JPS60501607A - High temperature production of benzene from natural gas - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to the production of higher hydrocarbons from methane.

More specifically, the present invention provides for a free radical initiator that is separately added to the reaction zone as a free radical initiator. Methane and methane-containing gases containing C2 and benzene in the presence of small amounts of oxygen It is concerned with high temperature conversion to higher hydrocarbons.

Background of disclosure For more than 50 years, scientists have been trying to make useful liquid hydrocarbon products from natural gas. Attempts have been made to find efficient ways to create 10 of 1931 In March, the U.S. Bureau of Mines announced that Smith's ``production of motor fuel from natural gas'' Report AR, I entitled Report Sergeant.

3143 was announced.・In this report, Mr. Smith and his collaborators Optimizing the production of benzene and C2 unsaturates from methane by high-temperature pyrolysis of It summarizes the results of extensive research devoted to In these methods, about t Furnace temperatures ranging from 150 to 1,240°C are used, and under these optimal conditions They have a feedstock conversion of 29% and a weight of 18.5% of the feedstock converted. % benzene production selectivity was obtained. Other generations of the Mr. Smith surname generated by the method The materials were ethylene, acetylene, hydrogen, and tar and carbonaceous solids. Ta The selectivity of the feedstock converted to coal was 21% by weight.

Selectivity refers to the amount of product produced from the converted feedstock. Hidden For methane 11b converted to higher hydrocarbons, 21% by weight of the product was and 18.5% by weight was benzene. In these experiments, Sumi Suh and his collaborators first purge air from the reactor using a flow of nitrogen to remove the reaction zone. methane or methane-containing natural gas. It is introduced directly into the reactor. Shortly after this, Mr. Smith and his collaborators reaction time to maximize benzene production over a decomposition range of 200 °C. No. 2,061,597 directed to optimizing the . t At the optimum conversion temperature of 150°C, the reaction time was determined to be 42 ms. Ta. Mr. Smith recommends a relatively short reaction time to avoid the formation of tar and carbonaceous material. It should be noted that time was used. Mr. Smith, in his report, 1. A benzene to tar yield ratio of approximately 16 was obtained at a furnace temperature of 200°C. (Tar does not include solid carbonaceous material).

1. Calculate that the reaction time at 200°C was approximately 270 milliJ seconds. be able to.

In U.S. Pat. No. 2.063.133, Hens Trobutusz Paraffinic and olefinic coals under relatively low temperature conditions of ~1,000℃ It is disclosed that a liquid product could be obtained from hydrogen chloride gas.

Thermal decomposition occurred in the presence of about 081-10% chlorine or chlorine-containing compounds, but 10% % is considered an upper limit. Unfortunately, the details of the Trobutsu method have not been disclosed. do not have. That is, Mr. Trobutusz said that the tar and carbon produced using his method He did not mention the amount. Produce benzene from methane or low molecular weight hydrocarbons Another attempt to create a In some cases, a two-step contact method is used to produce liquid products such as benzene. .

Many of the conventional techniques related to thermal decomposition of low molecular weight hydrocarbon gases such as methane, ethane, etc. as disclosed in U.S. Pat. No. 2,721.227 and U.S. Pat. No. 2.912.475. As shown, it relates to the production of acetylene therefrom. US Patent No. 2 ．． No. 8,75,148 and No. 2.912.475 both include It should be noted that the authors teach how to specifically eliminate the presence of oxygen in . Thus, the reactions disclosed in these patents do not, strictly speaking, open free radical reactions. Concerning pyrolysis without adding to the reaction zone substances that can initiate or accelerate Ru. Also, these do not disclose the production of benzene, and the hydrocarbon feedstock is molecular It must contain at least 2 carbon atoms. Disclosed preferred supplies Feedstocks include ethylene, benzene and naphtha streams.

Robinson's U.S. Patent No. 2.608.594 is a patent for producing benzene. Discloses a two-step methane decomposition method4 Ru. In this method, the methane feedstock is heated to about 1567K and then about 1.5K. To produce a mixture of feedstock and hydrogen-rich gas at a temperature of 900 K is mixed with hot combustion gases containing free hydrogen and no oxygen. this hot mixture is held at 1,900 K for about 0.01 seconds and contains hydrogen-rich acetylene. Produces gas. This acetylene-containing gas is then enriched with additional cold hydrogen. quenched to a temperature of about 1422° C. and at this temperature about α8 seconds mass. to produce products enriched in benzene. This method also produces substantial amounts of tar and solids. It should be noted that carbonaceous products are produced.

5 activities aimed at attempting to thermally decompose low-molecular rice gas into liquid hydrocarbons such as benzene. Despite being carried out for more than 0 years, this objective has been achieved with negligible or relatively low Comparison where the feedstock is converted to benzene-rich liquid hydrocarbons with tar production There remains a need for methods that achieve selective selectivity.

In the present invention, free radical-initiated thermal conversion of methane or methane-containing gas feedstock Useful higher hydrocarbon products, including benzene-rich liquids, can be produced by with relatively high selectivity of feedstock conversion to An alternative method has been found to produce a product that is possible. This method uses methane-containing gas The gas feed is contacted with oxygen in the reaction zone, which acts as a free radical initiator. The key part of this method is that the oxygen and gas feedstocks are not premixed. It should be introduced separately into the reaction zone.

Thus, the present invention provides a meth/containing gas feedstock with oxygen and at least about 1,300 sufficient to convert at least a portion of the feedstock to benzene at a temperature of the oxygen is introduced separately into the reaction zone and the oxygen is introduced separately into the reaction zone. the feedstock by a method comprising the presence of α5 volume t% or more of tan. C2 and it) higher gaseous hydrocarbons and benzene-rich hydrocarbon liquids. It is about manufacturing. Of course, liquid hydrocarbons are defined as Refers to hydrocarbons that are liquid at atmospheric pressure. What is methane-containing gas feedstock?Natural Gas 1, meth produced by partial combustion of coal, coke or other carbonaceous materials Negligible tar and solid carbonaceous material, which refers to syngas containing This means less than about 2% by weight of the product.

Additionally, heating methane to a relatively high temperature of over 1,300 °C in the presence of alumina It was discovered that carbon can be formed on the alumina surface in this case. , which also forms part of this disclosure. This means that methane is about 9 It is known to those skilled in the art that at temperatures as low as 23°C it begins to decompose and cause surface contamination. This is surprising considering the fact that it is well known. So shift, Meta. aluminum as a heat exchanger to preheat the water without decomposing it into carbonaceous materials. It was also found that it is possible to use the na.

detailed description of the invention The reaction time, temperature and amount of oxygen required in the method of the invention are interrelated. There is. Higher reaction temperatures require shorter reaction times and lower amounts of oxygen, and vice versa. You can also say Generally, the reaction temperature ranges from about 1300 to 1.800K. good The desired and optimum reaction temperature depends on the reaction pressure. At atmospheric pressure, the reaction temperature is Preferably about 1.400 to 1,700, more preferably about 1,400 to 1.60 It is in the range of 0. Under these conditions, the reaction time is generally about 0.1 to 1 seconds, preferably It is preferably in the range of 0.2 to 0.05 seconds, more preferably about 0.2 to 0.3 seconds. If against If the reaction continues for a short period of time, the selectivity for benzene formation decreases. and significant amounts of undesired tar-like and carbonaceous materials are formed.

For the method of the invention, oxygen and methane are mixed until the methane reaches the reaction temperature. and then combine them to achieve an oxygen-initiated free radical reaction. Mix as quickly as possible at the reaction temperature, thereby avoiding unwanted reactions and their associated It is important to minimize the formation of undesirable compounds. Practical things As such, this can be introduced separately into all reaction zones as oxygen and methane containing gas feedstocks. easily achieved by Similarly, methane avoids its destructive thermal decomposition. It should be heated to the reaction temperature as quickly as possible to ensure that the reaction temperature is maintained. If desired, meta In the absence of oxygen, the carbonaceous material or its precursor material is decomposed or polymerized. It can be preheated to a high temperature of 975~t　O'75　K in a relatively short period of time. Ru. Thus, in order to minimize the heat usage of the reactor or reactor feed heater. It may be advantageous to preheat the methane by any convenient means to a temperature of In some cases. In the examples below, methane is approximately 10 to 10' in one step. It was heated from room temperature to the reaction temperature at a rate of K/sec.

If desired, the methane or methane-containing gas feedstock may be combusted to combust some of the feedstock. mix the combustion products with the unburned feedstock and introduce this mixture into the reaction zone. and then at least partially by contacting it with oxygen or an oxygen precursor substance. Can be heated in minutes.

Additionally, the reaction products formed by the method of the present invention can be used to stop subsequent reactions. sufficient to minimize the associated loss of desired product to tar and carbonaceous material. It is also important to quickly cool or quench to a temperature level as low as possible, and it is also important to saturated or unsaturated hydrocarbon ice gas, or liquids such as benzene and toluene), (b ) the time the product is held at that temperature and (C) the time at which no decomposition occurs from that temperature. Typically about 500-1 m depending on the secondary cooling rate to ambient temperature such as ,0QOK. Of course, benzene and other reaction products (especially acetate) decomposition of unsaturates such as olefins, ethylene, and other olefins is as low as 500 Even temperature can occur, and the extent of such decomposition is a function of time and temperature. I would like you to understand that. The quenching rate used depends on the desired reaction product. . Thus, if acetylene is the desired product, then the desired product is benzene. Faster quenching rates may be required if acetylene is not desired and acetylene is not desired. will be understood. - By way of example, but not limitation, the method of the invention When the methane reaction product is quenched from the reaction temperature of about 1500 to about 500K Quenching rates ranging from 10' to 7 seconds to 10' to 7 seconds have been successfully used. 10' A quench rate of 7 seconds for Cool from 1.500K to 500K.

As previously mentioned, for the method of the present invention, the methane content of the feed gas is As much as 0.5% by volume of oxygen is required. Preferably at least o 7% by volume and preferably at least about 10% by volume of oxygen is used. this Oxygen content is based on molecular oxygen.

However, this oxygen is present either as molecular oxygen or as RO on oxygen atoms upon heating. Oxygen-containing compounds with one or more unpaired electrons such as O.peroxy compounds, RO., etc. It may also exist as a compound that generates free radicals. bound by a particular theory Although it is not desired that free radicals such as the hydrocarbon free radicals formed in the present invention Therefore, it seems that it will start. Maximum amount of oxygen used as free radical initiator depends on yield and product selectivity considerations, but generally depends on feedstock It is preferred not to exceed about 10% by volume of oxygen, preferably 5% by volume, based on the methane content. Delicious. Thus, it is clear to those skilled in the art that the process of the present invention can be carried out using conventional combustion or partial oxidation methods. It will be understood that there is no

Although benzene is a particularly desirable product of the process of the invention, other useful C2 and higher gaseous and liquid hydrocarbon products are also produced. Example 2 below The following table obtained using the procedure shows the reaction of 1.425 with 2,0% by volume of oxygen Typical product components from methane feedstock contacted for 250 milliseconds at temperature This shows the results of the analysis. The methane conversion rate was about 25iii%.

Negligible amounts of solid carbonaceous products and tar-like substances were detected.

As mentioned above, negligible means that based on the total product , about 0.4 to 2% by weight of tarry and solid carbonaceous materials (or methane) based on the total product. 01-2.5% by weight based on the tan feedstock) was found to be produced. this Another way to express is the amount of tar and tar produced relative to the amount of benzene produced. The proportion of solid carbonaceous material (which is 11-5.7% by weight). This is Based on the converted methane, 21% tar and 1B, 5% benzene ( This can be expressed as a tar/benzene ratio of 113.5% by weight). This is in marked contrast to prior art methods such as the generated Smith surname method. Ru.

Product Hydrocarbon product selectivity, methyl acetylene vinyl acetylene Tar and solid carbonaceous products 1 Total 100.0 Brief description of the drawing FIG. 1 is a schematic diagram of the apparatus used in each example.

Figure 2 shows the percentage of methane converted to higher hydrocarbon products at 1,425. Reaction temperature and 250mm! The graph shown as a function of the oxygen content at a reaction time of J seconds. It is f.

Figure 3 shows the hydrocarbon product distribution at a reaction time of 250 ms and 2% oxygen. This is a plot of the reaction time as a function of the reaction time.

Figure 4 shows the hydrocarbon product distribution at 2% oxygen and a reaction temperature of 1.425 This is a plot of the reaction time as a function of the reaction time.

The invention will be easily understood by reference to the following examples.

The experimental reactor apparatus used is shown schematically in FIG. This is graphite An aperture with a length 6t0 and an inner diameter of ZOclI surrounded by a heating element 12 Lumina tube 10 was getting worse. Graphite heating element 12 and alumina tube on top of the alumina tube so that there is a space 11 of approximately α5cm between the outer wall of the Placed. Thus, the graphite heating element did not come into contact with the alumina tube. . The space 11 between the element 12 and the tube 10 is filled with an inert gas such as helium or argon. continuously purged at Then about 6.41 graphers are placed on top of the heating element 12. It felt insulator 13 was arranged. Water-cooled aluminum is placed on top of the graphite insulator. Comes with 1s mini jacket! did. Fitting the alumina honeycomb 14 into the tube 10, One end was then capped with an aluminum end plate 16. The other end of the tube 10 has a warm The water cooled assembly 54 was installed and capped with aluminum end plates 18. Miscellaneous During operation, methane-containing feed gas enters the reaction chamber via inlets 20 and 22. , from there it passed Honeycomb 14. This honeycomb straightens the gas flow and served to heat it to the reaction temperature. After passing through the honeycomb 14, the feed source The feed gas then entered reaction zone 24. The reaction zone 24 includes a line 26 and an injector. After Head 28, @cum was introduced. The oxygen and hydrocarbon feedstock stream is reaction zone to ensure initiation of the free radical reaction of methane at the desired temperature. It was introduced separately in 24. The reaction zone 24 includes a honeycomb heater 14 and a movable sample processor. It was determined by the distance between the tip of the tube 30 and the tip of the tube 30.

The reaction products were quenched and cooled using a hydrothermal system consisting of three concentric stainless steel tubes. Samples were removed at various axial distances from the honeycomb 14 using a sample globe 30. . To sample the gaseous products, the globe 50 is moved from the bottom of the furnace to the intended shaft. into the reaction zone up to the directional position.

Next, a sampling pump (not shown) connected to the probe is activated and its The probe was adjusted so that a uniform gas sample was extracted from the tip of the globe through the globe.

The quenched sample is then placed in a gas chamber equipped with flame ionization and thermal conductivity detectors for analysis. Passed through a chromatograph (not shown).

The reaction time for a particular experiment is determined by the time between the tip of the probe 3o and the honeycomb 14. determined by the distance and increasing or decreasing the distance between the probe 30 and the honeycomb 14 can be varied by adjusting the axial distance of the probe 30 to did it.

The cooling water used for probe 50 provides both external and internal condensation of the product. It was preheated to about 75°C to avoid. Is the probe 3o hot water instead of steam? It should be noted that the The reaction life provided by this glove The quenching rate of the product ranged from approximately 10'7 seconds to 100'7 seconds. Teflon The probe 30 was connected to a gas chromatograph by a conduit (not shown); The pipes were heated to 110°C to prevent product adsorption and condensation therein. It was. Gaseous products not removed by sample probe 30 during operation system, pipes 10 and cooling assembly 34 and is extracted via discharge line 32. .

The temperature of the reactor is maintained through the insulator 15 and immediately adjacent to the heating element 12 ( controlled and monitored by a boron-graphite/graphite thermocouple located at Ta. The outer wall temperature of the alumina tube 10 is determined by the temperature of the cooling jacket 15 and the graphite insulator. Checked using a light pyrometer observed by a peephole in the wall of 13 . The temperature of the reaction zone 24 is controlled by the temperature of the zirconium oxide inserted into the reaction zone through the bottom of the furnace. was measured using a rubber-coated platinum/platinum-15% rhodium thermocouple.

The ceramic honeycomb 14 has a large number of straight holes with a nominal hole diameter of 0.318 cm. , thickness 2 formed with axially aligned and radially spaced holes. 54, and to maximize heat transfer between it and the reactor wall. It was cut into a cylindrical shape so as to fit exactly into the inner diameter of the alumina tube 1o. This honey The cam served to heat and straighten the feed gas stream.

Heat transfer calculations show that under the experimental conditions used, the honeycomb It was shown that a heating rate of 7 seconds provided approximately 104 to IO'. These calculated values means that when the gas leaves the honeycomb, its temperature is close to that of the honeycomb itself. It shows. These calculations determine the temperature of the reaction zone for the zirconium oxide coated white Confirmed by measuring the gold/platinum-16% rhodium heat pair. to tube 10 Under typical experimental conditions at a wall temperature of 1.500 K, the reaction zone 24 The average temperature of the gas during the reaction time was approximately 1.425K. for all experiments However, there was no evidence of carbon adhesion on the alumina honeycomb 14, and there were many signs of carbon adhesion. There was no blockage of the honeycomb or any pressure drop due to it even after hours of use. I would like to add something.

The oxygen injector assembly consisted of a supply tube 26 attached to the cylindrical head.

The head 28 has six holes of diameter α022 located at the same height near its closed end. It had holes drilled in the radial direction. This syringe assembly is placed inside the honeycomb 14. is inserted through the central passage and the hole in the head 28 is just below the bottom of the honeycomb 14. It was positioned to the side. During the experiment, oxygen is transferred from the center of the reaction zone to the outside. It was injected through the hole as a radial jet directed toward the According to the calculation of cross-flow jet mixing For example, under the conditions used in the experiment, the complete interaction between oxygen and hydrocarbon feed gas streams is The time required for jet mixing is negligible compared to the reaction time in the reaction chamber. It was shown that

The surface-to-volume ratio of the reaction zone 24 is selected to ensure that dust effects are negligible. It was relatively small, about 0.57α-1. An experiment was conducted to prove this Ta. To measure this, a gas flow restrictor was placed on top of the honeycomb 14.

This restrictor fits exactly inside the alumina tube 1o and has a hole with a diameter of 2.77 mm. It was a ring-shaped alumina plate. Thus, the methane gas stream is directed to the reaction zone 24. The central part of the reaction zone 24 (which covers the entire cross-section of the reaction chamber) before expanding again downstream (approximately 15% of the product). Compare the distribution of production dynamics at the same reaction time , the product from the reactor with or without a gas flow restrictor is There is almost no difference between 16 This proved that there was no l9 on the wall at all.

Example 1 This experiment investigated the effect of oxygen concentration on the degree of conversion of methane to higher hydrocarbons. using the equipment and procedures described under the experimental procedure section above. It was conducted. The temperature of the reaction zone was 1,425°C, and the reaction time was 250mm. It was seconds. Mix 10 n/min of methane with 1 n/min of argon and The mixture is transferred to the reactor shown in Figure 1 via a henecum 14 which heats the methane to the reaction temperature. supplied. Argon is used for carbon balance measurements (on average, in the range of 98-100% carbon (showing income and expenditure) was used as a tracer. This range is within experimental error. there were. This is due to the negligible amount of solid carbonaceous material formed in the reaction zone. (i.e., 1% by weight of the product) as there was only evidence of formation. At the same time, the influx A mixture of oxygen and helium at 0.2 n/min is added to the reactor via port 26 and head 28. were supplied separately. The oxygen-helium flow has the same mixing ratio as the nitrogen-argon flow. It is introduced in such a way that its movement cover is always kept constant so as to protect the turns. Ta. For this purpose, the amount of HCQ is determined by the amount of acid The elementary concentration was varied to remain constant at 0.2 J for 7 minutes. Approximately 1 After ~2 minutes, the reaction reached steady state. During the reaction, the products are transferred to the sample globe 3 0 and is continuously removed from the reaction zone 24 and fed to the gas chromatograph. It was done.

The volume percent of oxygen present based on the methane content in the feed gas varies from 0 to 2%. It was done.

Figure 2 is a plot of the results of this experiment, which shows the free radical initiated methane conversion. at least about 0.5% by volume of oxygen required in the reaction zone to achieve This clearly illustrates the unexpected and surprising effects of minimal amounts.

In all cases, the selectivity for benzene formation from methane is approximately 35 wt. % and about 75% of the C2 was acetylene. Significant amount at the end of each experiment It should be noted that carbonaceous products were found to be deposited at the bottom of the reaction chamber. Ru. This means that most of the reaction products are removed from the reaction chamber by the sample probe. This was due to the fact that the aircraft continued to descend to the exhaust port. They are hot As they continue to progress down the chamber, they continue to react and polymerize, eventually Forms tar and carbonaceous products.

However, in this example and each side below, either in the reaction zone or in the sample probe. Solid carbon formed in the product extracted from the reaction zone by the mineral sample pump We would like to emphasize that the amount of diathesis and tarry substances was negligible.

Example 2 This experiment was similar to that of Example 1, except that the oxygen concentration was 2% by volume of methane. The reaction time was maintained at 250 ms. In this experiment, methane Temperature was used to investigate the effect of temperature on the conversion rate and product distribution of converted methane. A series of experiments were conducted at varying degrees.

The results of this experiment are shown in Figure 3, which shows the increase in benzene production as the temperature increases. Figure 2 illustrates increasing and increasing amounts of C2 hydrocarbon (75% acetylene) production.

Example 3 This experiment was similar to Example 1, except that the reaction zone temperature was maintained at 1,425 K. and oxygen was 2% by volume of the methane feed. In this experiment, the reaction time is , to investigate the degree of methane conversion and its influence on the product distribution of converted methane. It was changed due to The results are shown in Figure 4, and as the reaction time increases, shows a gradual increase in C2 and benzene production (again, about 75% of C2 acetylene).

Example 4 This experiment shows that if methane and oxygen are premixed before the methane reaches the reaction temperature, This example illustrates that the method of the present invention does not result. In this experiment, two separate reactors was used. The reactor name is used to illustrate the case of separate addition, and the reaction Vessel B was used to illustrate the premix case. Both reactors have 14 It is made by fitting a quartz tube with a cylindrical inner diameter into a cylindrical T-heat type Matsufuru furnace in the axial direction. It was. The reaction products were analyzed by gas chromatography, and the reaction temperature was 1 ．． It was 373K.

In reaction DA, a 0.6 to 1 volume ratio of oxygen to argon is preheated and the inside of the reactor tube is The reaction zone was fed through a quartz tube with an inner diameter of 7 mm and an outer diameter of 9 mm, which was placed axially on the side. . The preheat zone was 12.5 cIn long and the reaction zone was 94 CM long. methane The reaction occurs through the annular space between the inside of the reactor tube and the outside of the oxygen/argon injection tube. added separately to the zone. The preheating zone for methane was also 12.5 cm long. .

The total ratio of CH4:02:Ar supplied to the reaction zone was 1:o, o6:α1. there were.

In reactor B, CH4:Oz:Ar with a volume ratio of 1:α06:α1 is premixed. , and 3ws]) to the reaction zone via a quartz preheating tube. preheat The length of the five tubes inside the zone or furnace was 28 cm. The reaction zone has a length of 79 It was 1.

In both cases, the reactions were carried out with reaction times of approximately 250, 380 and 500 ms. It was. The presence of oxygen is not in reactor B, which is the case of premixing, but in the case of separate addition. It was found that methane conversion and benzene yield increased only in certain reactors. Ivy. In the case of premixing, no improvement was observed with oxygen. In other words, the forecast In the case of premixing, essentially the same results were obtained without the use of oxygen.

The results obtained in the case of a separate legal entity apply to the equipment used to obtain the data in Examples 1.2 and 6. essentially the same methane conversion rate as at showed the upper level.

Engraving (no changes to the content) FIG.1 [=:１也熾-I faced and tΣ1 ちょうう;さ」）1 1Bump Summer 8FIG, 3 FIG.4 Procedural amendment (formality) July 4, 1985 Director General of the Patent Office Shizuku Shiga Incident display--111 reference PCT/US 84100949 person who makes corrections Relationship to the incident: Patent applicant 〒103 Address: Oil and Fat Industry Hall, 3-13-11 Nihonbashi, Chuo-ku, Tokyo Telephone: 273-64 No. 36 Date of notification of amendment order: June 11, 1985 Target of amendment Translation of the written application for the name of the invention pursuant to the provisions of Article 184-5, Paragraph 1 of the Patent Act ( 1. Name of invention column) Translation of the first page of the specification One translation of the drawing Address certificate and translation: 1 copy each Contents of the amendment as shown in the attached sheet Engraving of the translation of the drawing (no changes to the content) Specification The present invention relates to the production of higher hydrocarbons from methane.

More specifically, the present invention provides for the addition of a diluting group initiator separately to the reaction zone. Methane and methane-containing gases containing C7 and benzene were added in the presence of a small amount of acid residue. It relates to high temperature conversion to higher hydrocarbons.

Background of disclosure For more than 50 years, scientists have been trying to make useful liquid hydrocarbon products from natural gas. Attempts have been made to find efficient ways to create 10 of 1931 In March, the U.S. Bureau of Mines announced that Smith's ``production of motor fuel from natural gas'' The report entitled Revo-) AR, I.

3143 was announced. In this report, Mr. Smith and his collaborators Optimizing the production of benzene and C2 unsaturates from methane by high temperature pyrolysis of It summarizes the results of extensive research devoted to this topic. In these methods, about j, Furnace temperatures in the range 150-1,240°C were used, and under these optimal conditions They have a feedstock conversion rate of 29% and a weight of 18.5% of the feedstock converted. % benzene production selectivity was obtained. Other raw materials produced by the Mr. Smith surname method The products were ethylene, acetylene, organic material, and tar and carbonaceous solids.

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Claims (1)

[Claims] 1 Liquid hydrocarbons and 2 or more carbon atoms in the molecule from the methane-containing gas feedstock In a method for producing gaseous hydrocarbons having a methane in the presence of oxygen at a temperature of at least about 1,300° C. for a sufficient period of time to react with the gaseous and liquid hydrocarbon products to produce the gaseous and liquid hydrocarbon products. , in which case the oxygen is added in the reaction zone to zero of the methane content in the feedstock. ．． present in amounts as high as 5% by volume, and the oxygen and feedstock are separate from the reaction zone. A manufacturing method characterized by being introduced into individual pieces. 2. Oxygen and feedstocks are not premixed before their introduction into the reaction zone. The method of claim 1 further characterized by: 3 The hydrocarbon products are removed from the reaction temperature to prevent decomposition and disintegration of the products. Claim 1 or 2 further characterized in that the temperature is rapidly cooled to an even lower temperature. Method described. 4. Claim No. 4 further characterized in that the reaction time is in the range of about [L1 to 1 second]. The method according to any one of items 1 to 5. 5. Further characterized in that the reaction temperature is in the range of about 1.300 to 1.800 K. A method according to any one of claims 1 to 4. &　The claims further characterized in that the quenching temperature is no higher than about 1,0OOK. The method according to any one of paragraphs 3 to 5. 1. Claims further characterized in that the quenching rate is at least about 10' to 7 seconds. The method according to any one of items 3 to 6. & The reaction products so formed are prevented from decomposing and disintegrating. be rapidly cooled to a temperature in the range of about 500 to 1,0 OOK from the reaction temperature. 8. A method according to any one of claims 3 to 7, further characterized by: 9 Oxygen in the reaction does not exceed about 10% by volume of the methane content in the feedstock According to any one of claims 1 to 8, further characterized in that it exists in the world. the method of. 1α Oxygen in the reaction zone is at least about 0.7 volume of the methane content in the feedstock 10. Any one of claims 1 to 9 further characterized in that the compound is present in an amount of %. The method described in. 11. Further characterized in that the C2 gaseous hydrocarbon formed comprises acetylene. A method according to any one of claims 1 to 10. 12. Claim No. 1 further characterized in that the liquid hydrocarbon product comprises benzene. Described in any one of paragraphs 1 to 1122 How to put it on. 1 & further characterized in that negligible tar-like or carbonaceous products are produced. 13. A method according to any one of claims 1 to 12. 14, in particular from a methane-containing gas feedstock substantially as described with respect to the Examples. Production method of gaseous and liquid hydrocarbons0