CN1306939A - Fluidized bed process for producing nitrogen-contg. synthesis gas by air partial oxidation of methane - Google Patents
Fluidized bed process for producing nitrogen-contg. synthesis gas by air partial oxidation of methane Download PDFInfo
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- CN1306939A CN1306939A CN00110061A CN00110061A CN1306939A CN 1306939 A CN1306939 A CN 1306939A CN 00110061 A CN00110061 A CN 00110061A CN 00110061 A CN00110061 A CN 00110061A CN 1306939 A CN1306939 A CN 1306939A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Feedstock gases including methane, natural gas or refinery gas and air or oxygen-riched air are converted into nitrogen containing synthetic gas in fluidized bed reactor with catalyst in high conversion and high selectivity. The reaction conditions includes 600-950 deg.c temperature, 0.1-3 MPa pressure and the natural gas to air as feedstock ratio of 1-3 or the ratio of natural gas to oxygen is oxygen riched feedstock of 1.4-5. The method has the advantages of low power consumption, less equipment investment and low cost.
Description
The invention relates to a fluidized bed reaction process for preparing nitrogen-containing synthetic gas by partial oxidation of methane air, in particular to a method for directly converting methane (or natural gas or refinery gas) and air (or oxygen-enriched air) into nitrogen-containing synthetic gas in a fluidized bed reactor by using a catalyst with nickel as an active component, which needs to be adjustedCO and H in reaction product2In the case of the above ratio, an appropriate amount of steam and/or carbon dioxide may be added to the reaction system.
The synthetic gas is an important chemical production raw material, and is mainly used as a raw material gas in the processes of synthesizing ammonia, methanol, dimethyl ether, Fischer-Tropsch synthesis and the like. At present, the synthesis gas is industrially prepared mainly by reforming natural gas and steam:
this reaction is a strongly endothermic reaction and, therefore, this process has the obvious disadvantage of high energy consumption. In addition, the reaction produces synthesis gas H2/CO =3/1, the synthesis gas is rich in hydrogen and not suitable for the synthesis of methanol, dimethyl ether, ethanol, fischer-tropsch synthesis, etc. as feed gas.
The production of synthesis gas by partial oxidation of methane with pure oxygen has attracted widespread interest at home and abroad since the nineties (Ashcroft a.t.et al., Nature,344,319,1990; Ashcroft a.t.et al., Nature,352,225,1991; Hickman d.a., and Schmidt, l.d., Science,259,343,1993). Compared with the existing industrialized steam reforming method, the process has the obvious advantage of low energy consumption because the process changes from strong heat absorption into mild heat release, and in addition, the reaction can be carried out at a large space velocity, and the scale and investment of the device can be reduced. At present, the pure oxygen partial oxidation reaction of methane carried out in a fixed bed has the following disadvantages: (1) carbon deposition on the surface of the catalyst under a pressurizing condition; (2) hot spots exist in the catalyst bed layer; (3) loss of the active component nickel of the catalyst; (4) pure oxygen requires expensive air separation plant investment and increases the cost of oxygen production.
The invention aims to provide a fluidized bed reaction method for preparing nitrogen-containing synthesis gas by air partial oxidation of methane, which can eliminate carbon deposition on the surface of a catalyst; the hot spots of the catalytic bed are reduced, so that the safety of the system is further ensured; the problem of loss of the active component nickel of the catalyst is avoided; and can avoid expensive air separation equipment investment and increase the cost of oxygen production.
The invention provides a fluidized bed reaction method for preparing nitrogen-containing synthesis gas by air partial oxidation of methane, which is characterized by comprising the following steps: introducing raw material gas comprising methane, natural gas or refinery gas and air or oxygen-enriched air into a fluidized bed reactor filled with a catalyst, and converting the raw material into nitrogen-containing synthesis gas in the fluidized bed reactor with high conversion rate and high selectivity; the reaction conditions are as follows: the temperature is 600-950 ℃, the reaction pressure is 0.1-3 MPa, the ratio of natural gas/air is = 1/1-1/3 when air is used as a raw material, and the ratio of natural gas/oxygen is = 1/0.2-1/0.7 (O in oxygen-enriched air) when oxygen-enriched air is used as a raw material2/N2=1/3.5～1/0.1)。
In the fluidized bed reaction method for preparing the nitrogen-containing synthesis gas by the air partial oxidation of the methane, provided by the invention, water andor carbon dioxide, CH can be added into raw material gas4/H2O=0.2～2.5,CH4/CO2=0.2～2.5。
The catalyst used in the invention can adopt a supported nickel catalyst, and the supporting amount of metallic nickel is 2-12% (weight). The catalyst can be modified by one or two of rare earth, mixed rare earth and alkaline earth metal, and the modification amount is as follows: 0.5 to 6% by weight of a rare earth metal and 0.5 to 5% by weight of an alkaline earth metal.
The invention uses air (or oxygen-enriched air) to replace pure oxygen as raw material gas, which can avoid using expensive air separation equipment and increase the cost of oxygen production. The synthetic gas prepared by the invention contains nitrogen, on one hand, the synthetic gas can be used as raw material gas in the process of synthesizing ammonia, on the other hand, the methanol or the ethanol can be synthesized with high conversion rate by adopting a slurry bed technology or a supercritical low-temperature method, in addition, the synthetic gas can also obtain higher yield in the reaction processes of converting the synthetic gas into dimethyl ether, mixed alcohol ether fuel, Fischer-Tropsch synthetic diesel oil, synthetic wax and the like, and the reaction raw material gas does not need to be circulated in a reaction system, so that the influence of the nitrogen on the consumption of compression work is relatively small, and the production method of the synthetic gas with low energy consumption can also be provided for the reaction processes of synthesizing the methanol or the ethanol at low temperature, synthesizing the dimethyl ether, the. The technical details of the invention are described in detail by the following examples:
FIG. 1 shows Ni/Al in a fluidized bed2O3Experimental results on catalyst stability
Example 1
Weighing Ni/Al with the nickel content of 7 wt%2O35g of catalyst is filled into a fluidized bed reactor made of quartz glass by burning, the inner diameter of the reactor is 2.2cm, and a temperature measuring thermocouple and a sampling tube are arranged in a catalyst bed layer and can move up and down to measure the temperature and the reaction performance of different bed layers. Catalyst via H2Reducing and activating for half an hour at 700 ℃, introducing raw material gas methane and air for reaction, and reacting with CH4Air =1/2.4, gas flow rate is 1000ml/min, fluidized height of the catalyst bed is about 6cm, reaction pressure is 0.1Mpa, reaction temperature is 600-800 ℃, and reaction results and catalyst bed temperature distribution results are shown in tables 1 and 2. The results show that the methane conversion rate and the selectivity of hydrogen and carbon monoxide are obviously increased along with the temperature rise, when the temperature reaches 800 ℃, the catalyst has high activity and selectivity, and H in the product2Ratio of/COClose to 2, can provide raw material gas with proper composition for the reaction processes of synthesizing methanol, dimethyl ether, ethanol, Fischer-Tropsch synthesis and the like. As can be seen from the results inTable 2, the catalyst bed has no hot spot in the fluidized bed, and particularly when the external control temperature is 800 ℃, the temperature difference of the catalyst bed is 2 ℃, which indicates that the hot spot problem of the catalyst bed in the fixed bed can be well solved by using the fluidized bed.
TABLE 1 Effect of reaction temperature on the air partial Oxidation reaction Performance of methane the external temperature controlled inlet temperature conversion Selectivity (%) H2Degree (%) (° c)/CO CH4CO H2600 610 63.0 63.1 89.5 2.80650 650 74.1 77.2 93.9 2.40700 690 84.6 84.3 96.3 2.26750 740 88.4 91.7 98.0 2.10800 790 94.2 96.1 98.9 2.06
TABLE 2 results of catalyst bed temperature distribution in fluidized bed reactor (C.) external control temperature (C.) of 01 cm 2cm 3cm 4cm 5cm 6cm
600 614 611 605 596 585 574 564
700 696 696 692 683 677 674 671
800789789789788788788787 positive with the direction of air flow as the axis
Example 2
Weighing warp CeO2Modified Ni/Al2O35g of the catalyst was charged in a fluidized bed reactor made of quartz glass, the inner diameter of the reactor was 2.2cm, the nickel content of the catalyst was 7 wt%, and CeO was added2The content is 5%.The catalyst is reduced and activated for half an hour at 700 ℃ by H2, raw material gas methane and air are introduced for reaction, CH4The air =1/2.4, the fluidization height of the catalyst bed layer is about 6cm, the reaction pressure is 0.1Mpa, the external control temperature of the reaction is 800 ℃, and the flow rate of the reaction raw material gas is 450-1800 ml/min. The reaction performance at the catalyst outlet and at the reactor outlet, which were located 6cm above the distributor, was measured by moving the sampling tube up and down, respectively, and the results are shown in Table 3. Therefore, the catalyst has high catalytic activity and selectivity for preparing the nitrogen-containing synthesis gas H by partially oxidizing methane in the air under the fluidized bed state2The ratio of/CO is close to 2, and the raw material gas with proper composition can be provided for the reaction processes of synthesizing methanol, dimethyl ether, ethanol, Fischer-Tropsch synthesis and the like. It can also be seen that the methane conversion at the reactor outlet is slightly lower than at the catalyst outlet, since a small amount of fine catalyst powder is suspended above the catalyst bed at a lower temperature, andone step is caused by methanation reaction.
TABLE 3 Effect of feed gas flow on methane air partial oxidation reaction Performance
| Catalyst bed Layer(s) | Flow of reactant gas | Conversion (%) | Selectivity (%) | H2/CO | |
| (l/m) | CH4 | CO | H2 | ||
| Catalyst discharge Mouth piece | 0.45 | 94.0 | 96.6 | 98.5 | 2.05 |
| 0.90 | 95.2 | 97.0 | 99.2 | 2.05 | |
| 1.35 | 95.9 | 96.5 | 99.3 | 2.08 | |
| 1.80 | 95.6 | 96.6 | 99.0 | 2.07 | |
| Reactor outlet Mouth piece | 0.45 | 93.9 | 96.5 | 98.5 | 2.05 |
| 0.90 | 94.9 | 96.8 | 99.3 | 2.06 | |
| 1.35 | 92.1 | 95.1 | 97.3 | 2.09 | |
| 1.80 | 89.0 | 93.3 | 96.7 | 2.10 | |
Example 3
Respectively called warp La2O3And MgO-modified Ni/Al2O3Catalyst 1g and 5g were packed in a reactor made of quartzIn the fluidized bed reactor, the inner diameter of the reactor was 2.2cm, the catalyst nickel content was 7 wt%, the Mg content was 2%, CeO2The content is 5%. Catalyst via H2Reducing and activating for half an hour at 700 ℃, introducing raw material gas methane and air for reaction, and reacting with CH4Air=1/2.4, reaction pressure is 0.1Mpa, reaction external control temperature is 800 ℃, and total flow of raw material gas is 1000 ml/min. The results of the effect of catalyst loading on the air partial oxidation performance of methane are shown in table 4.
TABLE 4 influence of catalyst loading on the performance of the air partial oxidation of methane reaction the catalyst loading inlet temperature conversion (%) selectivity (%) H2/CO(g) (℃) CH4CO H21 800 94.6 95.4 98.9 2.085 798 93.7 95.6 99.1 2.10
Example 4
Weighing Ni/Al with the nickel content of 7 wt%2O35g of the catalyst was charged into a fluidized bed reactor made of quartz glass, and the inner diameter of the reactor was 2.2 cm. Catalyst via H2Reducing and activating for half an hour at 700 ℃, introducing raw material gas methane and air for reaction, and reacting with CH4Air =1/2.4, gas flow rate is 1000ml/min, fluidization height of catalyst bed layer is about 6cm, reaction pressure is 0.1Mpa, and reaction external control temperature is 800 ℃. The reaction results of the catalyst used over 200 hours are shown in FIG. 1. The results show that the methane conversion rate is always kept above 94% within 200 hours of the experiment, and CO and H2The selectivity is always kept above 95% and 99%, respectively. The results show that, in the fluidized bed state, Ni/Al2O3The catalyst has high activity and selectivity for methane air partial oxidation reaction, and has high carbon deposition resistance and stability. The elemental analysis results showed that the nickel content of the fresh catalyst was 7.1 wt%, respectively 100 wt%The nickel contents of the catalysts after the use for hours and 200 hours were 6.9 wt% and 7.0 wt%, respectively, indicating that the active component nickel of the catalyst was hardly lost in the fluidized bed state.
Example 5
Separately weighing Ni/Al2O3Catalyst 5g and mixed rare earth modified Ni/Al2O35g of catalyst is put into a fluidized bed reactor made of quartz glass, the content of the catalyst nickel is 7 percent, and the content of the mixed rare earth is 4 percent. Catalyst via H2Reducing and activating for half an hour at 700 ℃, introducing a raw material gas of natural gas/oxygen-enriched air/water vapor (volume ratio) =1/1.46/0.3 for reaction, wherein the oxygen content in the oxygen-enriched air is 34 mol%, the reaction pressure is 0.1Mpa, the reaction outlet temperature is 800 ℃, and the natural gas flow is 300 ml/min. The reaction results are shown in Table 5. The result shows that the prepared nitrogen-containing synthesis gas is suitable for being used as raw material gas for synthesizing ammonia.
TABLE 5 reaction results for preparing nitrogen-containing syngas by converting natural gas, oxygen-enriched air and steam
Catalyst CH4CO2H2O CO H2N2R* Ni/Al2O30.402.365.1819.749.223.03.00 mixed rare earth modified Ni/Al2O30.38 2.28 5.29 20.3 48.8 22.9 3.02*R=(H2+CO)/N2
Example 6
Weighing MgO-modified Ni/Al2O35g of catalyst is put into a fluidized bed reactor made of stainless steel, the content of nickel in the catalyst is 7 percent, and the content of Mg is 1.5 percent. Catalyst via H2Reducing and activating for half an hour at 700 ℃, introducing a raw material gas of natural gas/oxygen-enriched air/water vapor (volume ratio) =1/1.46/1.9 to react (the oxygen volume content in the oxygen-enriched air accounts for 34%), the reaction pressure is 1Mpa, and reacting outThe mouth temperature is 850 ℃, and the natural gas flow is 300 ml/min. The results of the reaction at 100 hours are shown in Table 6. The result shows that the prepared nitrogen-containing synthesis gas is suitable for being used as raw material gas for synthesizing ammonia. The process requires little endotherm.
TABLE 6 reaction results of reaction of natural gas, steam and oxygen-enriched air to prepare feed gas for ammonia synthesis
CH4CO2H2O CO H2N250.256.4628.39.8939.116.03.06200.366.7228.39.6339.016.13.02400.246.3828.410.139.016.03.05600.276.4728.29.9139.116.03.06800.276.5428.29.8839.016.13.041000.356.2428.610.038.716.13.02R = (H)2+CO)/N2
Claims (5)
1. A fluidized bed reaction method for preparing nitrogen-containing synthesis gas by methane air partial oxidation is characterized in that: introducing raw material gas comprising methane, natural gas or refinery gas and air or oxygen-enriched air into a fluidized bed reactor filled with a catalyst, and converting the raw material into nitrogen-containing synthesis gas in the fluidized bed reactor with high conversion rate and high selectivity; the reaction conditions are as follows: the temperature is 600-950 ℃, the reaction pressure is 0.1-3 MPa, when air is used as a raw material, the ratio of natural gas/air is = 1/1-1/3, and when oxygen-enriched air is used as a raw material, the ratio of natural gas/oxygen is = 1/0.2-1/0.7.
2. The fluidized bed reaction process for the air partial oxidation of methane to produce a nitrogen-containing synthesis gas as claimed in claim 1, wherein: adding water and/or carbon dioxide, CH to the feed gas4/H2O=0.2～2.5,CH4/CO2=0.2～2.5。
3. A fluidized bed reaction process for the air partial oxidation of methane to produce nitrogen containing synthesis gas as claimed in claim 1 or 2 wherein: o in oxygen-enriched air2/N2=1/3.5～1/0.1
4. The fluidized bed reaction process for the air partial oxidation of methane to produce a nitrogen-containing synthesis gas as claimed in claim 1, wherein: a supported nickel catalyst is adopted, and the supporting amount of metallic nickel is 2-12% (by weight).
5. The fluidized bed reaction process for the air partial oxidation of methane to produce a nitrogen-containing synthesis gas as claimed in claim 4 wherein: the catalyst is modified by one or two of rare earth, mixed rare earth and alkaline earth metal, and the modification amount is as follows: 0.5 to 6% by weight of a rare earth metal and 0.5 to 5% by weight of an alkaline earth metal.
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| CN111484394A (en) * | 2020-04-08 | 2020-08-04 | 华南农业大学 | Method and system for synthesizing methanol by in-situ catalytic gas preparation of combustible ice |
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| CN111484394A (en) * | 2020-04-08 | 2020-08-04 | 华南农业大学 | Method and system for synthesizing methanol by in-situ catalytic gas preparation of combustible ice |
| CN111484394B (en) * | 2020-04-08 | 2022-01-25 | 华南农业大学 | Method and system for synthesizing methanol by in-situ catalytic gas preparation of combustible ice |
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