CN1266880A - Process for synthesizing liquid hydrocarbon with natural gas and its synthesizing catalyst - Google Patents
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Abstract
A process for synthesizing liquid hydrocarbon includes two-stage air oxidization to obtain nitrogen-containing synthetic gas, cooling via heat exchanger, synthesis reaction in Fischer-Tropsch synthesis reactor in the presence of Co-base alumina catalyst to produce the liquid hydrocarbon whose main component is the paraffine-base hydrocarbons and gas-liquid separation to separate liquid resultant from reaction tail gas. Said catalyst is a Co-base alumina catalyst using La or Ce and Mg or K as assistant. Its advantages are high CO conversion higher than 80%, high yield of liquid hydrocarbon higher than 80%, no pollution of S, N and heavy metals, simple process and less investment.
Description
The invention relates to a technology for synthesizing liquid hydrocarbon by natural gas, which comprises a reaction process, a catalyst for reaction and preparation of the catalyst, in particular to a method for synthesizing liquid hydrocarbon by natural gas and a synthetic catalyst.
Abundant natural gas resources (including natural gas, oil field associated gas and coal bed gas), especially natural gas of small and medium natural gas fields and oil-gas symbiotic oil and gas fields in dispersed blocks in remote areasThe yield of the natural gas liquefaction product can not reach the scale economic benefit of long-distance pipeline transportation, and when the natural gas liquefaction product is far away from the consumption market, the storage and transportation become the key links of development and utilization of the natural gas liquefaction product, and the natural gas liquefaction is a convenient method for solving the problem. However, the current natural gas liquefaction process is complex, pollution is large and investment is high. In recent years, the technology for preparing the synthesis gas by directly oxidizing the methane is more utilized, and compared with the traditional steam reforming and non-catalytic partial oxidation, the technology has the advantages of high space velocity, low energy consumption and H product2the/CO ratio is close to 2: 1, and the methane partial oxidation utilized by the method for preparing the synthesis gas is a mild exothermic reaction: Δ H is 9kcal/mol, but since the space velocity of the reaction is high, the amount of heat generated per unit catalyst surface is large, and hot spots and temperature runaway are likely to occur. And the feed gas methane/oxygen is within the explosive limits at high temperatures, requiring safety considerations for the process.
Chinese patent applications 99100701.8 and 99111080.3disclose a method of combining low temperature catalytic combustion and partial oxidation of methane to make syngas. It is characterized in that the reaction of preparing the synthesis gas by partial oxidation of the natural gas is realized by two fixed bed reactors connected in series and two stages of oxygen feeding. Air is used as an oxygen source, so that the expensive investment and operation cost of an oxygen preparation part can be saved. Air accounting for about 20-50% of the total amount and the total natural gas are added into the raw material of the first stage reactor, methane is subjected to low-temperature catalytic combustion in the first stage reactor to consume a part of oxygen, so that the ratio of methane to oxygen in the whole reaction is deviated from an explosion region, meanwhile, the methane is completely combusted, the raw material gas can be preheated to 700-1000 ℃, and the second reactor is provided with the raw material gas containing partial steam and CO2The raw material gas of (1). Adding 80-50% of the air in the first stage outlet gas, feeding the mixture into a second stage reactor, and adding nickel base/Al with lanthanum-alkaline earth metal oxide as an auxiliary agent2O3Partial oxidation of methane with exothermic reaction and endothermic steam/CO with the aid of a catalyst (CN99100701.8)2Reforming reaction is carried out simultaneously, basically adiabatic reaction is realized, temperature runaway of a second section catalyst bed layer is avoided, and the reaction for preparing synthesis gas by partial oxidation of methane can be industrially realized by adopting two ordinary fixed bed adiabatic reactorsShould be used. In order to smooth the operation and to facilitate the increase of the methane conversion, it is sometimes possible to add part of the steam to the first-stage or (and) second-stage reaction feed. The method for preparing the synthesis gas by combining the low-temperature catalytic combustion and the partial oxidationof the methane opens up a new channel for the technology of synthesizing the liquid hydrocarbon by the natural gas.
The invention aims to provide a method and a synthesis catalyst for synthesizing liquid hydrocarbon by natural gas, which have the advantages of shorter process, less investment, paraffin-based hydrocarbon as a main component, no sulfur, no nitrogen and no heavy metal pollution and can convert the natural gas (including natural gas, oilfield associated gas and coal bed gas) into high-quality liquid.
The byproduct fuel gas can supplement partial natural gas or be used for gas-steam combined cycle power generation or gas turbine power generation through catalytic combustion, and can also be directly used as fuel gas.
The purpose of the invention is realized by the following technical scheme:
the natural gas is first two-stage air oxidation to prepare synthetic gas, and the synthetic gas is then Fischer-Tropsch synthesized to prepare liquid hydrocarbon, and the process includes the following steps: the nitrogen-containing synthesis gas prepared by two-stage air oxidation enters a Fischer-Tropsch synthesis reactor after being cooled by a heat exchanger, liquid hydrocarbon mainly comprising paraffin-based hydrocarbon is generated under the action of a cobalt-based alumina catalyst taking lanthanide and/or alkali metal and/or alkaline earth metal oxide as an auxiliary agent, and the liquid product and reaction tail gas are separated from each other by a reaction product at the outlet of the Fischer-Tropsch synthesis reactor through a gas-liquid separator.
The catalyst for Fischer-Tropsch synthesis reaction consists of Co-base alumina catalyst with La or Ce and Mg or K as assistant.
The purpose of the invention can be realized by the following technical scheme:
the tail gas of Fischer-Tropsch synthesis reaction contains hydrogen, carbon monoxide, gaseous hydrocarbon and nitrogen, and after gas-liquid separation, it can be used for supplementing natural gas or making catalytic combustion to make gas-steam combined cycle power generation or gas turbine power generation, also can be directly used as fuel gas.
The catalyst for the Fischer-Tropsch synthesis reaction adopts a cobalt-based alumina catalyst taking alkaline earth metal as an auxiliary agent.
The catalyst of the Fischer-Tropsch synthesis reaction adopts a cobalt-based alumina catalyst taking alkali metal as an auxiliary agent.
The catalyst for the Fischer-Tropsch synthesis reaction adopts a cobalt-based alumina catalyst taking lanthanum and magnesium as auxiliaries.
The catalyst for the Fischer-Tropsch synthesis reaction adopts a cobalt-based alumina catalyst with lanthanum and potassium as auxiliaries.
The catalyst for the Fischer-Tropsch synthesis reaction adopts a cobalt-based alumina catalyst taking lanthanum or cerium as an auxiliary agent.
The attached drawing of the invention is a process flow diagram.
The invention has the advantages that the conversion rate of CO of more than 80 percent and the yield of liquid hydrocarbon of more than 80 percent can be converted into high-quality hydrocarbon products which are mainly paraffin-based hydrocarbon and have no sulfur, nitrogen and heavy metal pollution, the process flow is shorter, the investment is less, the natural gas is applied in various types, the fuel gas of the byproduct can supplement partial natural gas or be used for gas-steam combined cycle power generation or gas turbine power generation through catalytic combustion, and the fuel gas can also be directly used as the fuel gas.
The technological process of the invention comprises three parts: firstly, preparing synthesis gas (CN99100701.8 and CN99111080.3) by two-stage air catalytic oxidation of natural gas; secondly, preparing liquid hydrocarbon by Fischer-Tropsch synthesis of nitrogen-containing synthesis gas and a catalyst; and thirdly, gas-liquid separation and tail gas utilization of the Fischer-Tropsch synthesis product. The liquid state process and catalyst part of the nitrogen-containing synthesis gas are synthesis gas prepared by two-stage air catalytic oxidation of natural gas, the synthesis gas is cooled to the reaction temperature of Fischer-Tropsch synthesis through a heat exchanger, usually 160-280 ℃, and enters a Fischer-Tropsch synthesis reactor, and the Fischer-Tropsch synthesis reactor can adopt a slurry bed, a tubular reactor or a fluidized bed reactor according to specific situations, and under the action of a cobalt-based alumina catalyst taking lanthanum, cerium, alkali metal and/or alkaline earth metal oxide as an auxiliary agent, the CO conversion rate of more than 80 percent and the liquid hydrocarbon yield of more than 80 percent are converted into hydrocarbon products taking paraffin-based hydrocarbons as main components. In order to simplify the process, reduce investment and operating costs, the unconverted CO and H from the Fischer-Tropsch synthesis outlet is generally not recycled2. Fischer-Tropsch synthesisThe reaction product passes through a gas-liquid separator, and the liquid product and the reaction are carried outThe tail gas is separated. The tail gas part comprises gaseous hydrocarbon and a small amount of carbon dioxide which are byproducts of Fischer-Tropsch synthesis, and a small amount of unconverted methane, hydrogen, carbon monoxide and a large amount of unconverted nitrogen, and can be used for gas-steam combined cycle power generation or gas turbine power generation and also can be directly used as fuel gas.
The invention is described in detail below with reference to examples:
one example of two-stage air catalytic oxidation of natural gas to produce synthetic gas
Reaction example one: two sections of pressurized fixed bed reaction devices connected in series are adopted, the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 25 percent of the total oxygen are added into an inlet of a first section reactor, and the inlet temperature is 350 ℃. The catalyst used in the first stage is a Pd/Pt catalyst, and the addition amount depends on the capacity of the reactor. Adding the rest 75% of oxygen between the second stage reactor and the first stage reactor to mix the reaction products in the first stage, and selecting LnxOy-Ni base/M Al2O3The adding amount of the catalyst (priority term CN99100701.8) is determined by the capacity of the reactor, the temperature of a catalyst bed layer is 850 ℃, and the space velocity GHSV of raw material gas is 10000/h. The reaction results were as follows:
| pressure of reaction system (MPa) | CH4Conversion rate ％ | CO Selectivity ％ | H2Selectivity is ％ |
| 0.1 | 92.2 | 97.3 | 97.2 |
| 0.5 | 90.4 | 95.2 | 94.2 |
| 1.0 | 89.3 | 91.0 | 92.4 |
| 2.0 | 77.7 | 89.1 | 88.2 |
Reaction example two: the wholeThe ratio of methane to oxygen in the reaction raw materials is 2: 1, all natural gas and oxygen accounting for 25 percent of the total oxygen are added into the inlet of the first-stage reactor, and the inlet temperature is 350 ℃. The catalyst used in the first stage is a Pd/Pt catalyst. Adding the rest 75% of oxygen between the second-stage reactor and the first-stage reactor, and selecting LnxOy-Ni base/M Al2O3The adding amount of the catalyst (priority term CN99100701.8) is determined by the capacity of a reactor, the temperature of a catalyst bed layer is 850 ℃, and the space velocity GHSV of raw material gas is 20000/h. The reaction results were as follows:
| pressure of reaction system Force (MPa) | CH4Conversion rate ％ | CO Selectivity ％ | H2Selectivity is ％ |
| 0.1 | 91.0 | 95.1 | 97.2 |
| 0.5 | 90.2 | 94.3 | 92.3 |
| 1.0 | 86.3 | 90.5 | 90.1 |
| 2.0 | 75.1 | 86.7 | 84.3 |
Reaction example three: the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 25% of the total oxygen are added into the inlet of the first stage reactor, and the inlet temperature is 350 ℃. The catalyst used in the first stage is CuO/Co2O3A catalyst. Replenishing it between the second stage reactor and the first stage reactorThe balance being 75% oxygen. Selecting LnxOy-Ni base/M Al2O3The adding amount of the catalyst (priority term CN99100701.8) is determined according to the capacity of a reactor, the temperature of a catalyst bed layer is 850 ℃, the space velocity GHSV of raw material gas is 10000/h, and the reaction pressure is 2.5 MPa. The reaction results were as follows:
| pressure of reaction system (MPa) | CH4Conversion rate ％ | CO Selectivity ％ | H2Selectivity is ％ |
| 2.5 | 73.2 | 89.9 | 86.6 |
Reaction example four: the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 25% of the total oxygen are added into the inlet of the first stage reactor, and the inlet temperature is 350 ℃. The catalyst used in the first stage is CuO/Cr2O3A catalyst. The remaining 75% of the oxygen was added between the second stage reactor and the first stage reactor. Selecting LnxOy-Ni base/M Al2O3The catalyst (priority term CN99100701.8) is added according to the capacity of the reactor, the temperature of the catalyst bed is 850 ℃, the space velocity GHSV of the raw material gas is 150000/h, and the reaction pressure is 0.4 MPa. The reaction results were as follows:
| pressure of reaction system (MPa) | CH4Conversion rate ％ | CO Selectivity ％ | H2Selectivity is ％ |
| 2.5 | 82.1 | 90.7 | 93.1 |
Reaction example five: the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 10% of the total oxygen are added into the inlet of the first stage reactor, and the inlet temperature is 350 ℃. The catalyst used in the first stage is TiO2A catalyst. The rest 90 percent of oxygen is supplemented between the second-stage reactor and the first-stage reactor. Selecting LnxOy-Ni base/M Al2O3The adding amount of the catalyst (priority term CN99100701.8) is determined according to the capacity of a reactor, the temperature of a catalyst bed layer is 850 ℃, the space velocity GHSV of raw material gas is 10000/h, and the pressure is normal. The reaction results were as follows:
| pressure of reaction system (MPa) | CH4Conversion rate ％ | CO Selectivity ％ | H2Selectivity is ％ |
| 0.1 | 90.3 | 91.7 | 98.8 |
Reaction example six: the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 45% of the total oxygen are added into the inlet of the first stage reactor, and the inlet temperature is 350 ℃. The catalyst used in the first stage is a Pd/Pt catalyst. The remaining 55% of the oxygen was added between the second stage reactor and the first stage reactor. Selecting LnxOy-Ni base/M Al2O3The adding amount of the catalyst (priority term CN99100701.8) is determined by the capacity of the reactor, the temperature of a catalyst bed layer is 900 ℃, the space velocity GHSV of raw material gas is 10000/h, and the pressure is normal. The reaction results were as follows:
| pressure of reaction system (MPa) | CH4Conversion rate ％ | CO Selectivity ％ | H2Selectivity is ％ |
| 2.5 | 80.0 | 90.9 | 95.4 |
Two, Fischer-Tropsch Synthesis reaction examples
1. Preparation example of Fischer-Tropsch Synthesis catalyst:
preparation example of fischer-tropsch synthesis catalyst one:
taking commercial gamma-Al2O3Soaking in proper proportion of Co (NO)3)2And La (NO)3)3Mixing the solutions, soaking for 72h step by step, drying at 60 deg.C, and calcining at 620 deg.C for 10 hr. The catalyst comprises the following components in percentage by weight: 11.6 wt.% Co, 2.8 wt.% La2O3，La/Co＝0.1(mol/mol)。
Preparation example b of fischer-tropsch synthesis catalyst:
taking commercial gamma-Al2O3Soaking in proper proportion of Co (NO)3)2And La (NO)3)3Mixing the solutions, soaking for 72h step by step, drying at 60 deg.C, and calcining at 600 deg.C for 10 hr. The catalyst comprises the following components in percentage by weight: 11.6 wt.% Co, 3.5 wt.% La2O3，La/Co＝0.14(mol/mol)。
Fischer-Tropsch Synthesis reaction catalyst preparation example III:
taking commercial gamma-Al2O3Soaking in proper proportion of Co (NO)3)2And Ce (NO)3)3Mixing the solutions, soaking for 72h step by step, drying at 60 deg.C, and calcining at 650 deg.C for 10 hr. The catalyst comprises the following components in percentage byweight: 11.6 wt.% Co, 3.2 wt.% CeO2，Ce/Co＝0.1(mol/mol)。
Fischer-Tropsch Synthesis reaction catalyst preparation example four:
taking commercial gamma-Al2O3Soaking in proper proportion of Co (NO)3)2And Ce (NO)3)3Mixing the solutions, soaking for 72h step by step, drying at 60 deg.C, and calcining at 600 deg.C for 10 hr. The catalyst comprises the following components in percentage by weight: 11.6 wt.% Co, 4.0 wt.% CeO2，Ce/Co＝0.14(mol/mol)。
Fischer-tropsch synthesis catalyst preparation example five:
taking commercial gamma-Al2O3Soaking in proper proportion of Co (NO)3)2And Mg (NO)3)2Mixing the solution, soaking for 72h step by step, drying at 60 ℃, and roasting at 630 ℃ for 10 h. The catalyst comprises the following components in percentage by weight: 11.6 wt.% Co, 2.1 wt.% MgO, Mg/Co 0.1 (mol/mol).
Fischer-Tropsch synthesis reaction catalyst preparation example six:
taking commercial gamma-Al2O3Soaking in proper proportion of Co (NO)3)2And KNO3Mixing the solutions, soaking for 72h step by step, drying at 60 deg.C, and roasting at 450 deg.C for 10 hr. The catalyst comprises the following components in percentage by weight: 11.6wt. -%)Co，1.3wt.％K2O，K/Co＝0.14(mol/mol)。
Fischer-Tropsch Synthesis reaction catalyst preparation example seven:
taking commercial gamma-Al2O3Impregnated with Mg (NO)3)2In solution, overnight. Drying at 80 deg.C for 12h, calcining at 900 deg.C for 10h, naturally cooling to room temperature to make the carrier or carrier surface form spinel structure, and soaking the prepared carrier in Co (NO) with proper proportion3)2And Ce (NO)3)3Mixing the solutions, soaking for 72h step by step, drying at 60 deg.C, and calcining at 620 deg.C for 10 hr. The catalyst comprises the following components in percentage by weight: 11.6 wt.% Co, 4 wt.% CeO2，Ce/Co＝0.10(mol/mol)。
2. Examples of Fischer-Tropsch reactions
Reaction example one:
Fischer-Tropsch synthesis was carried out using a fixed bed reactor with the catalyst of catalyst preparation example three. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 1.2MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
Reaction example two:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 81.7 | 11.3 | 80.2 | 140.3 |
the catalyst of catalyst preparation example one was subjected to fischer-tropsch synthesis using a fixed bed reactor. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 2.5MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
Reaction example three:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 82.4 | 13.7 | 81.6 | 137.1 |
fischer-tropsch synthesis was carried out using a fixed bed reactor with the catalyst of catalyst preparation example four. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 2.5MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
Reaction example four:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 88.4 | 10.8 | 81.5 | 153.5 |
a fixed bed reactor was used to prepare the catalyst of example five for fischer-tropsch synthesis. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 3.0MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
Reaction example five:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 83.4 | 14.6 | 80.1 | 136.8 |
preparation of catalyst example two Using a fixed bed reactorCarrying out Fischer-Tropsch synthesis by using the catalyst. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6h, and mixing the pre-mixed 1.81/1H of (A) to (B)2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 3.0MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
Reaction example six:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 84.4 | 12.7 | 82.1 | 140.4 |
Fischer-Tropsch synthesis was carried out using a fixed bed reactor, catalyst preparation example six. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 3.0MPa, and the raw materialsThe air space velocity is 500/h. The reaction results were as follows:
Reaction example seven:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 80.1 | 13.7 | 80.3 | 136.1 |
fischer-tropsch synthesis was carried out using a fixed bed reactor with the catalyst of catalyst preparation example seven. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 220 ℃, the pressure is 2.5MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
Reaction example eight:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 89.1 | 12.2 | 85.3 | 162.7 |
Fischer-Tropsch synthesis was carried out using a fixed bed reactor with the catalyst of catalyst preparation example three. The dosage of the catalyst is 1.2g, 60-80 mesh, and the dosage is 20ml/minH before reaction2Reducing for 6H, and mixing the premixed 1.81/1H2the/CO cut-in reactor. The reaction temperature is 250 ℃, the pressure is 1.2MPa, and the space velocity of the raw material gas is 500/h. The reaction results were as follows:
| conversion of CO (％) | CH4Selectivity is (％) | C5+ selectivity (％) | Liquid recovery (g/M)3 syngas) |
| 98.9 | 20.8 | 61.4 | 124.4 |
Third, natural gas two-stage air catalytic oxidation is used for preparing synthesis gas and Fischer-Tropsch synthesis combined reaction example:
reaction example one: two sections of pressurized fixed bed reaction devices connected in series are adopted, the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 25 percent of the total oxygen are added into an inlet of a first section reactor, the reaction condition is that the inlet temperature is 350 ℃, and the used catalyst is Pd/Pt catalyst. The remaining 75% of the oxygen was added between the second stage reactor and the first stage reactor. Selecting La-Mg oxide Ni base/MgAl2O4-Al2O3The temperature of the catalyst bed layer is 850 ℃, the space velocity GHSV of the raw material gas is 10000h-1. The synthesis gas prepared by two-stage air oxidation method directly enters the CeO filling device2-Co/Al2O3The Fischer-Tropsch synthesis fixed bed reactor of the catalyst has the following Fischer-Tropsch synthesis reaction conditions: 220 ℃, 2.0MPa and 500h of synthesis gas-1The reaction results were as follows:
Composition of the tail gas from the Fischer-Tropsch reaction: h2：8.4％ CO 5.6％ CH411.6％ CO20.7％ C2 -C40.7 N273.0％
| CH4conversion rate (％) | CO conversion (%) | C5+ selectivity (％) | CH4Selectivity is (％) |
| 82.1 | 84.3 | 82.1 | 14.7 |
Reaction example two: two sections of pressurized fixed bed reaction devices connected in series are adopted, the ratio of methane to oxygen in the whole reaction raw material is 2: 1, all natural gas and oxygen accounting for 25 percent of the total oxygen are added into an inlet of a first section reactor, the reaction condition is that the inlet temperature is 350 ℃, and the used catalyst is Pd/Pt catalyst. The remaining 75% of the oxygen was added between the second stage reactor and the first stage reactor. Selecting La-Mg oxide Ni base/MgAl2O4-Al2O3The temperature of the catalyst bed layer is 950 ℃, and the space velocity GHSV of the raw material gas is 10000h-1. The synthesis gas prepared by two-stage air oxidation method directly enters the La filling2O3-Co/Al2O3The Fischer-Tropsch synthesis fixed bed reactor of the catalyst has the following Fischer-Tropsch synthesis reaction conditions: 220 ℃, 2.0MPa and 500h of synthesis gas-1The reaction results were as follows:
Tail gas composition of fischer-tropsch synthesis: h2：7.7％ CO 5.8％ CH48.1％ CO20.6％ C2 -C40.8N277.0％
| CH4conversion rate (％) | CO conversion (%) | C5+ selectivity (％) | CH4Selectivity is (％) |
| 90.1 | 82.3 | 84.1 | 13.7 |
Claims (8)
1. A method for synthesizing liquid hydrocarbon by natural gas is to prepare synthetic gas by two-stage air oxidation method of natural gas, and then prepare liquid hydrocarbon by Fischer-Tropsch synthesis reaction of synthetic gas, and is characterized in that: the nitrogen-containing synthesis gas prepared by two-stage air oxidation enters a Fischer-Tropsch synthesis reactor after being cooled by a heat exchanger, liquid hydrocarbon mainly comprising paraffin-based hydrocarbon is generated under the action of a cobalt-based alumina catalyst taking lanthanide and/or alkali metal and/or alkaline earth metal oxide as an auxiliary agent, and the liquid product and reaction tail gas are separated from each other by a reaction product at the outlet of the Fischer-Tropsch synthesis reactor through a gas-liquid separator.
2. A process for synthesizing liquid hydrocarbon from natural gas includes such steps as Fischer-Tropsch synthesis reaction, and features that the catalyst is a Co-base alumina catalyst containing La or Ce and Mg or K as assistant.
3. Catalyst for the fischer-tropsch synthesis reaction as claimed in claim 2, characterised in that an alkaline earth metal promoted cobalt based alumina catalyst is used.
4. Catalyst for the fischer-tropsch synthesis reaction as claimed in claim 2, characterised in that an alkali metal promoted cobalt based alumina catalyst is used.
5. The catalyst for Fischer-Tropsch synthesis reaction of claim 2, wherein a cobalt-based alumina catalyst with lanthanum and magnesium as promoters is used.
6. The catalyst for Fischer-Tropsch synthesis reaction of claim 2, wherein a cobalt-based alumina catalyst with lanthanum and potassium as promoters is used.
7. The catalyst for Fischer-Tropsch synthesis reaction of claim 2, wherein a cobalt-based alumina catalyst having lanthanum or cerium as an auxiliary is used.
8. The method as claimed in claim 1, wherein the tail gas of the Fischer-Tropsch synthesis reaction contains hydrogen, carbon monoxide, gaseous hydrocarbons and nitrogen, and after gas-liquid separation, the tail gas can be used for supplementing natural gas or for gas-steam combined cycle power generation or gas turbine power generation by catalytic combustion, or can be directly used as fuel gas.
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| CN108722426A (en) * | 2017-04-19 | 2018-11-02 | 中国石油化工股份有限公司 | The preparation method of catalyst and preparation method and application and catalyst precarsor reduction activation method and low-carbon alkene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378194C (en) * | 2005-12-22 | 2008-04-02 | 上海兖矿能源科技研发有限公司 | Method of coproducing oil products and electric energy using synthetic gas as raw material |
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2000
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100338180C (en) * | 2001-10-05 | 2007-09-19 | 国际壳牌研究有限公司 | System for power generation in a process producing hydrocarbons |
| CN1642851B (en) * | 2002-02-05 | 2010-04-14 | 加利福尼亚大学董事会 | Production of synthetic transportation fuels from carbonaceous materials using self-sustained hydro-gasification |
| CN101663376B (en) * | 2007-02-12 | 2013-06-12 | 沙索技术有限公司 | Co-production of power and hydrocarbons |
| CN103361140A (en) * | 2012-03-30 | 2013-10-23 | 通用电气公司 | Systems and methods for converting gases to liquids |
| CN103361140B (en) * | 2012-03-30 | 2017-04-12 | 通用电气公司 | Systems and methods for converting gases to liquids |
| CN108722426A (en) * | 2017-04-19 | 2018-11-02 | 中国石油化工股份有限公司 | The preparation method of catalyst and preparation method and application and catalyst precarsor reduction activation method and low-carbon alkene |
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| Publication number | Publication date |
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| CN1125866C (en) | 2003-10-29 |
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