the oxide is ZnCr composite oxide, and the molecular sieve is SAPO-18 molecular sieve; the lower section is SAPO-18 molecular sieve catalyst, the total mass of the upper section catalyst is 1.5g, and the loading of the lower section catalyst is 0.05g, as shown in FIG. 1. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
[ example 6 ]
The catalyst filling method for directly preparing olefin from synthesis gas adopts two-section filling for filling the catalyst in a fixed bed, wherein the upper section is mixed catalyst of oxide and molecular sieve, and the mixing ratio is 1:1 (mass ratio)The oxide is ZnCr composite oxide, and the molecular sieve is SAPO-34 molecular sieve; the lower section is provided with AlPO-18 molecular sieve catalyst, the total mass of the upper section catalyst is 1.5g, and the loading of the lower section catalyst is 0.05g, as shown in figure 1. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
Comparative example 1
The catalyst in the fixed bed is filled in a single section, and the mixed catalyst of the oxide and the molecular sieve is filled, wherein the mixing ratio is 1:1 (mass ratio), the oxide is ZnCr composite oxide, the molecular sieve is SAPO-34 molecular sieve, and the total mass of the catalyst is 1.5 g. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
Comparative example 2
The catalyst in the fixed bed is filled in a single section, and mixed catalyst of oxide and molecular sieve is filled, the mixing ratio is 1:1 (mass ratio), the oxide is ZnAl composite oxide, and the molecular sieve is SAPO-34 molecular sieve. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
Comparative example 3
The catalyst in the fixed bed is filled in a single section, and mixed catalyst of oxide and molecular sieve is filled, the mixing ratio is 1:1 (mass ratio), the oxide is ZnZr composite oxide, and the molecular sieve is SAPO-34 molecular sieve. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
Comparative example 4
The catalyst in the fixed bed is filled in a single section, and mixed catalyst of oxide and molecular sieve is filled, the mixing ratio is 1:1 (mass ratio), the oxide is ZnCr composite oxide, and the molecular sieve is SAPO-18 minAnd (5) screening by using a secondary screen. The reaction conditions are 400 ℃, 4.0Mpa and 4800h-1Under the conditions of (1), control of H2The reaction is carried out for 100 hours under the condition that CO is 1:1, the reaction product is monitored on line by adopting a gas chromatograph, and the reaction result is shown in table 1.
Table 1.
In Table 1, the C5+ hydrocarbon means a hydrocarbon having not less than 5 carbon atoms.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst unit for direct synthesis gas to olefins comprising at least one catalyst sub-unit comprising a first catalyst section and a second catalyst section; the first catalyst is a mixed catalyst of an oxide and a molecular sieve, and the second catalyst is a molecular sieve catalyst.
2. The catalyst of claim 1 wherein the first catalyst sections and the second catalyst sections of the different catalyst units are arranged alternately.
3. The catalyst of claim 1 or 2, wherein the weight ratio of the first catalyst section to the second catalyst section is (10-50): 1.
4. the catalyst of any of claims 1-3, wherein the weight ratio of the oxides to the molecular sieve in the first catalyst section is from (1: 6) to (6: 1); preferably (1: 4) to (4: 1).
5. A catalyst according to any one of claims 1 to 4, characterized In that the oxide is an oxide having CO conversion activity, preferably comprising at least one of the oxides of Zn, Cr, In, Zr, Al, Ga and their composite oxides.
6. The catalyst of any one of claims 1 to 5, wherein the molecular sieve is selected from AlPO and SAPO molecular sieves; preferably includes at least one of AlPO-18, AlPO-17, AlPO-34, AlPO-14, AlPO-11, AlPO-5, SAPO-18, SAPO-17, SAPO-11, and SAPO-5.
7. A method for preparing olefin directly from synthesis gas, which comprises the step of enabling the synthesis gas to pass through the catalyst unit of any one of claims 1 to 6, and reacting to obtain olefin.
8. The method of claim 7, wherein syngas is passed from the first catalyst section through the catalyst unit.
9. The method as claimed in claim 7 or 8, wherein the reaction temperature is 340-460 ℃; and/or the reaction pressure is 0.5-8 MPa; and/or the volume space velocity is 800--1。
10. A fixed bed reactor for direct synthesis of olefins from syngas packed with a catalyst unit according to any of claims 1-6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117380A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Process for production of hydrocarbons by synthetic gas conversion and catalysts used for process |
| CN107827691A (en) * | 2017-11-06 | 2018-03-23 | 中石化炼化工程（集团）股份有限公司 | A kind of method of synthesis gas preparing low-carbon olefins |
| CN109701602A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | For producing the catalyst system and its application method of hydro carbons |
| CN109701634A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Synthesis gas prepares carbon monoxide-olefin polymeric of lower carbon number hydrocarbons and application thereof |
| CN109701631A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Catalyst by the direct preparing low carbon hydrocarbons of synthesis gas and application thereof method |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104117380A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Process for production of hydrocarbons by synthetic gas conversion and catalysts used for process |
| CN109701602A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | For producing the catalyst system and its application method of hydro carbons |
| CN109701634A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Synthesis gas prepares carbon monoxide-olefin polymeric of lower carbon number hydrocarbons and application thereof |
| CN109701631A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Catalyst by the direct preparing low carbon hydrocarbons of synthesis gas and application thereof method |
| CN107827691A (en) * | 2017-11-06 | 2018-03-23 | 中石化炼化工程（集团）股份有限公司 | A kind of method of synthesis gas preparing low-carbon olefins |
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