CN1240757A - Process for preparing synthetic gas by two-stage catalytic oxidization of natural gas - Google Patents
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Abstract
A process for preparing synthetic gas by the integration of low-temp catalytic combustion of natural gas with partial oxidization of natural gas features that catalysis and oxidizationtake place in two-stage reactor. In the first stage, the 10-60% of total oxygen amount is fed. In the second stage, rest of oxygen is fed. The catalyst contains nickel oxide and alkali-earth or rare-earth oxides and has the chemical formula: LnxOy-Ni base/M Al2O4. The contents of components by carrier of catalyst are Ni (1-20%), Ln (1-20%) and M (1-15%). Its advantages are high conversion (more than 94% for methane), high selectivity (98% for H2 and 96% for CO) and no explosion possibility. Its reactor features simple structure, low cost and high reliability. Its catalyst features high stability, and sinter resistance, better regeneration power and low cost.
Description
The invention relates to a technology for preparing synthesis gas by combining natural gas low-temperature catalytic combustion and partial oxidation, which comprises a catalyst required by a reaction process and preparation thereof, in particular to a method for preparing synthesis gas by two-stage catalytic oxidation of natural gas.
The synthesis gas prepared by the catalytic partial oxidation of natural gas is a natural gas utilization method with great industrial application prospect, but the natural gas and air or pure natural gas are adoptedThe oxygen mixture has explosion risk, and the explosion limit range is widened along with the increase of temperature and pressure, such as the lower explosion limit of 5.6% and the upper explosion limit of 14.3% of methane when the original pressure is 101.3 kPa; at an original pressure of 1013.0kPa, the lower explosion limit of methane is 5.9%, and the upper limit is 17.2; at an initial pressure of 12662.5kPa, the lower explosive limit of methane was 5.7% and the upper limit was 45.7. Syngas production at a certain pressure is more practical since the downstream utilization of syngas is required to be performed at a certain pressure. However, if the reaction pressure is 5X 106And when Pa is reached, the composition of the feed gas of methane and oxygen theoretically fed at the moment is close to the upper limit of the explosion limit, the production is dangerous, meanwhile, the oxidation reaction of natural gas is an exothermic reaction, the reaction heat needs to be removed out of the reactor in time, otherwise, catalyst sintering and damage to the material of the reactor can be caused, and a lot of difficulties are brought to the operation. Patent 91108515 discloses a reaction method for producing synthesis gas from natural gas by burning and reforming respectively, but the method of introducing methane in stages in the reaction flow cannot effectively avoid the explosion risk in the reaction, and the process uses platinum group metals as catalysts, especially rhodium, ruthenium, palladium and platinum as active components in the reaction, and these metal elements are expensive, high in production cost and difficult to be widely used in industry.
The invention aims to provide a technology for producing synthesis gas, which is safe, reliable and low in cost, comprises a required catalyst and preparation thereof, and is a method for preparing synthesis gas by two-stage catalytic oxidation of natural gas.
The invention is realized by the following technical scheme:
a method for preparing synthetic gas by two-stage catalytic oxidation of natural gas is characterized in that the catalytic oxidation of the natural gas is carried out in sections in two connected normal-pressure fixed bed reactors, 10-60% of total oxygen input is added into a first-stage reactor, and the following reactions are carried out: the burning temperature of the reactor is 200-; adding residual oxygen into the second stage reactor to perform the following reactionThe following steps are required: the combustion is at 700-1000 deg.C and 0.1-5.0MPa, the catalyst used in the reactor contains nickel oxide, alkaline earth or rare earth oxide, and the component formula is as follows: lnxOy-Ni base/M Al2O4(ii) a Wherein the loading capacity (weight) of each component relative to the carrier is as follows: 1.0-20% of Ni0, 1-20% of Ln and 1-15% of M; the first stage reaction product is mixed with the second stage added oxygen or water between the first and secondstage reactors.
The invention is also realized by the following technical scheme:
the side reaction of the first stage reactor oxygenation is Oxygen adding pair of second stage reactorThe reaction is And . The first stage reactor is burnt at the temperature of 200-500 ℃ and the pressure of 0.1-5.0MPa, and the second stage reactor is burnt at the temperature of 700-1000 ℃ and the pressure of 0.1-5.0 MPa.
The first stage reaction is added with an oxidation metal catalyst or an oxide catalyst.
The catalyst used in the second stage reactor contains nickel oxide, alkaline earth or rare earth oxide, and the component formula is as follows: lnxOy-Ni base/M Al2O4(ii) a Wherein the loading capacity (weight) of each component relative to the carrier is as follows: 1.0-20% of Ni0, 1-20% of Ln and 1-15% of M.
In each component, Ln can be La, Ce, Mg, Ca, Ba, Co and Pd, and M can be Ni, Co, Mg, Ca and Ba. The carrier or the surface of the carrier is in a spinel structure.
The preparation method of the catalyst used in the second-stage reactor comprises the following steps:
a. taking appropriate amount of Al (NO)3)3And a second component (M) Ni, Co, Mg, Ca, Ba in solution with NH3·H2O、NH4HCO3Or (NH)4)2CO3The solution is a precipitator, and the carrier precursor is prepared by complete precipitation, aging, washing and drying;
b. roasting the precursor prepared in the step a for 5-24 hours at 700-1200 ℃, and forming a spinel structure on the carrier or the surface of the carrier;
c. b, soaking the carrier containing the spinel structure prepared in the step b into a mixed solution of an active component (Ni) and an auxiliary agent (Ln) with a proper composition to be initially wet;
d. and c, placing the catalyst precursor prepared in the step c, and drying at the activation temperature of 550-650 ℃ for 5-15 hours.
Step a can adopt gamma-Al2O3Soaking in Ni, Co, Mg, Ca and Ba solution, and oven drying.
The invention is described in detail below with reference to the examples:
in the invention, the catalytic oxidation of natural gas is carried out in two connected reactors in sections, 10-60% of total oxygen input is added into the first reactor, and the following reactions are carried out: side reaction of So that the feed gas at the inlet of the reactor consists of methaneThe proportion deviates from the explosive limit. The low-temperature catalytic conversion of methane is adopted in the reactor to replace non-catalytic combustion, so that the requirement on the material of the reactor is reduced. Air or oxygen-enriched air is used as an oxygen source to avoid N under high-temperature conditions in non-catalytic combustion2And O2The possibility of generating NOx by reaction reduces the environmental pollution. The adiabatic temperature rise of the combustion reaction in the first-stage reactor is 300-600 ℃, and the feed gas can be effectively heated to the reaction temperature of 700-1000 ℃ required by the second-stage reactor. The inlet of the second-stage reactor is supplemented with residual oxygen, oxygen-enriched air or air, the first-stage reaction product and the oxygen or water added in the second stage are mixed between the first-stage reactor and the second-stage reactor, and the following reactions are carried out in the second stage: . The side reaction is And . Due to the fact thatThe stage has consumed part of the oxygen and the product of the first stage reactor has H2O、CO2The presence of the inert components makes the composition of the feed gas at the inlet of the second stage reactor deviate from the explosion limit. The first stage reactor adopts low-temperature feeding and generated H2O and CO2Reforming reaction in the second stage reactor, partial oxidation reaction and steam reforming in the second stage reactor, CO2The reforming is carried out simultaneously, so that the adiabatic temperature rise of the second-stage reactor can be reduced, and the industrial production of preparing the synthesis gas by catalytic oxidation of natural gas can be realized by adopting a fixed bed adiabatic reactor.
The catalyst used in the first stage reactor of the present invention can adopt the currently common combustion catalyst, the combustion catalyst is divided into a metal catalyst and an oxide catalyst, the metal catalyst can comprise Pt, Pd, Cu, etc., and the oxide comprises TiO2、CeO2、V2O3And the like. The catalyst carrier is Al2O3。
The catalyst used in the second stage reactor of the invention contains nickel oxide, alkaline earth or rare earth oxide, and the component formula is as follows: lnxOy-Ni base/M Al2O4(ii) a Wherein the loading capacity (weight) ofeach component relative to the carrier is as follows: ni1.0-20%, Ln 1-20%, M1-15%, Ln can be La, Ce, Mg, Ca, Ba, Co and Pd, M can be Ni, Co, Mg, Ca and Ba, and the catalyst carrier or the surface of the carrier is in a spinel structure.
The following are examples of the preparation of the catalyst used in the second stage reactor:
catalyst preparation example one:
0.5 g of commercial gamma-Al is taken2O3Impregnated with 0.09ml of 2M Mg (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 900 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 0.10ml of 1M Ni (NO)3)2And 0.76ml of 0.1M La (NO)3)3Soaking the solution for 24h, drying at 80 ℃, and roasting at 630 ℃ for 6 h. The components being relative to the carrierThe carrying capacity is as follows: ni 1%, Ln ═ La 2%,and M is Mg 1%. Catalyst preparation example two:
0.5 g of commercial gamma-Al is taken2O3Impregnated in 0.59ml of 1M Co (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 1100 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 0.60ml of 1M Ni (NO)3)2And 0.63ml of 1M Mg (NO)3)2Soaking the solution for 24h, drying at 80 ℃, and roasting at 630 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 8%, Ln ═ Mg 3%, M ═ Co 5%. Catalyst preparation example three:
taking 1 g of commercial gamma-Al2O3Impregnated in 0.72ml 2M Mg (NO)3)2Solution, overnight. Oven drying at80 deg.C for 12h, calcining at 1100 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 0.60ml of 1M Ni (NO)3)2And 3.16ml of 0.1M Ba (NO)3)2Soaking the solution for 24h, drying at 80 ℃, and roasting at 550 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni3.5%, Ln ═ Ba 12%, and M ═ mg3.5%. Catalyst preparation example four:
200ml of 1M Al (NO)3)3And 14.69ml of 2M Mg (NO)3)2Solution, concentrated NH4The OH solution was slowly dropped into the solution until the pH of the solution was 14, the temperature of the solution was maintained at 40 ℃ during the precipitation, and the stirring speed was increased from 1200 rpm to 1800 rpm with the increase in the solution viscosity. After the reaction is finished, the same temperature and stirring speed are maintained for two hours, stirring and heating are stopped, precipitation and arraying are carried out for 100 hours, and the mixture is filtered, filtered and washed overnight. Drying at 80 deg.C for 12h and 120 deg.C for 12h, calcining at 900 deg.C for 10h, and naturally cooling to room temperature to form spinel structure on the carrier or carrier surface. The prepared carrier was immersed in 12.16ml of 1M Ni (NO)3)2And 2.68ml of 1M Ca (NO)3)2Soaking the solution for 24h, drying at 80 ℃, and roasting at 500 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 71%, Ln ═ Ca 9%, M ═ Mg 7%. Catalyst preparation example five:
2 g of commercial gamma-Al are taken2O3Impregnated in 5ml of 1M Mg (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 900 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 5ml of 1M Ni (NO)3)2And 30ml of 1M Ba (NO)3)2Solution, impregnationDrying at 80 deg.C for 24h, and calcining at 600 deg.C for 6 hr. The loading capacity of each component relative to the carrier is as follows: ni 15%, Ln ═ Co 20%, and M ═ Mg 15%. Catalyst preparation example six:
100ml of 2M Al (NO) was taken3)3And 7.5ml 2M Mg (NO)3)2Solution, 320ml of 1M (NH)4)2CO3The solution is slowly dropped into the solution, the temperature of the solution is maintained at 40 ℃ during the precipitation process, the stirring speed is increased from 1200 rpm at the beginning, and the solution viscosity is gradually increased to 2000 rpm. After the reaction is finished, the same temperature and stirring speed are maintained for two hours, stirring and heating are stopped, precipitation and arraying are carried out for 100 hours, and the mixture is filtered, filtered and washed overnight. Drying at 80 deg.C for 12h and 120 deg.C for 12h, calcining at 1100 deg.C for 10h, and naturally cooling to room temperature to form spinel structure on the carrier or carrier surface. The prepared carrier was immersed in 12.16ml of 1MNi (NO)3)2And 14.65ml of 1M La (NO)3)3Soaking the solution for 24h, drying at 80 ℃, and roasting at 500 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 7%, Ln ═ La 20%, and M ═ Mg 3%. Catalyst preparation example seven:
2 g of commercial gamma-Al are taken2O3Impregnated with 0.5ml of 1M Ca (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 900 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 5ml of 1M Ni (NO)3)2And 2ml of 0.5M Ce (NO)3)2Soaking the solution for 24h, drying at 80 ℃, and roasting at 600 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 15%, Ln ═ Ce 2%, and M ═ Ca 1%. Catalyst preparation example eight:
taking 1 g of commercial gamma-Al2O3Dipping inAt 1.44ml 2M Mg (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 1100 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 2ml of 1M Ni (NO)3)2And 0.15g of 0.88 wt% PdCl2Soaking the solution for 24h, drying at 80 ℃, and roasting at 600 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 12%, Ln — Pd 1%, and M — Mg 7%. Catalyst preparation example nine:
taking 1 g of commercial gamma-Al2O3Impregnated in 0.165ml of 0.5M Mg (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 1100 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 0.5ml of 1M Ni (NO)3)2And 0.72ml of 0.1M La (NO)3)3Soaking the solution for 24h, drying at 80 ℃, and roasting at 600 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 3%, Ln ═ La 1%, and M ═ Mg 1%. Catalyst preparation example ten:
taking 1 g of commercial gamma-Al2O3Impregnated in 3.09ml of 2M Mg (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 1100 deg.C for 10h, naturally cooling to room temperature to formspinel structure on the carrier or carrier surface, and soaking the prepared carrier in 2.9ml of 1M Ni (NO)3)2And 10.8ml of 0.1M La (NO)3)3Soaking the solution for 24h, drying at 80 ℃, and roasting at 600 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 17%, Ln ═ La 15%, and M ═ Mg 15%. Catalyst preparation example eleven:
2 g of commercial gamma-Al are taken2O3Dipped in 0.5ml of 1M Ba (NO)3)2Solution, overnight. Oven drying at 80 deg.C for 12h, calcining at 900 deg.C for 10h, naturally cooling to room temperature to form spinel structure on the carrier or carrier surface, and soaking the prepared carrier in 5ml of 1M Ni (NO)3)2And 2ml of 0.5M Ce (NO)3)2Soaking the solution for 24h, drying at 80 ℃, and roasting at 600 ℃ for 6 h. The loading capacity of each component relative to the carrier is as follows: ni 15%, Ln ═ Ce 2%,M＝Ba1％。
the synthesis gas reaction of the present invention is further illustrated by the following examples.
Reaction example one: two sections of mutually connected normal pressure fixed bed reaction devices are adopted, natural gas (the total ratio of methane to oxygen is 2: 1) and oxygen accounting for 10 percent of the total oxygen are added into the inlet of a first section reactor, and the inlet temperature is 350 ℃. The oxide catalyst used in the first stage is TiO2The amount added depends on the reactor capacity. The rest 90% of oxygen is added between the second stage reactor and the first stage reactor to be mixed with the first stage reaction product, the catalyst in the second stage catalyst preparation example is selected, the adding amount is determined according to the capacity of the reactor, the reaction temperature is 700 ℃, and the space velocity GHSV of the raw material gas is 5000/h. The results of the reaction are shown in the following table:
| CH4transformation of Percentage (%) | Yield of CO (％) | CO2Yield of (％) | CO Selectivity (％) | H2Yield of (％) | H2Selectivity is (％) |
| 90.3 | 82.8 | 7.5 | 91.7 | 89.3 | 98.8 |
Reaction example two: oxygen, which was 12% of the total oxygen, was added to the inlet of the first stage reactor at an inlet temperature of 300 ℃. The oxide catalyst used in the first stage is CeO2. Between the second stage reactor and the first stage reactorThe rest 88 percent of oxygen is added, the catalyst in the second stage catalyst preparation example is selected, the reaction temperature is 750 ℃, and the space velocity GHSV of the raw material gas is 5000/h. The rest of the reaction conditions were the same as in example one. The results of the reaction are shown in the following table:
| CH4transformation of Percentage (%) | Yield of CO (％) | CO2Yield of (％) | CO Selectivity (％) | H2Yield of (％) | H2Selectivity is (％) |
| 90.8 | 86.5 | 4.3 | 95.2 | 88.4 | 97.3 |
Reaction example three: oxygen, which was 15% of the total oxygen, was added to the inlet of the first stage reactor at an inlet temperature of 300 ℃. The oxide catalyst used in the first stage is Pd-Ni/Al2O3. The rest 85% of oxygen is added between the second-stage reactor and the first-stage reactor, the catalyst in the second-stage catalyst preparation example is selected, the reaction temperature is 800 ℃, and the space velocity GHSV of the raw material gas is 5000/h. The rest of the reaction conditions were the same as in example one. The results of the reaction are shown in the following table:
| CH4transformation of Percentage (%) | Yield of CO (％) | CO2Yield of (％) | CO Selectivity (％) | H2Yield of (％) | H2Selectivity is (％) |
| 96.6 | 94.8 | 1.8 | 98.2 | 95.8 | 99.2 |
Reaction example four: oxygen, 25% of the total oxygen, was added at the inlet of the first stage reactor, at an inlet temperature of 350 ℃. The oxide catalyst used in the first stage is Pd-Pt/Al2O3. And adding the rest 75 percent of oxygen between the second-stage reactor and the first-stage reactor, wherein the catalyst in the second-stage catalyst preparation example is selected, the reaction temperature is 850 ℃, the reaction pressure is 0.4Mpa, and the space velocity GHSV of the raw material gas is 50000/h. The rest of the reaction conditions were the same as in example one. The results of the reaction are shown in the following table:
| CH4transformation of Percentage (%) | Yield of CO (％) | CO2Yield of (％) | CO Selectivity (％) | H2Yield of (％) | H2Selectivity is (％) |
| 88.0 | 80.0 | 8.0 | 90.9 | 86.0 | 97.7 |
Reaction example five: oxygen, 60% of the total oxygen, was added at the inlet of the first stage reactor, at an inlet temperature of 450 ℃. The oxide catalyst used in the first stage is CeO2. Adding the rest 40% of oxygen between the second stage reactor and the first stage reactor, selecting the catalyst in the second stage catalyst preparation example, and reacting at the temperature of 950The reaction pressure is 2.5Mpa, and the space velocity GHSV of the raw material gas is 150000/h. The rest of the reaction conditions were the same as in example one. The results of the reaction are shown in the following table:
| CH4transformation of Percentage (%) | Yield of CO (％) | CO2Yield of (％) | CO Selectivity (％) | H2Yield of (％) | H2Selectivity is (％) |
| 80.2 | 73.2 | 7.0 | 91.2 | 71.1 | 88.6 |
Reaction example six: oxygen, 45% of the total oxygen, was added at the inlet of the first stage reactor at an inlet temperature of 400 ℃. The oxide catalyst used in the first stage was NiO. The rest 55% of oxygen is added between the second-stage reactor and the first-stage reactor, the catalyst in the second-stage catalyst preparation example is selected, the reaction temperature is 900 ℃, the reaction pressure is 1.5Mpa, and the space velocity GHSV of the raw material gas is 100000/h. The rest of the reaction conditions were the same as in example one. The results of the reaction are shown in the following table:
| CH4transformation of Percentage (%) | Yield of CO (％) | CO2Yield of (％) | CO Selectivity (％) | H2Yield of (％) | H2Selectivity is (％) |
| 88.0 | 80.0 | 8.0 | 90.9 | 86.0 | 97.7 |
The invention can use natural gas field gas, oil field associated gas or refinery gas, has the characteristics of high methane conversion rate and good product selectivity, eliminates the possibility of explosion under pressure operation, utilizes reaction heat to heat raw gas, adopts a conventional fixed bed adiabatic reactor to realize the industrial production of synthesis gas, and has the advantages of simple reactor structure, low manufacturing cost, simple and convenient operation, safety and reliability. The used catalyst has high stability, high selectivity, high activity, sintering resistance, loss resistance, good regeneration performance and carbon deposition resistance, and the price of the components is low.
Claims (10)
1. A method for preparing synthetic gas by natural gas two-stage catalytic oxidation is characterized in that the natural gas catalytic oxidation is carried out in two connected reactors in a stage, 10-60% of total oxygen input is added into a first stage reactor, and the following reactions are carried out: adding residual oxygen into the second stage reactor to carry out the following reaction: 。
2. the method for preparing synthesis gas by two-stage catalytic oxidation of natural gas according to claim 1, wherein the side reaction of the first stage reactor for adding oxygen is The side reaction of the second stage reactor for adding oxygen is And 。
3. the method as claimed in claim 1, wherein the first stage reactor is operated at 500 ℃ and 0.1-5.0MPa, and the second stage reactor is operated at 1000 ℃ and 700 ℃ and 0.1-5.0 MPa.
4. The method for producing synthesis gas by two-stage catalytic oxidation of natural gas according to claim 1, wherein the reaction product of the first stage is mixed with oxygen or water added in the second stage between the first and second stage reactors.
5. The method for preparing synthesis gas by two-stage catalytic oxidation of natural gas according to claim 1, wherein an oxidation metal catalyst or an oxide catalyst is added in the first stage reaction.
6. A catalyst used in a second-stage reactor of a method for preparing synthesis gas by two-stage catalytic oxidation of natural gas is characterized by comprising nickel oxide, alkaline earth or rare earth oxide and having the following component formula: lnxOy-Ni base/M Al2O4(ii) a Wherein the loading capacity (weight) of each component relative to the carrier is as follows: 1.0-20% of Ni0, 1-20% of Ln and 1-15% of M.
7. The catalyst for the second-stage reactor in the method for preparing the synthesis gas by the two-stage catalytic oxidation of the natural gas according to claim 6, wherein Ln in each component can be La, Ce, Mg, Ca, Ba, Co and Pd, and M can be Ni, Co, Mg, Ca and Ba.
8. The catalyst for the second-stage reactor in the method for preparing the synthesis gas by the two-stage catalytic oxidation of the natural gas according to the claims 6 and 7, characterized in that the carrier or the surface of the carrier has a spinel structure.
9. The catalyst for the second-stage reactor of the method for preparing the synthesis gas by the two-stage catalytic oxidation of the natural gas according to claim 6, which is characterized by comprising the following steps:
a. taking appropriate amount of Al (NO)3)3And a second component (M) Ni, Co, Mg, Ca, Ba in solution with NH3·H2O、NH4HCO3Or (NH)4)2CO3The solution is a precipitator, and the carrier precursor is prepared by complete precipitation, aging, washing and drying;
b. roasting the precursor prepared in the step a for 5-24 hours at 700-1200 ℃, and forming a spinel structure on the carrier or the surface of the carrier;
c. b, soaking the carrier containing the spinel structure prepared in the step b into a mixed solution of an active component (Ni) and an auxiliary agent (Ln) with a proper composition to be initially wet;
d. and c, placing the catalyst precursor prepared in the step c, and drying at the activation temperature of 550-650 ℃ for 5-15 hours.
10. The catalyst for the second-stage reactor in the method for preparing synthesis gas by two-stage catalytic oxidation of natural gas according to claims 6 and 9, characterized in that r-Al is used in step a of the preparation method of the catalyst2O3Soaking in Ni, Co, Mg, Ca and Ba solution, and oven drying.
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| US5112527A (en) * | 1991-04-02 | 1992-05-12 | Amoco Corporation | Process for converting natural gas to synthesis gas |
| US5338488A (en) * | 1992-09-10 | 1994-08-16 | Council Of Scientific Research | Process for the production of synthesis gas by oxidative converson of methane (or natural gas) using composite catalyst containing transitional and alkine earth metal oxides |
| EP0640561B1 (en) * | 1993-08-24 | 1998-11-11 | Shell Internationale Researchmaatschappij B.V. | Process for the catalytic partial oxidation of hydrocarbons |
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| CN100462299C (en) * | 2007-05-10 | 2009-02-18 | 天津大学 | Method for producing synthetic gas by reforming by-product glycerin vapor of biological diesel production |
| CN102086146A (en) * | 2010-12-15 | 2011-06-08 | 西南化工研究设计院 | Process for preparing glycol by oxalate hydrogenation in heat insulation reaction system |
| CN102086146B (en) * | 2010-12-15 | 2012-10-17 | 西南化工研究设计院 | Process for preparing glycol by oxalate hydrogenation in heat insulation reaction system |
| WO2016150268A1 (en) * | 2015-03-25 | 2016-09-29 | 武汉凯迪工程技术研究总院有限公司 | Online furnace drying method for heat-insulation natural gas catalytic oxidizing furnace |
| RU2675014C1 (en) * | 2015-03-25 | 2018-12-14 | Ухань Кайди Инджиниринг Текнолоджи Рисерч Инститьют Ко., Лтд. | Method of interactive drying of heat-insulated oven of natural gas catalytic oxidation |
| CN108622855A (en) * | 2017-03-15 | 2018-10-09 | 单岩崑 | A kind of method that natural gas catalysis oxidation prepares synthesis gas |
| CN108825411A (en) * | 2018-06-20 | 2018-11-16 | 沈阳腾力科技有限公司 | Natural gas catalytic unit and using natural gas as the device of power source |
| CN115779900A (en) * | 2022-10-25 | 2023-03-14 | 中船动力(集团)有限公司 | Tail gas CH for natural gas engine of ship 4 Purified oxidation catalyst, method for the production thereof and use thereof |
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| CN1093506C (en) | 2002-10-30 |
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