JPS61500731A - Method for producing hydrocarbons from hetero-substituted alkanes - 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] Process for producing hydrocarbons from hetero-substituted alkanes The present invention provides a method for producing hydrocarbons from hetero-substituted alkanes. The present invention relates to a method for producing hydrocarbons from carbon.

Recent predictions of a long-term shortage of petroleum, with regard to the production of chemicals and fuels from other feedstocks. Research is stimulated.

In particular, coal and natural gas, both of which have large reserves, are conventionally referred to as syngas. can be easily converted into a gas mixture of carbon monoxide and hydrogen using established technology. , is being investigated to be sequentially converted to methanol. methanol is acetic acid An effective intermediate book for the production of valuable chemical products such as ethanol, esters, acetic anhydride, etc. Yes, and recently Ganlin mixed ingredients and US Patent No. 4138422 (Mobil) As shown in the figure, the liquid state due to the change of time on the synthetic crystalline aluminosilicate catalyst is methanol as a feedstock for the production of hydrocarbons) 11! ! intended for use ing.

U.S. Patent No. 3,894,107 (Mobil) has the formula R-X (where X is halo r 7. Aliphatic organic compound represented by at least one of oxygen, sulfur, and nitrogen) The material has a silica/alumina ratio of at least about 12 and a constrai nt　ndex) is about 1 to 12, in contact with a crystalline aluminosilicate. The aliphatic organic compound has more carbon atoms than the organic compound reactant and Organic compound reaction woodworking with a high carbon/heteroatom ratio and the highest of organic compound reactants. From a mixture of compounds, including hydrocarbon compounds with long carbon chains A method for converting the product into the following products is described. In addition, zeolite Hydrogen form or cation-exchanged or impregnated atom. It also works with ammonia or metal cation complement (complemθnt); the latter It is stated that metal cations from groups ① to TM of the periodic table may be used. The fixed cation ion-exchanged zeolites are desirable for the conversion of all of the reactants included in 2R-X. However, it is not recognized that any particular cation-exchange No conversion zeolites have been described as desirable for the conversion of general grade R-X compounds. stomach. The example only describes the use of a hydrogen-type zeolite catalyst, and the example 2 4 and 26 are directed to alkanol conversion, and the remaining two columns are methyl mercazo. It is aimed at replacing tan and tri-n-butylamine. For alkanol conversion The majority of these examples involved the use of methanol as a feedstock. is directed towards.

US Patent No. 3894104 Niha, (R)Il-X type (where R is 1 carbon number) It is a lower carbonized leaf part, and X is oxygen, hydroxyl, sulfur, nitrogen, halogen, and nitrogen. A hetero moiety selected from the group consisting of anides, where n corresponds to the valence of X a silica/alumina ratio of at least about 1. 2, a crystalline aluminosilicate zeolite catalyst having a compression index of 1 to 12; At a high temperature of about 500 to about 7 eO″E′ and a space velocity of about 0.1 to 50 LH8V , to convert it into another compound with a higher R/X ratio than the raw material by contacting it. process, i.e. producing a product which is a normally liquid hydrocarbon containing a large amount of aromatics, and I’p+na, IrblII[a lrV&, $1 gold of the periodic table Utilizing the zeolite modified by mixing it with at least one of the genus as a catalyst. This paper describes an improvement method consisting of: Typical feed materials are column 5, lines 63-3 Line 8 states that alcohol should be replaced with methanol, ether, especially dimethyl ether. esters, ketones especially acetone, and analogues and congeners such as mercaptans and amines. substances are referred to as mixtures of each and/or mixtures with other substances. specific Metals are mixed into the catalyst to increase the aromatic content of the product. Total of 25 The example concerns the conversion of methanol.

The cost of converting methane, the main component of natural gas, into hydrocarbons with a boiling point range of VC. An alternative method is to convert methane to monohalomethane, which is then catalytically converted to hydrocarbons. It is to exchange. This process is more attractive than the methanol process, and why? For example, methane is first converted to synthesis gas to produce methanol feedstock. Compared to conventional processes, this process omits one step and allows methane to be directly and highly selectively monitored. This is because it is converted to Nono Lomethane. In addition, by-products of monohalomethane conversion and The hydrogen halide produced can be recycled into the mono-romethane production process. However, the by-product of the methanol conversion process cannot be used. Generally, methanol, The chemistry of conversion of alcohols is quite different compared to monohalomethanes; For example, methanol is converted to dimethyl ether at low temperatures; This is not possible with the horn/Rometan. Other important differences include methanol conversion In the case of , water is produced as a by-product, but in the case of conversion to monohalomethane, hydrogen halide is produced as a by-product. This), hydrogen rhodide (, engineering), crystalline aluminosilicate enzyme is released from the second structure. Aluminum (dealuminate) causes skeletal collapse and reduces catalytic activity. It is known that this is a reversible loss. Dealumination is easier than in the presence of water. The problem is more serious in the presence of hydrogen hydride. Therefore, derived from the prior art of methanol conversion, The conclusions drawn cannot necessarily be applied to Monono Rometa.

Japanese Patent Publication No. J55073-619 describes the conversion of methane to methyl chloride. It is taught that hydrocarbons with a minimum carbon number of 2 can be produced by dehydrochlorination using a zeolite catalyst. It is shown. The zeolite used is 5io2. A12o3 and alkali metals is a silicate mineral composed of alkaline earth metals.

Using cation-exchanged synthetic crystalline aluminosilicate catalysts, monohalogen Methane is efficiently converted to hydrocarbons in the gasoline boiling range, and over a temperature range consisting of: Desirable selectivity towards aliphatic hydrocarbons, especially towards alkanes and alkenes We found that sex is increased. Furthermore, the activity of the catalyst depends on the zeolite used. It depends on the nature of the ion and the nature of the cation. Even more surprisingly, the activity of the catalyst is We have discovered that the catalyst is effective for a considerable period of time and that at least a portion of the catalyst is renewable. did.

Therefore, the present invention converts monohalomethane into hydrocarbons having at least two carbon atoms. The present invention provides a method for converting silica and alkali into products containing the molar ratio of mina is at least 12:1 and is capable of forming hydrogen, copper or amphoteric oxides; Synthetic crystalline aluminosilicate zeolites containing cations of any of the metals and mono-lomethane at elevated temperature, the cation being exchanged. and/or by deposition, as described in European Patent No. As explained and claimed in 7049B, when the cation is hydrogen, zeola It is theta-1.

For monohalomethanes, the 710 site is preferably chloro- or bromo. chloro- is preferred. Monohalometa/mixture and/or seven horned lome Mixtures of ethane with other monohalomethanes such as mono/10ethane can also be used. Mo Nohalomethane can be used in its pure form or as a polyhalodanized analogue. substances or inert diluents, nitrogen, hydrogen, oxygen, air, carbon dioxide or hydrocarbons. used together. Concerning mixtures of borino-rhodanated methane and monohalomethane , the allowable amount of polyheronated methane in the mixture, the degree of halo substitution, the zeolite depends on the nature of the cation and the nature of the cation. For example, monochloromethane as feed material and dichloromethane using tin-exchanged zsM-5 type crystalline alumina as a catalyst. When using silicate zeolites, the maximum allowable amount of dichloromethane in the feed is , approximately 40 capacitances. Of course, the proportion of dihalomethane is much lower than the critical amount. It is preferable to treat it with Monohalomethane is preferably a halogenated or Ethane, obtained by oxyhalogenation or more preferably in the form of natural gas. and/or obtained from a mixture of propane and methane. Selective monohalomethane A preferred method for producing is described in our co-pending UK application publication no. (BP Case No. 5550) and jointly filed European Application Publication No. 01177 51 (BP Case No. 5568), the main contents of which are quoted here. Use and incorporate.

Synthetic crystalline aluminosilicate zeolite has a molar ratio of silica and alumina of at least 12:1, preferably from 15:1 to 150:1, and more Suitable synthetic crystalline aluminosilicate zeolites are disclosed in US Pat. and ZSM-4 described in No. 1321460, and ZSM-4 described in OSP No. 3709979. Shiri ZSM-11, ZSM-5/ZSM described in σ5PIr4229422 -11, aspK4016245 zsM-35, oB-A-a! 1 It contains ZsM-34 and Zeolite Nu-1 described in No. 559367. good A newly synthesized crystalline aluminosilicate was submitted to the Structure Committee of the International Zeolite Association. Zeolite structure type by W. H. Meyertori and H. Ornun published by There is one called MFFJ olite and theta-1 in the formula diagram. Features that can be used Fixed M? Any zeolite and its manufacturing method are described, for example, by USWF [370288 No. 6, No. 3709979, No. 4205053, No. 4166099, No. 41 39600 and 4151189, UK patents 1365318 and 1567 No. 948, EP-A-No. 2899 and @2900, which MF Anyfjl ('5th A) Ha, FJ, tha, EP-A-IE! IO No. 911, trspl! No. 4199556,! -oB-A-g2018232 It is synthesized from Dell without the use of an organic base as described in .

A crystalline aluminosilicate called Theta-1 is expressed as the molar ratio of oxides. It has the following composition, 0.9±[1,2M2/a o:u2o5: :ts 02th : 7H2OM is at least one cation with valence n, and X is At least 12, y/x is 0 to 25, and the fired hydrogen type aluminosilicate has the X-ray diffraction pattern shown in Table A.

8.15fO,511,5-1(L2 50tO10010,16=t=0.5 829-9.14 5t02512.77±0.5 7.20-6.66 1 0t02016.36e0.5 5.58-5.25 5t01519.42± 0.5 4.6B-4,455t01520.35±0.5 4.47-4.2 6 50 to 10024.22±0.5 3.75-3.60 50tO1 0024,65±0.5 3.6B-3,5450to 9025.75±0. 5 3.52-3.39 15 to 4555.65±0.5 2.55-2 ．． 48 15 to 402 theta = 361 scan Aluminosilicate creates a mixture of all reactants and transforms the mixture into a homogeneous gel. Maintain at a temperature of 0-100°C, preferably 20-60°C, until formed, 70°C ℃ or higher, preferably 100-220℃ for at least 2 hours, preferably The entire reaction was carried out by simply mixing while the mixture crystallized over a period of 6 to 240 hours. It is manufactured as follows. For more information on crystalline aluminosilicates and their production, please refer to European Patent No. 0057049, which is incorporated herein by reference. and transfer.

In addition to associating with the crystalline structure, the aforementioned crystalline aluminosilicate also Contains thione, such as alkali metal and/or alkaline earth metal cations, organic nitrogen cations, or ammonium cations, and their pores or It also contains organic bases or acids deposited on the surface. Producing active catalysts by the method of the invention In order to prepare some of the exchangeable cations of crystalline aluminosilicate or all require replacement with other cations and/or surface deposited cations.

In zeolites other than Theta-1, activated cations form copper or amphoteric oxides. An amphoteric oxide is a possible metal cation, and simply expressed, it has the characteristics of an acid and a base. Note: Regarded as an oxide. Metals capable of forming amphoteric oxides are, for example, Liumium, titanium, zirconium, hafnium, iron, cobalt, rhodium, silver , gold, zinc, aluminum, gallium, indium, silicon, derma, Discussed including tin, lead, and turanium. Of the metals mentioned above, zinc and galaxies It is preferable that aluminum and silver be heated at a low temperature, preferably 200 to 260°C. Theta-1 is as mentioned above Activated by at least one of the cations, but activated theta-1 by hydrogen ions It is preferable to do so. The hydrogen type of Theta-1 is more active than the hydrogen type of MF ezeolite. We discovered that it is a powerful catalyst.

Cation exchange can be performed using conventional ion-exchange techniques. cation The deposition can be done by injection or precipitation or other techniques. Deposition is done with appropriate compounding. This is done by injecting a solution of, for example, a metal salt, to transfer exchangeable cations to other cations. It is completed by exchanging it with On. When using cation exchange, all Initially, it is preferred to substantially exchange the exchangeable cations. use sedimentation the amount of metal deposited is calculated as metal based on the total weight of the catalyst. , preferably up to 25% by weight, preferably from 0.1 to 15% by weight.

After and optionally prior to cation substitution, the crystalline aluminosilicate is calcined. It is preferable to Firing in air, oxygen, inert gas, or 7? C-cum or those At temperatures ranging from 200 to 600°C, or above, under a combination of airflow. , by heating for 0.5 hours or more.

The method of converting monohaloalkanes to hydrocarbons is carried out at high temperatures of 80 to 600°C. Ru. Although high pressure or low pressure may be used as desired, the pressure is usually atmospheric pressure.

80-600°CI7) In the a degree range, below 330°C, aromatic carbonization Hydrogen is not produced in major proportions.

Below 330°C, monohalomethane is a hydrocarbon containing mainly aliphatic hydrocarbons. Surprisingly, a substantial portion of the bi-aliphatic hydrocarbons is converted into chemical In-alkane, a highly preferred component as feedstock and Ganlin mixed additive was discovered to be an inalkene. In the production of aliphatic hydrocarbons, 2 00 is preferably produced in the temperature range of 6,200 to 260'C, and even higher temperatures. Note that at 327°C, methanol is converted to dimethyl ether. You should keep an eye on it.

This item f: can be operated in batch mode, but it is preferable to operate it continuously. continuous In the case of operation, it is defined as the volume of reaction gas per volume of catalyst per hour at room temperature and pressure. The space velocity per hour (GW SV) is preferably 1 to 1 ooooo capacity. volume/volume/time. Methane is optionally mixed with ethane and/or propane. The mixture is supplied to the first zone, and halodanized and/or oxybadened to 80% Monohalomethane is selectively produced by the above methane supply, and monohalomethane and Monohaloethane and/or monohalopropane are separated and used in the method of the invention passed as a feedstock, after which the hydrocarbon product is a by-product of halodanized water. separated from the element. Hydrogen halide can be reused for oxyhalogenation or acid The by-product of this process, halide, is reused for halodane conversion.

The catalyst in the process of the invention is used in fixed bed or fluidized bed form.

The method of the invention is illustrated in more detail by the following examples.

In the examples, the expressions ``in-content'' and aliphatic content are used. In-containing The amount is the in-alkanes present as part of the total C4-11 aliphatic hydrocarbon content. / Indicates the minimum molar amount (%) of alkene. The aliphatic content is similarly , total 03 to 14 aliphatic and aromatic hydrocarbons present in the composition It concerns the smallest elementary quantity. Asahi/Ar ratio is c-nee aliphatic and ci-aromatic It concerns the ratio of hydrocarbon selectivity. These reveal variations in the product range. This is an expression defined for accurate display.

Implementation group] 1 to 4 A second stage of synthesized crystalline aluminosilicate with a silica and alumina molar ratio of 41:1. The cation-exchange type reactor specified in Table 1, which is a monochrome ZSM-5, was Lolomethane was fed continuously. The reactor is heated externally using an electric furnace. The range was maintained at a specified temperature. Table 1 shows GH8V per hour at normal temperature and pressure. show. The product stream was analyzed by on-line chromatography.

The composition of the product stream, excluding unreacted monohalomethane and hydrogen chloride, is summarized in the experimental details. Both are shown in Table 1.

According to Table 1, using metal cation-exchanged 28M-5 zeolite, the experimental conditions Under these conditions, aromatic hydrocarbons cannot be obtained.

The aliphatic hydrocarbon product had a high in-content.

Comparative test A Using the hydrogen type of ZSM-5 zeolite used in Examples 1 to 4, the The methods of Examples 1-4 were repeated using the conditions.

This method is not an example of the present invention because it used the hydrogen form of zeolite. . The hydrogen form of zeolite has been found to give only low conversions under the experimental conditions. Proven.

Comparative test B Using the hydrogen form of ZSM-5 reverse-exchanged with sodium cations (15%), and At the liquid hourly space velocity compared to the monochloromethane location, the feed material Examples 1 to 4 were repeated using methanol as the solvent. Main generation book (9 1% conversion) was dimethyl ether.

This) uses methanol as the feed material and does not use monohalomethane. In the examples related to the present invention, Ao is a monohaloalkane and an alkanol. This was done with the aim of emphasizing the differences in the chemical relationships between the two.

Under the conditions of use, methanol mainly contains its condensation adduct, dimethyl ether, and a small amount. 02-03 hydrocarbons were formed, but monochloromethane was mainly composed of C, -C11 fatty acids. Aliphatic hydrocarbons were formed.

Using the ZSM-5 zeolite used in Examples 1 to 4, the conditions and specifications specified in Table 2 were The method of Examples 1-4 was repeated using the on-exchange format. Unreacted monochloromethane The composition of the product stream, excluding tungsten and hydrogen chloride, is shown in Table 2 along with a summary of experimental details.

From Table 1, it can be seen that high temperature increases the conversion rate of monochloromethane and at the same time, a high proportion of in- It can be seen that high aliphatic hydrocarbon products containing hydrocarbons can be produced. Examples 6 and 1 0, the ferrite/Ar ratios are 6.4 and 7.6, respectively, indicating a high aliphatic content in the product stream. Indicated. Feed material (327°C; Using methanol as 1h-1WH3V), hydrocarbon production was carried out under similar conditions. The conversion rate to the body is low (1%), and the majority of the product (94% conversion rate) is dimethyl ether. It was tell.

For example 5 (copper-exchanged), the monochloromethane conversion after 18 hours of flow was (to 70%).

This was confirmed using the hydrogen form of zeolite (327°0; 200h-1) and at 9 hours of flow. [after] reduction in conversion (from 89% to 24%) and stability of the catalyst of the present invention. It shows that the quality has improved. Furthermore, the activity of copper-exchanged zeolides is However, with hydrogen-exchanged zeolide, no recovery was observed. It was.

Examples 14-19 The method of Examples 1-4 was repeated with the feed composition and cations shown in Table 3. unrebelled The methyl chloride and hydrogen chloride of the reaction were removed, and the composition of the product stream was determined to approximate the details of the experiment. It is shown in Table 4 along with the main points.

Comparative test C and D The method of Examples 1-4 was repeated with the feed composition and cations shown in Table 3. unrebelled After removing the haloalkanes and hydrogen chloride, the composition of the product stream was determined along with a summary of the experimental details. It is shown in Table 4.

These compounds are not practical in accordance with the present invention, but include dichloromethane in the feed mixture. It is emphasized that high hydrocarbon conversion cannot be obtained when the amount is greater than 40% V/V. I inserted it to do so.

Implementation rows 20-24 I repeated steps 1 to 4, but the cation exchange used in 3 Instead of the modified 28M-5 zeolite, as specified in Table 5, the aforementioned European patent 5. Various types of Theta-1 zeolite produced as described in No. 57G and No. 49B. A cation-exchange type was used.

After removing unreacted monochloromethane and hydrogen chloride, the product is The composition of the stream is shown in Table 5.

For comparison, the related materials of Comparative Test A are inserted in Table 5.

Remarks: a = liquid wood time vs. space velocity b=conversion rate of rainbow methyl ether 91ch international research report ξshi〈:;::+Q5. :fi:::Q::QsaHad, Mi32p2zup4mi ? 0λτCN

Claims (10)

[Claims] 1. Monohalomethanes to products containing hydrocarbons with at least two carbon atoms A method for converting monohalomethanes into silica and alumina at elevated temperatures. metals having a molar ratio of at least 12:1 and capable of forming hydrogen, copper or amphoteric oxides; contact with a synthetic crystalline aluminosilicate zeolite containing any of the following cations. the cations by either exchange and/or deposition. and when the cation is hydrogen, the zeolite is as described in European Patent No. 5 Modification of monohalomethane characterized by being theta-1 claimed in No. 7049B Exchange method. 2. Zeolites contain cations of copper or of any metal capable of forming amphoteric oxides. The method according to claim 1, characterized in that the MFI-type zeolite containing . 3. A claim characterized in that the zeolite is sheeter 1 containing hydrogen ions. The method described in Scope 1. 4. The above claim, characterized in that the elevated temperature is in the range of 80 to 600°C. The method according to any one of the ranges 1 to 3. 5. the temperature is below about 330°C and the hydrocarbon product consists primarily of aliphatic hydrocarbons. 5. The method according to claim 4, characterized in that: 6. Claim 5, characterized in that the temperature is in the range of 200 to 330°C. How to put it on. 7. Metals that can form amphoteric oxides include beryllium, titanium, zirconium, Hafnium, iron, cobalt, rhodium, silver, gold, zinc, aluminum, gallium , indium, silicon, germanium, tin, lead, polonium, or uranium Any of claims 1, 2, 4, 5 and 6, characterized in that The method described in paragraph 1. 8. The metal is zinc, gallium or silver, and the temperature is 200-260℃ The method according to claim 7, characterized in that the method is within the range of . 9. Methane mixed with ethane and/or propane can be halogenated or Claims characterized in that monohalomethane is obtained by halogenation. The method according to any one of items 1 to 8. 10. The above claim characterized in that the monohalomethane is monochloromethane. 10. The method according to any one of items 1 to 9.