CN1359884A

CN1359884A - Process for producing other organics from hydrocarbon

Info

Publication number: CN1359884A
Application number: CN 01124020
Authority: CN
Inventors: 肖钢
Original assignee: Individual
Current assignee: Individual
Priority date: 2000-12-19
Filing date: 2001-08-07
Publication date: 2002-07-24
Anticipated expiration: 2021-08-07
Also published as: CN1314635C

Abstract

A process for preparing esters, alcohols, esters, phenols, or olefines, such as methanol, dimethylether and dimethyl sulfate, from hydrocarbons is characterized by that the hydrocarbon can be oxidized to become oxygen-containing esters or others, its initial reaction takes place in acidic medium, said oxidizing reaction takes place in the presence of oxidant and catalyst, the methyl sulfuric acid is distilled to become dimethyl sulfate, and the alkylsulfuric acid and ester derivative are hydrolyzed to become relative alcohol and ether. Its advantages are high selectivity and conversion, high yield, and no toxicity and low cost of catalyst.

Description

Process for producing other organic compounds from hydrocarbons

The invention relates to a process for generating other organic matters from hydrocarbon in the field of chemical engineering.

Currently, methane is an abundant and important natural resource as a major component of natural gas. However, due to the limitations of both factors, it is today mainly used as a fuel and cannot be used on a large scale as a chemical feedstock. First, the transporting armorAlkane gas or liquefied natural gas is not economical and therefore must be converted to a readily transportable feedstock or product. Second, the methane molecule is very stable and it is very difficult to convert it directly into a usable chemical feedstock. More than 90% of the methane produced today is consumed as fuel. Also, since the transmission of natural gas over long distances is expensive, it is believed that natural gas, i.e., methane, should be converted into a liquid fuel that is easier to transport. Methane has two main uses as a feedstock in the chemical industry, namely for the production of methanol and synthetic ammonia. Before methanol or ammonia synthesis can be carried out, methane must first be converted into synthesis gas (H)₂+ CO). It is evident that this method makes the synthesis gas production process the primary step in methane reforming. Today, the main production process for synthesis gas is steam reforming of methane. The reaction equation can be expressed as

A considerable disadvantage of this steam reforming of methane is that it is an endothermic reaction. This reaction requires a large energy input to complete. In addition to the syngas process, some literature describes some other processes for converting methane to other high molecular weight species. Several U.S. patents have been filed by Mobil Oil Corporation which disclose the production of methyl intermediates by non-catalytic reaction with methane using sulfur or some sulfur-containing compound as a reactant. This methyl intermediate can be further converted to high molecular weight hydrocarbons. In U.S. patent No.4,543,434, zhang describes a process comprising the following steps:

here, "[ CH]₂]"is a hydrocarbon having at least two carbon atoms.

Korean et al in another Mobil patent (u.s.pat)ent No.4,864,073)Said a process for converting methane into CH in the presence of ultraviolet light₃Methods for SH. The reaction process is as follows:

( )

the selectivity of the first reaction was around 81%. However, the conversion is very low.

Another patent similar to Zhang is U.S. Pat. No.4,864,074 issued to Korean et al. As in Zhang, methane and sulfur are contacted, however, the process conditions are changed, and thus CS is produced₂Or CH₃And (5) SH. These sulfur-containing compounds continue to be converted into hydrocarbons having two or more carbon atoms.

Other methods capable of converting stable methane substitutes to heavier hydrocarbons are also known. U.S. patent No.4,804,797 issued to milait et al describes a methane chlorination process. A similar process is described in U.S. Pat. No.3,979,470 to non-Habo et al (patent requires C)₃Hydrocarbons are required as the initial reactant).

Euler, in U.S. patent No.4,523,040, describes a process for the vapor phase methane halogenation to produce methyl halides with solid strong acid catalysts or attached group VIII metals, particularly platinum and palladium.

A Methane conversion process using Palladium as a catalyst is described in an article by Sensen et al (Homogeneous Palladium (II) mediated oxidation of Methane ", Platinum Metals Review, (1991), Vol 35, No.3, pp.126-132). However, the reaction rate was very low (4.2X 10)^-9Sec.) of the catalyst. The conversion and selectivity of methane is not described herein.

Other methane conversion processes have also been investigated. Of importance are the direct oxidation of methane to methanol, formaldehyde or the dimerization products ethane and ethylene. None of the above reactions has realized the prospect of large-scale industrial applications due to their very limited catalytic activity, short catalytic life, or very low product selectivity.

Pirana et al in a Patent (International Patent Application No. wo92/14738) disclose a homogeneous system for the catalytic oxidation of methane and the formation of methanol from methyl sulfate. This homogeneous reaction takes place in concentrated sulfuric acid and uses palladium, thallium, platinum, gold and mercury as catalysts. Among them, divalent mercury is the most preferable catalyst. They are said to have achieved a 43% yield. The conversion of methane and the selectivity to methylsulfate were 50% and 85%, respectively (Piraniana et al, J.Sci., volume 259, p.340, 1993). The same group of researchers have recently published a paper using platinum complexes as catalysts (Piraniann et al, J.Sci., volume 280, p.560, 1998), which states that the yield of methane to methanol derivatives has reached 72%. This reaction process uses sulfuric acid as the reaction medium. The above catalytic process has problems in that most of the catalysts used therein are expensive in cost, and the mercury-containing catalysts therein are toxic and harmful to the environment. Therefore, the development of a process for producing other organic compounds from hydrocarbons has been a new problem to be solved urgently at home and abroad.

The invention aims to provide a process for generating other organic matters from hydrocarbon, which has scientific and novel conception, practical process method, moderate manufacturing cost, cheap and non-toxic catalyst, high methanol yield under milder reaction conditions and can be used for producing various products such as methanol, dimethyl ether, dimethyl sulfate and the like.

The purpose of the invention is realized as follows: the production of esters, alcohols, ethers, phenols, olefins and other organic compounds from hydrocarbons is carried out by an initial chemical reaction of the hydrocarbon in an acidic medium (e.g. sulfuric acid) and oxidation in the presence of an oxidizing agent and a catalyst; the catalyst for the reaction is mainly simple substance or contains any compound stateBromine, tungsten and lead species of (a); when the hydrocarbon is alkane and the acidic medium is sulfuric acid, the main product of the reaction is alkyl sulfuric acid; when the hydrocarbon is methane, the main product of the reaction is methylsulfate (CH)₃OSO₃H) (ii) a The reaction product or its derivatives can be isolated here as the final product; methyl sulfuric acid can be converted into dimethyl sulfate during distillation separation; the separated sulfuric acid can be used as a reaction medium for repeated use; the alkyl sulfuric acid and the ester derivative can be further hydrolyzed to generate corresponding alcohol or ether; for example, when methane is the initial hydrocarbon, the corresponding product produced is methanol or (and) dimethyl ether; taking methane as an example, the reaction process is as follows:

first step of

Second step of

Or

(CH₃O)₂SO₂+2H₂O→2CH₃OH+H₂SO₄

(acid condition)

The third step

Total reaction CH₄+1/2O₂→CH₃OH

Sulfuric acid plays several roles in the reaction process, firstly, it is a strong acid that has a super-strong acid effect on the catalytic system; secondly, the sulfuric acid is reduced to sulfur dioxide as a transfer medium of oxygen; third, it is also a reactant that binds methane; at the same time, it is a methane and reactionA solvent for the product; the catalyst is selected from the group consisting of: bromine, bromine-containing compounds, tungsten-containing compounds, lead-containing compounds; the hydrocarbon is selected from the group consisting of methane, ethane, propane, butane and other alkanes; the hydrocarbon is selected from the group consisting of alkenes, alkynes, and all other aromatic compounds; the oxidizing agent is selected from the group consisting of halogen-containing substances (F)₂、Cl₂、Br₂、I₂)、HNO₃Perchloricacid, hypochloric acids, peroxides (H)₂O₂、CH₃CO₃H、K₂S₂O₈)、O₂、O₃、SO₃、NO₂、H₂SO₄And cyanogen; the acidic medium is selected from the group consisting of HNO₃、H₂SO₄、CF₃CO₂H、CF₃SO₃H、H₃PO₄HPA's (heteropolyacids), B (OH)₃Anhydrides of the above acids (e.g. H)₄P₂O₇And H₂S₂O₇) And mixtures of two or more of the foregoing acids or acids and anhydrides. The oxygen-containing ester or the derivative thereof contained in the reaction product can be hydrolyzed to generate alcohols and ethers or be used for generating other compounds; the produced alcohols and ethers can be further dehydrated to produce olefins; the hydrocarbon is methane and the product is methyl sulfuric acid (which can be further converted to methanol, dimethyl ether and other compounds); in the catalytic system, the active reaction medium is relatively concentrated sulfuric acid, or sulfuric acid containing 0-65% by weight of sulfur trioxide (or the solubility limit of sulfur trioxide in sulfuric acid), or pure sulfur trioxide; in the catalytic system, the catalyst is a substance containing bromine or any compound of bromine; in the catalytic system, the catalyst is a substance containing tungsten or any compound of tungsten; in the catalytic system, the catalyst is a substance containing lead or any compound of lead; in the catalytic system, the generated methyl sulfuric acid is distilled and separated into dimethyl sulfate, and the separated sulfuric acid is used as a reaction medium for repeated use; catalytic converterIn the chemical system, the separated dimethyl sulfate is hydrolyzed to generate methanol; sulfuric acid separated from the catalytic systemDimethyl ether is generated by hydrolysis; in the catalytic system, the separated dimethyl sulfate is hydrolyzed to generate methanol and dimethyl ether; when the hydrocarbon is ethane, ethanol or ethylene glycol can be prepared; when the hydrocarbon is benzene, phenol can be prepared. The gist of the invention resides in the process of generating other organic substances from hydrocarbons.

Compared with the prior art, the process for generating other organic matters from hydrocarbon has the advantages of scientific and novel conception, practical process method, moderate manufacturing cost, cheap and nontoxic catalyst, high methanol yield under milder reaction conditions, and capability of producing various products such as methanol, dimethyl ether, dimethyl sulfate and the like, and can be widely applied to the field of chemical industry.

The examples of the invention are as follows:

the following examples describe batch processes, and methane is used as an example to illustrate the alkyl esterification process.

1. 80 ml of oleum and 100 mmol of bromine (Br)₂) Was placed in a 200 ml pressure reactor. When the temperature of the reactor was stabilized at 180 ℃, 40 atmospheres of methane was passed into the reactor. After the temperature and the pressure are stabilized, the magnetic stirrer is started to stir the reactants, and meanwhile, the pressure in the reactor is monitored through the pressure sensor. When the pressure in the reactor reached equilibrium (the reaction reached equilibrium), the stirring was stopped and the reactor was water-cooled to room temperature. The gas in the reactor was collected and analyzed by gas chromatography. The liquid in the reactor was sampled for hydrolysis and then analyzed for methanol content by liquid chromatography. The calculation processing of the results of the gas chromatograph and the liquid chromatograph shows that the yield of the methanol in the reaction process is 90 percent.

2. To illustrate that other bromine-containing compounds also have catalytic effects, 100 millimoles of potassium bromate (KBrO)₃) Was used to repeat the experiment described in experiment 1 and gave essentially the same methanol yield as experiment 1.

3. 100 millimoles of tungsten trioxide (WO)₃) Was used as a catalyst to repeat the experiment described in 1 and gave essentially the same methanol yield as experiment 1.

4. To illustrate that other tungsten-containing compounds also have catalytic effects, 100 mmol Na₂WO₄Was used to repeat the experiment described in experiment 1 and gave essentially the same methanol yield as experiment 1.

5. 100 millimoles of lead dioxide (PbO)₂) Was used to repeat the experiment described in experiment 1 and gave essentially the same methanol yield as experiment 1.

Claims

1. A process for producing other organic materials from hydrocarbons, characterized by: the production of esters, alcohols, ethers, phenols, olefins and other organic compounds from hydrocarbons is carried out by an initial chemical reaction of the hydrocarbon in an acidic medium (e.g. sulfuric acid) and oxidation in the presence of an oxidizing agent and a catalyst; the catalyst for the reaction is mainly a simple substance or a substance containing bromine, tungsten and lead in any combination state; when the hydrocarbon is alkane and the acidic medium is sulfuric acid, the main product of the reaction is alkyl sulfuric acid; when the hydrocarbon is methane, the main product of the reaction is methylsulfate (CH)₃OSO₃H) (ii) a And the reaction product or its derivative can be isolated here as the final product. Methyl sulfuric acid can be converted into dimethyl sulfate during distillation separation; the separated sulfuric acid can be used as a reaction medium for repeated use; the alkyl sulfuric acid and the ester derivative can be further hydrolyzed to generate corresponding alcohol or ether; for example, when methane is the initial hydrocarbon, the corresponding product produced is methanol or (and) dimethyl ether; taking methane as an example, the reaction process is as follows:

first step of

Second step of

Or

(acid condition)

The third step

General reaction

Sulfuric acid plays several roles in the reaction process, firstly, it is a strong acid that has a super-strong acid effect on the catalytic system; secondly, the sulfuric acid is reduced to sulfur dioxide as a transfer medium of oxygen; third, it is also a reactant that binds methane. At the same time, it is a solvent for methane and reaction products.

2. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: said catalyst is selected from the group consisting of: bromine, bromine-containing compounds, tungsten-containing compounds, lead-containing compounds.

3. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: the hydrocarbon is selected from the group consisting of methane, ethane, propane, butane and other alkanes.

4. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: the hydrocarbon is selected from the group consisting of alkenes, alkynes, and all other aromatic compounds.

5. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: the oxidizing agent is selected from the group consisting of halogen-containing substances (F)₂、Cl₂、Br₂、I₂)、HNO₃Perchloric acid, hypochloric acids, peroxides (H)₂O₂、CH₃CO₃H、K₂S₂O₈)、O₂、O₃、SO₃、NO₂、H₂SO₄And cyanogen.

6. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: the acidic medium is selected from the group consisting of HNO₃、H₂SO₄、SO₃、CF₃CO₂H、CF₃SO₃H、H₃PO₄HPA's (heteropolyacids), B (OH)₃Anhydrides of the above acids (e.g. H)₄P₂O₇And H₂S₂O₇) And mixtures of two or more of the foregoing acids or acids and anhydrides.

7. A process according to claims 1 and 3 for the production of other organic materials from hydrocarbons, characterised in that: the oxygen-containing ester or its derivative contained in the resultant of said reaction can be hydrolyzed to produce alcohols, ethers or other compounds.

8. A process according to claims 1 and 7 for the production of other organic materials from hydrocarbons, characterised in that: the alcohols and ethers produced may be further dehydrated to produce olefins.

9. A process according to claims 1 and 3 for the production of other organic materials from hydrocarbons, characterised in that: the hydrocarbon is methane and the product is methyl sulfuric acid (which can be further converted to methanol, dimethyl ether and other compounds).

10. A process according to claims 1 and 3 for the production of other organic materials from hydrocarbons, characterised in that: in the catalytic system, the active reaction medium is relatively concentrated sulfuric acid, or sulfuric acid containing 0 to 65% by weight of sulfur trioxide (or the solubility limit of sulfur trioxide in sulfuric acid), or pure sulfur trioxide.

11. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: in the catalytic system, the catalyst is a substance containing bromine or any compound of bromine.

12. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: in said catalytic system, the catalyst is a substance containing tungsten or any compound of tungsten.

13. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: in said catalytic system, the catalyst is a substance containing lead or any compound of lead.

14. A process according to claims 1 and 9 for the production of other organic materials from hydrocarbons, characterised in that: in the catalytic system, the generated methyl sulfuric acid is distilled and separated into dimethyl sulfate, and the separated sulfuric acid is used as a reaction medium for reuse.

15. A process according to claims 1 and 14 for the production of other organic materials from hydrocarbons, characterised in that: in the catalytic system, the separated dimethyl sulfate is hydrolyzed to generate methanol.

16. A process according to claims 1 and 14 for the production of other organic materials from hydrocarbons, characterised in that: in the catalytic system, the separated dimethyl sulfate is hydrolyzed to generate dimethyl ether.

17. A process according to claims 1 and 14 for the production of other organic materials from hydrocarbons, characterised in that: in the catalytic system, the separated dimethyl sulfate is hydrolyzed to generate methanol and dimethyl ether.

18. A process according to claims 1 and 3 for the production of other organic materials from hydrocarbons, characterised in that: when the hydrocarbon is ethane, ethanol or glycol can be prepared.

19. A process according to claim 1 for the production of other organic materials from hydrocarbons, wherein: when the hydrocarbon is benzene, phenol can be prepared.