WO2005037962A1

WO2005037962A1 - Method for producing liquefied petroleum gas containing propane or butane as main component

Info

Publication number: WO2005037962A1
Application number: PCT/JP2004/015215
Authority: WO
Inventors: Kaoru Fujimoto; Kenji Asami; Sachio Asaoka; Xiaohong Li
Original assignee: Japan Gas Synthesize, Ltd.
Priority date: 2003-10-16
Filing date: 2004-10-15
Publication date: 2005-04-28
Also published as: CN1867652B; JPWO2005037962A1; CN1867652A

Abstract

A method for producing a liquefied petroleum gas containing propane or butane as a main component, which comprises preparing a synthesis gas from a carbon-containing raw material such as natural gas, and then forming the LPG gas containing propane or butane as a main component from a material gas containing the above resulting synthesis gas and carbon dioxide in the presence of a catalyst. The method allows the production of LPG with more ease with improved economy.

Description

Specification

Method for producing liquid distillery petroleum gas containing propane or butane as a main component

Technical field

[0001] The present invention relates to a method for producing a shiroi petroleum gas whose main component is propane or butane from synthesis gas. Further, the present invention relates to a method for producing a liquid petroleum gas whose main component is pulp bread or butane from a carbon-containing raw material such as natural gas.

Background art

[0002] Liquefied petroleum gas (LPG) refers to a gaseous petroleum or natural gas-based hydrocarbon that exhibits a gaseous state at normal temperature and pressure, or is simultaneously cooled to a liquid state, and its main component is propane or butane. It is. LPG, which can be stored and transported in a liquid state, is highly portable and can be supplied anywhere in a cylinder filled state unlike natural gas, which requires a pipeline for supply There is a feature. For this reason, propane-based LPG, that is, propane gas, is widely used as a fuel for domestic and commercial use. At present, propane gas is supplied to about 25 million households in Japan (more than 50% of all households). LPG is also used as a fuel for mobile objects (mainly butane gas) such as cassette stoves and disposable lighters, industrial fuels, and automotive fuels, in addition to household and commercial fuels.

[0003] Conventionally, LPG has been 1) a method of recovering wet natural gas power, 2) a method of recovering crude oil from a stabilizing (vapor pressure adjustment) process, and 3) separating and extracting products produced in a petroleum refining process and the like. It is produced by methods.

[0004] LPG, especially propane gas used as a fuel for home and business use, is expected to be expected in the future and is very useful if a new production method that can be implemented industrially can be established.

[0005] As a method for producing LPG, Patent Document 1 discloses a Cu—Zn-based, CrZn-based, Pd-based, etc. methanol synthesis catalyst, specifically, a CuO—ZnO—AlO catalyst, a PdZSiO catalyst. , Average hole

2 3 2

It consists of hydrogen and carbon monoxide in the presence of a mixed catalyst physically mixed with a zeolite having a diameter of about 10 A (lnm) or more, specifically a methanol conversion catalyst consisting of Y-type zeolite. A method is disclosed in which a synthesis gas is reacted to produce a liquid hydrocarbon gas or a hydrocarbon mixture having a composition similar thereto.

[0006] However, it is difficult to say that the content of carbon dioxide in the product obtained by the method described in Patent Document 1 is sufficiently low. When the yield of hydrocarbons is the highest at 36.0%, the yield of carbon dioxide is 33.9%. When the yield of hydrocarbon is 35.7%, the yield of carbon dioxide is 30.7%. Since carbon dioxide has a low utility value and is difficult to reuse, it is not economically preferable that a large amount of carbon dioxide is by-produced.

[0007] In the example described in Patent Document 1 described above, a synthesis gas having a HZCO molar ratio of 2Z1 is used as a raw material gas for liquefied petroleum gas (LPG) synthesis. And patent document 1

2

However, in this example, even when any of the catalyst systems was used, an amount of dioxygenated carbon equivalent to that of hydrocarbons was produced. This is for performing a CO shift reaction (CO + H 0 → CO + H), and an appropriate amount of CO

2 2 2 2

It is described that the co-production can be controlled by co-existing with. However, Patent Document 1 specifically describes CO that coexists in syngas, including its amount.

2

Not listed.

[0008] As a method for producing LPG, Non-Patent Document 1 discloses 4wt% Pd / SiO, a mixed oxide of Cu—Zn—A1 [Cu: Zn: Al = 40: 23: 37 (atomic ratio)] or

2

Hybrid catalyst consisting of Cu-based low-pressure methanol synthesis catalyst (trade name: BASF S3-85), water-steamed at 450 ° C for 1 hour, and high silica Y-type zeolite (SiO ZA1 O = 7.6)

2 2 3

A method for producing C2-C4 paraffin from a synthesis gas via a methanol and dimethyl ether with a selectivity of 69-85% using a solvent is disclosed. However, the method described in Non-Patent Document 1 does not say that the content of carbon dioxide in the obtained product is sufficiently low as in the method described in Patent Document 1 described above. , Difficult,.

[0009] As described above, in order to commercialize the process for producing LPG, the process for producing LPG, and also for the process for producing LPG for carbon-containing raw materials such as natural gas, the economic efficiency must be improved, and more specifically, LPG must be improved. It is desired to suppress the by-product of carbon dioxide in LPG synthesis.

Patent Document 1: JP-A-61-23688

Non-Patent Document 1: Selective synthesis of LPG from Synthesis Gas, Kaor u Fujimoto et al., Bull. Chem. Soc. Jpn., 58, p. 3059-3060 (1985) Disclosure of the Invention

Problems to be solved by the invention

[0010] An object of the present invention is to provide a method capable of easily and more economically producing LPG having a high concentration of propane and Z or butane from synthesis gas.

[ooii] Another object of the present invention is to provide a method for easily and economically producing LPG having a high concentration of propane and Z or butane from a carbon-containing raw material such as natural gas. It is.

Means for solving the problem

According to the present invention,

a synthesis gas production process for producing a synthesis gas from an ω carbon-containing raw material,

(ii) In the presence of a catalyst, contains the synthesis gas obtained in the synthesis gas production step and carbon dioxide, and the content of carbon dioxide is the same as that of mono-orientated carbon, di-orientated carbon and hydrogen. A liquefied petroleum gas production process for producing a liquefied petroleum gas containing propane or butane as a main component from a source gas that is 5 to 35 mol% based on the total

The present invention provides a method for producing liquid liquefied petroleum gas containing propane or butane as a main component (1-1-1 method for producing LPG).

[0013] Further, according to the present invention, the liquid-dyeing petroleum gas production process! /,hand,

The content of monoacid I匕炭oxygen in the feed gas, the total amount of carbon monoxide and carbon dioxide and hydrogen, 3 30 mol ^_0/0 above the 1-1 method of LPG production is Is provided.

According to the present invention,

(i) a synthesis gas production process of producing a synthesis gas from a carbon-containing raw material,

(ii) In the presence of a catalyst, contains the synthesis gas obtained in the synthesis gas production process and carbon dioxide, and the content of carbon dioxide is 0.2— A liquid gas production process for producing liquid gas containing propane or butane as a main component from a 1 mol raw material gas;

The present invention provides a method for producing liquid liquefied petroleum gas containing propane or butane as a main component (the method for producing LPG 1-2). [0015] Further, according to the present invention, in the production process of liquid and petroleum gas! /,hand,

The content of monoacid I匕炭oxygen in the feed gas, the total amount of carbon monoxide and carbon dioxide and hydrogen, 3 30 mol ^_0/0 above the 1-2 method of LPG production is Is provided.

Further, according to the present invention,

(ii) In the presence of the catalyst, the synthesis gas obtained in the synthesis gas production process was separated from the gas power containing lower paraffin in the separation process, and was recycled as a raw material in the lower paraffin production process in the recycling process. From a raw material gas containing a carbon dioxide-containing gas, a low-grade paraffin-containing process for producing a raffin-containing gas containing carbon dioxide, wherein the main component of the contained hydrocarbon is propane or butane;

(iii) In the lower paraffin production step, the lower paraffin-containing gas obtained is also separated from the diacid carbon-containing gas containing diacid carbon, and the liquefied petroleum gas containing propane or butane as a main component is separated. A separating step to obtain;

(iv) in the separation step, a recycling step in which part or all of the carbon dioxide-containing gas separated from the lower paraffin-containing gas is recycled as a raw material in the lower paraffin production step.

The present invention provides a method for producing liquid liquefied petroleum gas containing propane or butane as a main component (second LPG production method).

[0017] Further, according to the present invention, in the lower paraffin production step,

The above-mentioned second method for producing LPG, wherein the content of carbon dioxide in the raw material gas is 5-35 mol% with respect to the total amount of carbon monoxide, carbon dioxide and hydrogen.

[0018] Further, according to the present invention, the process for producing a liquid oil petroleum gas! /,hand,

The above-mentioned second method for producing LPG, wherein the content of carbon dioxide in the raw material gas is 0.2-1 mol per 1 mol of carbon monoxide.

[0019] Further, according to the present invention, the low-grade paraffin production process! /,hand,

The above-mentioned second method for producing LPG is provided, wherein the content of carbon monoxide in the raw material gas is 3 to 30 mol% with respect to the total amount of carbon monoxide, carbon dioxide and hydrogen. .

Further, according to the present invention, (i) In the presence of a catalyst, it contains carbon monoxide, hydrogen and carbon dioxide, and the content of carbon dioxide is 5 to 5% with respect to the total amount of carbon monoxide, carbon dioxide and hydrogen. A liquid manufacturing process for producing a liquid gas containing propane or butane as a main component from a raw material gas of 35 mol%.

A method for producing a liquid liquefied petroleum gas containing propane or butane as a main component (3-1-3 LPG production method) is provided.

[0021] Further, according to the present invention, in the production process of liquid petroleum gas,

The content of monoacid I匕炭oxygen in the feed gas, the total amount of carbon monoxide and carbon dioxide and hydrogen, 3 30 mol ^_0/0 above the 3-1 method of LPG production is Is provided.

According to the present invention,

(i) Propane or butane is converted from a raw material gas containing carbon monoxide, hydrogen, and carbon dioxide in the presence of a catalyst and having a carbon dioxide content of 0.2 to 1 mole per mole of carbon monoxide. Liquefied petroleum gas production process to produce liquefied petroleum gas as the main component

And a method for producing a liquid liquefied petroleum gas containing propane or butane as a main component (the third method for producing LPG).

Further, according to the present invention, in the production process of liquid oil and gas! /,hand,

The content of monoacid I匕炭oxygen in the feed gas, the total amount of carbon monoxide and carbon dioxide and hydrogen, 3 30 mol ^_0/0 above 3-2 The method of producing LPG is Is provided.

[0024] Here, the synthesis gas refers to a mixed gas containing hydrogen and carbon monoxide, and is not limited to a mixed gas composed of hydrogen and carbon monoxide. The synthesis gas may be a mixed gas containing, for example, carbon dioxide, water, methane, ethane, ethylene and the like. The synthesis gas obtained by reforming natural gas usually contains carbon dioxide and water vapor in addition to hydrogen and carbon monoxide. Also, the synthesis gas may be a water gas from which coal coat power is also produced.

The invention's effect

[0025] In the case of producing a liquid-based petroleum gas containing propane or butane as a main component by reacting hydrogen-containing carbon and hydrogen, first, the hydrogen-containing gas is reacted with hydrogen according to the following formula (1). Is synthesized from methanol, and then carbene (HC :) is generated by dehydration of methanol according to the following formula (2).

However, lower olefins are formed by the polymerization of the carbene, and It is believed that the in is hydrogenated to lower paraffin (LPG).

[0026] [Formula 1]

CO + 2H ₂ → CH ₃ OH (1)

[0027] [Formula 2]

CH ₃ OH → H ₂ C: + H ₂₀ (2) At this time, dimethyl ether is also produced by dehydration of methanol.

Conventionally, in Fischer-Tropsch synthesis (FT synthesis) or methanol synthesis, CO: H = 1: 1.8—1: 2: 2 is used as raw material gases by mixing carbon monoxide and hydrogen. Synthetic gas containing 5 (molar ratio)

2

Is often used.

[0029] On the other hand, in the present invention, carbon dioxide is added to the synthesis gas and used as a raw material gas. The content of carbon dioxide in the raw material gas is preferably 5 to 35 mol%, more preferably 7 to 17 mol%, based on the total amount of carbon monoxide, carbon dioxide and hydrogen. preferable. Also, the content of carbon dioxide in the raw material gas should be 0.2-1 monole per 1 mol of carbon monoxide, and 0.3-0.7 monole. Especially preferred! / ヽ.

[0030] By setting the composition of the source gas within the above range, LPG can be produced more easily and more economically. Specifically, it is possible to significantly suppress the generation of carbon dioxide without significantly reducing the yields of hydrocarbons and propane and butane.

[0031] The reason is considered as follows.

As represented by the following formula (3), in terms of stoichiometry for producing propane, the composition of the synthesis gas is preferably H ZCO (molar ratio) = 7Z3 2.33 force S. Also, as shown in the following equation (4),

2

Stoichiometry for production Speaking of the composition of synthesis gas, H / CO (molar ratio) = 9Z4 = 2

2

25 is preferred. On the other hand, as for the synthesis gas power in the conversion reaction to LPG, water is by-produced as shown in the following formulas (3) and (4). It is considered that this by-produced water reacts with carbon monoxide as shown in the following formula (5) to generate hydrogen. The reaction represented by the following equation (5) is called a shift reaction. [0033] [Formula 3]

3CO + 7H ₂ → C ₃ H ₈ + 3H ₂ 0 (3)

[0034] [Formula 4]

4CO + 9H ₂ → C ₄ H ₁₀ + 4H ₂ 0 (4)

[0035] [Formula 5]

CO + H ₂ 0 C 0 ₂ + H ₂ (5) Since the reaction represented by the above formula (5) is an equilibrium reaction, by adding carbon dioxide to the synthesis gas to obtain a raw material gas for LPG synthesis, By-product of carbon dioxide is suppressed. Furthermore, the synthesis gas, particularly, a synthesis gas produced by a steam reforming method, a combined reforming method, or an autothermal reforming method of natural gas (methane) is preferably mixed with carbon dioxide in an amount in the above range. By adding the calorie as raw material gas, it reacts with water produced as a by-product in the conversion reaction to LPG, reducing carbon monoxide and suppressing an increase in hydrogen, and suppressing the increase of LPG (propane and Z or butane). It is thought that the optimal source gas composition for the synthesis can be obtained, and as a result, the amount of carbon dioxide by-product can be significantly reduced while maintaining the yields of the target products propane and butane sufficiently high. Can be

[0036] When the content of carbon dioxide in the raw material gas is less than the above range, the effect of adding carbon dioxide to the above synthetic gas cannot be sufficiently obtained. On the other hand, when the content of carbon dioxide in the raw material gas is larger than the above range, the amount of carbon dioxide contained in the reaction product gas increases, and in addition, the yield of propane and butane as target products increases. Rates also tend to fall.

[0037] In addition, the lower paraffin-containing gas produced by the LPG synthesis reaction usually contains by-product carbon dioxide as a by-product. By separating such carbon dioxide from lower paraffin-containing gas and using it as carbon dioxide added to synthesis gas as in the second method for producing LPG of the present invention, LPG can be produced more economically. Can be manufactured. That is, as described above, by keeping the content of carbon dioxide in the raw material gas in the above range, the yield of propane and butane, which are the target products, can be maintained sufficiently high while the carbon dioxide side effect is maintained. Production It can be greatly reduced. On the other hand, carbon dioxide added to the source gas is a by-product of the LPG synthesis reaction. Therefore, the amount of carbon dioxide generated in the present process, that is, the amount of carbon dioxide discharged outside the system is greatly reduced. Therefore, according to the second method for producing LPG of the present invention, LPG can be produced more economically. Further, in terms of environmental friendliness, the second method for producing LPG of the present invention is more preferable.

Brief Description of Drawings

[FIG. 1] FIG. 1 shows a main configuration of an example of an LPG manufacturing apparatus suitable for carrying out the first or second LPG manufacturing method of the present invention. It is a process flow diagram.

FIG. 2 is a process flow chart showing a main configuration of an example of an LPG manufacturing apparatus suitable for carrying out a second LPG manufacturing method of the present invention.

FIG. 3 is a graph showing the changes over time in the yields of hydrocarbons and carbon dioxide and the composition distribution of generated hydrocarbons in Example 3.

FIG. 4 is a graph showing the change over time in the yield of hydrocarbons and carbon dioxide and the composition distribution of the generated hydrocarbons in Example 4.

FIG. 5 is a graph showing the change over time in the yield of hydrocarbons and carbon dioxide and the composition distribution of the generated hydrocarbons in Example 5.

Explanation of symbols

[0039] 11 Reformer

11a Reforming catalyst (Synthesis gas production catalyst)

12 reactor

12a Catalyst for lower paraffin production

13, 14, 15, 16, 17 lines

21 Reformer

21a Reforming catalyst (Synthesis gas production catalyst)

22 reactor

22a Catalyst for lower paraffin production 23 Separator

24, 25, 26, 27, 28 lines

29 Recycling line

BEST MODE FOR CARRYING OUT THE INVENTION

[Syngas Production Process]

In the synthesis gas production process, a synthesis gas is produced from a carbon-containing raw material. Usually, in the synthesis gas production process, the carbon-containing raw material and at least one selected from the group consisting of H 0, O and CO power are used.

2 2 2

From one type, syngas is produced.

[0041] The carbon-containing raw material is a substance containing carbon, and is a group consisting of H0, O, and CO power.

2 2 2

That can react with at least one selected to produce H and CO

2

it can. As the carbon-containing raw material, known raw materials for synthesis gas can be used. For example, lower hydrocarbons such as methaneethane and the like, and natural gas, naphtha, coal and the like can be used.

[0042] In the present invention, since there are usually a synthesis gas production process and a liquid gas production process! It is preferable that the content of catalyst poisoning substances such as sulfur and sulfur compounds is small. If the carbon-containing raw material contains a catalyst poisoning substance, a step of removing the catalyst poisoning substance such as desulfurization can be performed before the synthesis gas production step, if necessary.

[0043] In the presence of a synthesis gas producing catalyst (reforming catalyst), the synthesis gas reacts the above-described carbon-containing raw material with at least one selected from the group consisting of H0, O, and CO power. To make

2 2 2

It is manufactured by Synthetic gas is produced by a known method, for example, a steam reforming method, a combined reforming method or an autothermal reforming method of natural gas (methane).

[0044] The content ratio (on a molar basis) of hydrogen to carbon monoxide in the synthesis gas produced in the synthesis gas production process is preferably 1.5 [H ZCO] or more, 1.8 [H ZCO]. That's all

twenty two

More preferred. Further, the content ratio of hydrogen to carbon monoxide (based on mol) in the produced synthesis gas is preferably 3 [HZCO] or less, and more preferably 2.3 [HZCO] or less.

twenty two

[0045] The content of carbon monoxide in the synthesis gas produced in the synthesis gas production process is as follows: 20 mol% or more is preferable, and 25 mol% or more is more preferable. Further, the content of carbon monoxide in the produced synthetic gas is preferably 40 mol% or less, more preferably 35 mol% or less.

[0046] By setting the composition of the synthesis gas to the above range, the obtained synthesis gas and carbon dioxide (some are carbon dioxide-containing) in the next liquid petroleum gas production step or lower paraffin production step. ), A raw material gas having a suitable composition can be obtained. As a result, LPG can be produced more easily and more economically.

[0047] The synthesis gas having the above composition is widely produced, and is used, for example, as a raw material gas for methanol synthesis.

[0048] Further, for example, a shift reactor is provided downstream of a reformer, which is a reactor for producing a synthesis gas, as described above, and a synthesis reaction is performed by a shift reaction (CO + H0 → CO + H). of

2 2 2

The composition can be adjusted to the above range.

[0049] In order to produce a synthesis gas having a composition within the above range, a carbon-containing raw material and water (steam) are required.

), Oxygen and the supply ratio with at least one selected from the group consisting of

V. The type of synthesis gas production catalyst and other reaction conditions may be appropriately selected.

[0050] A synthesis gas having a composition within the above range can be produced, for example, by the following method.

[0051] In the presence of a reforming catalyst comprising a composite oxide having a composition represented by the following formula (I), a carbon-containing raw material (particularly, natural gas, methane), oxygen, carbon dioxide, and steam ( Water vapor) into the raw material gas to be introduced into the reactor with a (dioxide carbon + steam) Z carbon ratio of 0.5-3, an oxygen Z carbon ratio of 0.2-1 and an outlet of the reactor. By reacting at a temperature of 900-1100 ° C. and a pressure of 5-60 kg / cm ² , the synthesis gas used in the present invention can be produced.

[0052] aM-bCo-cNi-dMg-eCa-fO (I)

(Wherein, M is selected from the group consisting of Group 6A, Group 7A, Group 8 transition elements excluding Co and Ni, Group 1B, Group 2B, Group 4B and lanthanoid elements) A, b, c, d, and e represent the atomic ratio of each element, and when a + b + c + d + e = l, 0≤a≤0.1, 0. 001≤ (b + c) ≤0.3, 0≤b≤0.3, 0≤c≤0 3, 0.6 ≤ (d + e) ≤ 0.999, 0 <d ≤ 0.999, 0 ≤ e ≤ 0.999, and f is required to maintain charge balance with each elemental force S oxygen It is a number. )

The (carbon dioxide + steam) Z carbon ratio in the raw material gas introduced into the reactor is 0.5—

About 2 is preferred. The temperature at the outlet of the reactor is preferably 950-1050 ° C. The pressure at the outlet of the reactor is preferably 15-20 kgZcm ² .

[0053] The space velocity of the raw material gas is usually 500 to 200,000 hr- ¹ and 1000-1000OOhr- ¹ power S female <, 1000-70000hr- ¹ power female! / ヽ.

In the composite oxide having the composition represented by the above formula (I), MgO and CaO have a rock salt type crystal structure, and some of the Mg or Ca atoms located in the lattice are Co, Ni or M. It is a type of substituted solid solution that forms a single phase.

In the above formula (I), M is manganese, molybdenum, rhodium, ruthenium, platinum, palladium

Preferably, it is at least one element selected from the group consisting of copper, silver, zinc, tin, lead, lanthanum and cerium.

[0056] The content of M (a) is «0≤a≤0.1, preferably 0≤a≤0.05 0≤a≤0

03 is more preferable. If the M content (a) exceeds 0.1, the activity of the reforming reaction decreases.

[0057] The cobalt content (b) is 0≤b≤0.3, preferably 0≤b≤0.25, and more preferably 0≤b≤0.2. When the cobalt content (b) exceeds 0.3, it is difficult to sufficiently obtain the effect of preventing carbonaceous deposition.

[0058] The nickel content (c) is 0 ≤ c ≤ 0.3, preferably 0 ≤ c ≤ 0.25, and more preferably 0 ≤ c ≤ 0.2. If the nickel content (c) exceeds 0.3, the effect of preventing carbonaceous deposition cannot be sufficiently obtained.

[0059] Further, the total amount (b + c) of the cobalt content (b) and the nickel content (c) is 0.001≤ (b + c) ≤0.3, and 0.001≤ (b + c) ≤0.25 S is preferable, and 0.001≤ (b + c) ≤0.2 is more preferable. When the total content (b + c) exceeds 0.3, the effect of preventing carbonaceous deposition is not sufficiently obtained. On the other hand, when the total content (b + c) is less than 0.001, the reaction activity decreases.

[0060] The total amount (d + e) of the magnesium content (d) and the calcium content (e) is 0.6≤ (d + e ) ≤0.9998, 0.7≤ (d + e) ≤0.9998, S is preferred, and 0.77≤ (d + e) ≤0.9998 is more preferred than force! /ヽ.

[0061] Among these, the magnesium content (d) is 0 <d≤0.999, and 0.2≤d≤0.9998, and 0.337≤d≤0.9998. Better than being a power! / ,. Further, the content of canolesh (e) is 0≤e <0.999, preferably 0≤e≤0.5, and more preferably 0≤e≤0.3. The catalyst may not contain calcium.

[0062] The total amount (d + e) of the magnesium content (d) and the calcium content (e) is a balance between the M content (a), the cobalt content (b), and the nickel content (c). Is determined by (d + e) is a force that exerts an excellent effect on the reforming reaction at any ratio within the above range. If the content of calcium and M (a) is large, it is highly effective in suppressing carbonaceous deposition. However, there is a tendency for the catalytic activity to be lower than when magnesium is high. From the viewpoint of activity, the calcium content (e) is preferably 0.5 or less, and the M content (a) is preferably 0.1 or less.

[0063] The reforming catalyst used preferably has at least one of M, Co and Ni highly dispersed in the composite oxidized product. Here, the dispersion is defined as a ratio of the number of atoms exposed on the catalyst surface to the total number of atoms of the supported metal. That is, if the number of atoms of the Co, Ni or M metal element or its compound is A, and the number of these atoms exposed on the particle surface is B, BZA is the degree of dispersion. By using a reforming catalyst in which at least one of M, Co and Ni is highly dispersed in the composite oxide, the reaction becomes more highly active, the reaction proceeds stoichiometrically, Precipitation of carbon (carbon) is more effectively prevented.

[0064] Examples of a method for producing such a reforming catalyst include an impregnation-supporting method, a coprecipitation method, a sol-gel method (hydrolysis method), and a uniform precipitation method.

[0065] Usually, the above-mentioned reforming catalyst is subjected to an activation treatment before being used for production of synthesis gas.

The activation treatment is performed in the presence of a reducing gas such as hydrogen gas in a temperature range of 500 to 1000 ° C, preferably 600 to 1000 ° C, and more preferably 650 to 1000 ° C for about 0.5 to 30 hours. This is done by heating the catalyst. The reducing gas may be diluted with an inert gas such as nitrogen gas. This activation treatment can be performed in a reactor for performing a reforming reaction. The By this activation treatment, the catalytic activity is developed.

[0066] In the present invention, as another method for producing a synthesis gas used in the present invention, a carbon-containing raw material (particularly, natural gas or methane) is partially oxidized so that at least 600% of the carbon-containing raw material containing an unreacted carbon-containing raw material is contained. A mixed gas having a temperature of ° C is generated, and the unreacted carbon-containing raw material contained in the high-temperature mixed gas also becomes a metal oxide having an electronegativity of metal ions of 13 or less. Rhodium, ruthenium, iridium, palladium, and at least one metal (catalytic metal) selected from the group consisting of platinum metals are also supported on the carrier.The specific surface area is 25 m ² Zg or less. A method of producing a synthesis gas by reacting carbon dioxide and Z or steam under a pressurized condition in the presence of 0.0005 to 0.1 mol% of a catalyst with respect to the oxide. In addition, a mixed gas consisting of a carbon-containing raw material (especially natural gas and methane), an oxygen-containing gas (air, oxygen, etc.), carbon dioxide and Z or steam is used, and the electronegativity of metal ions is 13 or less. At least one metal (catalytic metal) selected from the group consisting of rhodium, ruthenium, iridium, palladium, and platinum is supported on a support made of a metal oxide.The specific surface area is 25 m ² Zg or less. In the presence of a catalyst in an amount of 0.0005 to 0.1 mol% of the supported metal oxide in terms of metal in terms of metal, the carbon-containing raw material in the mixed gas is partially oxidized to obtain unreacted carbon-containing material. A method of producing a mixed gas including a raw material and having a temperature of at least 600 ° C and reacting the unreacted carbon-containing raw material with carbon dioxide gas and / or steam under pressurized conditions. Be

Here, the catalyst metal may be supported in a metal state, or may be supported in a state of a metal compound such as an oxide. Further, the metal oxide used as the carrier may be a single metal oxide! / Or a composite metal oxide.

[0068] The electronegativity of metal ions in the carrier metal oxide is 13 or less, preferably 12 or less, more preferably 10 or less. If the electronegativity of the metal ion in the metal oxidized product exceeds 13, carbon precipitation becomes remarkable when the catalyst is used. In addition, the lower limit of the electronegativity of metal ions in the metal oxide sulfide for a carrier is usually about 4.

[0069] The electronegativity of the metal ion in the metal oxide is defined by the following equation. [0070] Xi = (l + 2i) Xo

Xi: electronegativity of metal ion,

Xo: electronegativity of metal,

i: the number of valence electrons of the metal ion.

[0071] When the metal oxide is a composite metal oxide, the average metal ion electronegativity is used, and the value is calculated based on the electronegativity of each metal ion contained in the composite metal oxide. The sum of the values obtained by multiplying by the mole fraction of each of the oxides therein.

[0072] The electronegativity (Xo) of a metal uses Pauling's electronegativity. Pauling's electronegativity is described in Table 15.4 of "Ryo Fujishiro, Moore Physical Chemistry (2) (4th edition), Tokyo Kagaku Dojin, p. 707 (1974)". The electronegativity (Xi) of the metal ion in the metal oxidized product is described in detail in, for example, “Catalysis Society of Japan, Catalyst Course, Vol. 2, p. 145 (1985)”.

[0073] Examples of such a metal oxide include metal oxides containing one or more metals such as Mg, Ca, Ba, Zn, Al, Zr, and La. Specific examples of such metal oxide films include magnesium (MgO), calcium oxide (CaO), barium oxide (BaO), zinc oxide (Ζηθ), alumina (Al 2 O 3), and zircon ( Single metal oxides such as ZrO), lanthanum oxide (LaO), and Mg

2 3 2 2 3

O / CaO, MgO / BaO, MgO / ZnO, MgO / Al O, MgO / ZrO, CaO / Ba

2 3 2

0, CaO / ZnO, CaO / Al O, CaO / ZrO, BaO / ZnO, BaO / Al O, BaO

2 3 2 2 3

/ ZrO, ZnO / Al O, ZnO / ZrO, Al O / ZrO, La O / MgO, La O / Al

2 2 3 2 2 3 2 2 3 2 3

O, La O ZCaO and other complex metal oxides.

2 3 2 3

The specific surface area of the catalyst to be used is 25 m ² Zg or less, preferably 20 m ² Zg or less, more preferably 15 mg or less, particularly preferably 10 m ² Zg or less. The lower limit of the specific surface area of the catalyst used is usually about 0.01 m ² Zg. By setting the specific surface area of the catalyst within the above range, the carbon deposition activity of the catalyst can be more sufficiently suppressed.

[0075] For the catalyst used here, the specific surface area of the catalyst is substantially the same as the specific surface area of the metal oxide as a carrier. Therefore, the specific surface area of the metal oxide as a carrier is not more than 25 m ^² Zg, 20m ² Zg is preferably less instrument 15 m ² Zg less less more preferably tool 10 mV g is particularly preferred. Further, the lower limit of the specific surface area of the metal oxide as a carrier is usually, 0. 01m is about ² Zg.

Here, the specific surface area of the metal oxide sulfide as a catalyst or a carrier is measured at a temperature of 15 ° C. by a BET method.

[0077] The catalyst having a specific surface area of 25 m ² / g or less is prepared by calcining the metal oxide as a carrier at 300 to 1300 ° C, preferably 650 to 1200 ° C before supporting the catalyst metal, Thereafter, the catalyst metal support obtained can be obtained by further calcination at 600 to 1300 ° C, preferably 650 to 1200 ° C. Alternatively, the catalyst metal can be obtained by supporting a catalyst metal on a metal oxide as a carrier and then calcining the obtained catalyst metal-supported material at 600 to 1300 ° C, preferably 650 to 1200 ° C. By controlling the firing temperature and the firing time, it is possible to control the specific surface area of the resulting metal oxide or catalyst or carrier.

[0078] The amount of the catalytic metal supported on the metal oxide serving as the support is 0.0005 to 0.1 mol% in terms of metal. The amount of the catalytic metal supported on the metal oxide as a support is preferably 0.001 mol% or more, more preferably 0.002 mol% or more, in terms of metal. Further, the amount of the catalytic metal supported on the metal oxide as the carrier is preferably 0.09 mol% or less in terms of metal.

[0079] Since the above-mentioned catalyst has a small specific surface area of the catalyst and a very small amount of supported catalyst metal, it has a sufficient synthesis gasification activity for the carbon-containing raw material and a carbon deposition activity. Is significantly suppressed.

[0080] Such a catalyst can be prepared according to a known method. As a method for producing a catalyst, for example, a metal oxide serving as a carrier is dispersed in water, a catalyst metal salt or an aqueous solution thereof is added and mixed, and then the metal oxide supporting a catalyst metal is separated from the aqueous solution. , Drying and baking (impregnation method), exhausting the metal oxide as a carrier, adding a small amount of a metal salt solution for the pore volume little by little to make the carrier surface uniformly wet, then drying and baking (Incipient-wetness method).

[0081] In the present invention, a carbon-containing raw material (particularly, natural gas or methane) is reacted with steam (water vapor) and Z or diacid carbon in the presence of the catalyst as described above. Syngas can be produced.

[0082] In the case of a method of reacting a carbon-containing raw material with carbon dioxide (CO reforming), the reaction temperature Degree 500-1200. C is 600-1000. C power S preferred ヽ. The reaction pressure is 5-40 kg / cm ² G, preferably 5-30 kg / cm ² G. When performing the reaction in a fixed bed system, gas space velocity (GHSV) is 1, 000- 10, a ^{OOOhr- 1, 2, 000- 8,} OOOhr- 1 force frame arbitrarily. The content of CO in the raw material gas introduced into the reactor is 1 mole of carbon in the carbon-containing raw material.

2

CO per 20-0.5 mol, preferably 101 mol.

2

[0083] In the case of a method of reacting a carbon-containing raw material with steam (steam reforming), the reaction temperature is 600 to 1200. C is 600-1000. C power S preferred ヽ. A reaction pressure ί or 1 one ^{40kg / cm 2 G, 5- 30kg} / cm 2 G are preferred. When this reaction is carried out in a fixed bed system, the gas hourly space velocity (GHSV) is 1,000-10, OOOhr- ¹ , and 2,000-8, OOOhr is preferable. The content of steam in the raw material gas introduced into the reactor is 20-0.5 mol of steam (H 0) per mol of carbon in the carbon-containing raw material, and 10-1 mol is preferable. Five

2

One mole is more preferred.

When producing a synthesis gas by reacting a mixture of steam and CO with a carbon-containing raw material,

2

The mixing ratio of the team and CO is not particularly limited, but H 2 O / CO (molar ratio) is usually 0.

2 2 2

One is ten.

[0085] In this synthesis gas production method, the energy required for the reforming reaction is such that a part of the carbon-containing material that is a reaction material for the reforming is partially oxidized (partially burned). Is supplied by combustion heat generated at that time.

[0086] The partial oxidation reaction of the carbon-containing raw material is carried out under the conditions of a temperature of 600 to 1500 ° C, preferably 700 to 1300 ° C, and a pressure of 5 to 50 kgZcm ² G, preferably 10 to 40 kgZcm ² G. . Oxygen is used as an oxidizing agent for partially oxidizing the carbon-containing raw material. As the oxygen source, in addition to pure oxygen, an oxygen-containing gas such as air or oxygen-enriched air is used. The oxygen content in the raw material gas introduced into the reactor is 0.1 to 14 in terms of the atomic ratio of oxygen to carbon (OZC) in the carbon-containing raw material, and is preferably 0.5-2.

[0087] By the partial oxidation of the carbon-containing raw material, a high-temperature mixed gas containing at least 600 ° C, preferably 700 to 1300 ° C, containing the unreacted carbon-containing raw material is obtained. By reacting unreacted carbon-containing raw material in the mixed gas with carbon dioxide and Z or steam under the above conditions, a synthesis gas can be produced. Diacidi carbon and Z or stee May be added to and mixed with the mixed gas obtained by the partial oxidation of the carbon-containing raw material, or may be added and mixed in advance with the carbon-containing raw material to be subjected to the partial oxidation reaction.ヽ. In the latter case, it is possible to simultaneously perform the partial oxidation of the carbon-containing raw material and the reforming reaction.

[0088] The reforming reaction of the carbon-containing raw material can be carried out in various types of reactors, but is usually preferably carried out in a fixed bed system or a fluidized bed system.

[Liquid oil petroleum gas production process, low-grade paraffin production process]

In the liquid and petroleum gas production process of the first and second LPG production methods and the first and second LPG production methods (both are also referred to as the first production method of LPG), a catalyst (for lower paraffin production) is used. In the presence of (catalyst) in the above synthesis gas production process, a lower paraffin-containing gas in which the main component of the contained hydrocarbon is propane or butane from the raw material gas containing the synthesis gas obtained and carbon dioxide If necessary, separates water, low-boiling components that have a boiling point or sublimation point lower than that of propane, higher than that of butane, and high-boiling components that have a boiling point. As a result, a liquid oil gas containing propane or butane as a main component is produced.

[0090] In the lower paraffin production step of the second LPG production method, in the presence of a catalyst (a catalyst for producing lower paraffin), the synthesis gas obtained in the above synthesis gas production step is mixed with the lower paraffin in the separation step described later. From the raw material gas containing the carbon dioxide-containing gas separated from the content gas, a lower paraffin-containing gas containing carbon dioxide, wherein the main component of the contained hydrocarbon is propane or butane. If necessary, the raw material gas may be further mixed with carbon dioxide.

[0091] Here, in the separation step, the carbon dioxide-containing gas separated from the lower paraffin-containing gas may be entirely recycled as a raw material in the lower paraffin production step, or a part of the gas may be removed from the system. It may be extracted and the remainder may be recycled as raw materials for the lower-grade paraffin production process. Further, a part of the carbon dioxide-containing gas separated from the lower paraffin-containing gas in the separation step can be recycled to the synthesis gas production step.

[0092] The carbon dioxide-containing gas may contain, for example, hydrogen, carbon monoxide, ethane, ethylene, methane, and the like, in addition to carbon dioxide. [0093] After separating components other than carbon dioxide from the carbon dioxide-containing gas separated from the lower paraffin-containing gas in the separation step, it is more likely to recycle as a raw material in the lower paraffin production step.

[0094] Examples of the catalyst for producing lower paraffins include one or more methanol synthesis catalyst components.

Catalysts containing one or more zeolite catalyst components are included.

[0095] Here, the methanol synthesis catalyst component is a catalyst in the reaction of CO + 2H → CH OH.

twenty three

Refers to those that show action. The zeolite catalyst component refers to a zeolite that exhibits a catalytic action in a condensation reaction of methanol to a hydrocarbon and a condensation reaction of Z or dimethyl ether to a hydrocarbon.

[0096] When carbon monoxide is reacted with hydrogen in the presence of the lower paraffin-producing catalyst, a reaction represented by the following formula (6) occurs, and paraffins whose main component is propane or butane are obtained. Can be manufactured.

[0097] [Formula 6]

CO

CH ₃ 0H-, CH ₃ OCH ₃

HLC: (6) H ₂

OLEFIN --- LPG First, methanol is synthesized from carbon monoxide and hydrogen on the methanol synthesis catalyst component. At this time, dimethyl ether is also produced by the dehydration of methanol. Next, the synthesized methanol is converted into a lower olefin hydrocarbon whose main component is propylene or butene at an active site in the pores of the zeolite catalyst component. In this reaction, carbene (H C:) is generated by dehydration of methanol, and lower olefins are formed by polymerization of the carbene.

2

Is considered to be generated. Then, the generated lower-olefin is a zeolite catalyst component. From the pores and rapidly hydrogenated on the methanol synthesis catalyst component to become paraffins whose main component is propane or butane.

[0098] The content ratio of the methanol synthesis catalyst component to the zeolite catalyst component (methanol synthesis catalyst component Z zeolite catalyst component; based on mass) is preferably 0.1 or more, more preferably 0.5 or more. It is particularly preferred that the ratio is 0.8 or more. Further, the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component (methanol synthesis catalyst component Z zeolite catalyst component; based on mass) is preferably 3 or less, more preferably 2.5 or less. It is particularly preferable that the number is 2 or less. By setting the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component in the above range, propane and Z or butane can be produced with higher selectivity and higher yield.

[0099] The methanol synthesis catalyst component has a function as a methanol synthesis catalyst and a function as a catalyst for hydrogenating olefins. Further, the zeolite catalyst component has a function as a solid acid zeolite catalyst whose acidity is adjusted for the condensation reaction of methanol and Z or dimethyl ether to a hydrocarbon. For this reason, the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component is reflected in the relative ratio between the methanol synthesis function and the hydrogenation function of the olefin, and the function of generating hydrocarbons from methanol, possessed by the catalyst. In the present invention, in producing paraffins whose main components are propane or butane by reacting carbon monoxide with hydrogen, the carbon monoxide and hydrogen are sufficiently converted to methanol by a methanol synthesis catalyst component. The produced methanol must be sufficiently converted by the zeolite catalyst component into olefins whose main component is propylene or butene, and the main component is propane or butane by the methanol synthesis catalyst component. I have to transfer it to paraffin.

[0100] The content ratio of the methanol synthesis catalyst component to the zeolite catalyst component (methanol synthesis catalyst component Z zeolite catalyst component; mass basis) is set to 0.1 or more, more preferably 0.5 or more. Carbon and hydrogen can be converted to methanol at a higher conversion ratio. Further, by setting the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component (methanol synthesis catalyst component Z zeolite catalyst component; mass basis) to 0.8 or more, the generated methanol can be more selectively converted to propane or butane. Paraffins as main components You can make it roll.

[0101] On the other hand, the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component (methanol synthesis catalyst component Z zeolite catalyst component; by mass) is set to 3 or less, more preferably 2.5 or less, and particularly preferably 2 or less. In addition, the produced methanol can be converted into paraffins whose main component is propane or butane at a higher conversion.

[0102] The content ratio of the methanol synthesis catalyst component to the zeolite catalyst component is not limited to the above range, and can be appropriately determined depending on the types of the methanol synthesis catalyst component and the zeolite catalyst component to be used.

[0103] As a catalyst component for methanol synthesis, it has a catalytic action in the reaction of CO + 2H → CH OH.

twenty three

Is not particularly limited as long as the catalyst shows the following, and a known methanol synthesis catalyst can be used.

[0104] Specific examples of the methanol synthesis catalyst component include Cu-Zn, Cu-Zn-Cr, and Cu-Zn.

Cu-Zn system such as Al system, Cu-Zn-Ag system, Cu-Zn-Mn-V system, Cu-Zn-Mn-Cr system, Cu-Zn-Mn-Al-Cr system and the third component Ni-Zn-based, Mo-based, Ni-carbon-based, and noble metal-based materials such as Pd. Also, a commercially available methanol synthesis catalyst can be used.

[0105] Preferable examples of the methanol synthesis catalyst component include Cu—Zn-based methanol such as copper oxide zinc oxide, copper oxide zinc oxide aluminum (alumina), copper oxide zinc oxide zinc oxide, and the like. Synthesis catalyst.

[0106] Other preferred methanol synthesis catalyst components include Pd-based methanol synthesis catalysts. Pd-based methanol synthesis catalysts include, among others, those in which 0.1 to 10% by weight of Pd is supported on a carrier such as silica, 0.1 to 10% by weight of Pd on a carrier such as silica, alkali metals such as Ca, Those carrying at least one element selected from the group consisting of alkaline earth metals and lanthanoid metal elements in an amount of 5% by weight or less (excluding 0% by weight) are preferred.

[0107] Note that Pd may not be contained in the form of a metal, but may be contained in the form of, for example, an oxide, a nitrate, or a salted sardine. In that case, since a higher catalytic activity can be obtained, a Pd-based methanol synthesis catalyst can be formed by, for example, performing a hydrogen reduction treatment before the reaction. It is preferable to convert Pd in the metal to palladium metal.

[0108] Other preferable methanol synthesis catalyst components include those in which an olefin hydrogenation catalyst component such as Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, or Pt is supported on a Zn-Cr-based methanol synthesis catalyst. No. Here, the catalyst for hydrogenation of olefins refers to those which have a catalytic action in the hydrogenation reaction of olefins to paraffins. Among the catalysts in which the olefin hydrogenation catalyst component is supported on a Zn—Cr-based methanol synthesis catalyst, Pd and Z or Pt, more preferably Pd is supported on a 0.005--5 wt% Zn—Cr-based methanol synthesis catalyst. What is done is preferred. The Zn—Cr-based methanol synthesis catalyst is usually a complex oxide containing Zn and Cr, and the complex oxide contains an element other than Zn, Cr and O, for example, Si, A1 and the like. It may be.

[0109] Note that Pd and Pt may not be contained in the form of a metal, but may be contained in the form of an oxide, a nitrate, a chloride, or the like. In this case, it is preferable to convert Pd and Pt to metal palladium and metal platinum before the reaction, for example, by performing a hydrogen reduction treatment from the viewpoint of obtaining higher catalytic activity.

[oiio] The zeolite catalyst component is not particularly limited as long as it is a zeolite that has a catalytic action in the condensation reaction of methanol to a hydrocarbon and the condensation reaction of Z or dimethyl ether to a hydrocarbon. Also, it is better to use commercially available products.

[0111] As the zeolite catalyst component, a medium-pore zeolite or a large-pore zeolite having three-dimensional expansion of pores through which reactive molecules can diffuse is preferable. These include, for example, ZSM-5, MCM-22, beta, and Y-type. In the present invention, small-pore zeolites such as SAPO-34, which generally exhibit high selectivity and high selectivity for condensation reactions to methanol and Z or dimethyl ether or lower olefin hydrocarbons, or in pores such as mordenite In general, ZSM-5 and MCM-22, which show higher selectivity and higher selectivity for condensation reaction of methanol and Z or dimethylethercaprol with alkyl-substituted aromatic hydrocarbons, than the non-three-dimensional diffusion of reactive molecules Preference is given to zeolites in which the reaction molecules are three-dimensionally diffused in the pores, such as medium-pore zeolites or large-pore zeolites such as the beta and Y types. Reactions in pores such as medium or large pore zeolites The use of zeolite, whose molecular diffusion is three-dimensional, allows the generated methanol to be more selectively converted to olefins containing propylene or butene as a main component and paraffins containing propane or butane as a main component. Can be.

[0112] Here, the medium pore zeolite has a pore diameter mainly formed by a 10-membered ring.

65 nm zeolite refers to zeolite, and large pore zeolite refers to zeolite having a pore diameter of 0.66-0.76 nm formed mainly by a 12-membered ring. The pore diameter of the zeolite catalyst component is more preferably 0.5 nm or more from the viewpoint of the selectivity of the C3 component and the C4 component in the gaseous product. The skeletal pore diameter of the zeolite catalyst component is more preferably 0.76 nm or less from the viewpoint of suppressing generation of liquid products such as aromatic compounds such as benzene and gasoline components such as C5 component.

[0113] As the zeolite catalyst component, a so-called high silica zeolite, specifically, SiO /

2

Zeolites with an Al O molar ratio of 10 150 are preferred. SiO / Al O molar ratio is 10 150

2 3 2 2 3

By using the high silica zeolite, the produced methanol can be more selectively converted to an olefin having propylene or butene as a main component, and further a paraffin having propane or butane as a main component. The SiO / AlO molar ratio of zeolite should be less than 20.

2 2 3

The upper part is more preferable, and 30 or more is particularly preferable. The zeolite SiO / Al O molar ratio is

2 2 3

Is more preferably 100 or less, and particularly preferably 50 or less.

[0114] As the zeolite catalyst component, the molar ratio of SiO / AlO is 10-150,

2 2 3

Medium-pore zeolites or large-pore zeolites in which the dispersible pores are three-dimensionally spread are particularly preferred. Such materials include, for example, solid acid zeolites such as USY and high silica type beta.

[0115] As the zeolite catalyst component, a solid acid zeolite as described above whose acidity has been adjusted by ion exchange or the like is used.

Examples of the zeolite catalyst component include zeolites containing metals such as alkali metals, alkaline earth metals, and transition metals, zeolites ion-exchanged with these metals, and zeolites carrying these metals and the like. The power of the proton type zeolite is preferred. By using a proton type zeolite having an appropriate acid strength and acid amount (acid concentration), the catalytic activity is further increased, and propane and Z or butane can be produced at high conversion and high selectivity. Can be synthesized.

[0117] The preferred zeolite catalyst component varies depending on the methanol synthesis catalyst component to be combined.

[0118] When used in combination with a Cu-Zn-based methanol synthesis catalyst, USY zeolite is preferred as the zeolite catalyst component. USY zeolite having a SiO / AlO molar ratio of 10-150 is preferred.

2 2 3

Particularly preferred is a USY zeolite having a SiO / AlO molar ratio of 10-50.

2 2 3

[0119] When used in combination with a Pd-based methanol synthesis catalyst, the zeolite catalyst component is preferably j8-zeolite, a proton-type j8-zeola having a SiO / AlO molar ratio of 10-150.

2 2 3

Especially preferred are protonated | 8-zeolites with a SiO / Al O molar ratio of 30-50.

2 2 3

Preferred.

When the olefin hydrogenation catalyst component is used in combination with a component supported on a Zn—Cr-based methanol synthesis catalyst, the preferred zeolite catalyst component is j8-zeolite, particularly preferably the SiO 2 / Al 2 O 3 molar ratio. Is a proton type zeolite having 10-150, more preferably SiO

2 2 3 2

Proton-type j8-zeolites having a molar ratio of 30-50 AlO / Al O are exemplified.

twenty three

[0121] As a catalyst for producing lower paraffin, a catalyst prepared by separately preparing a methanol synthesis catalyst component and a zeolite catalyst component and mixing them is preferable. By separately preparing the methanol synthesis catalyst component and the zeolite catalyst component, it is easy to optimally design the composition, structure, and physical properties for each function.

[0122] Some methanol synthesis catalysts require a reduction treatment to be activated before use. In the present invention, it is not always necessary to activate the methanol synthesis catalyst component by performing a reduction treatment in advance, and after the methanol synthesis catalyst component and the zeolite catalyst component are mixed and formed to produce a lower paraffin production catalyst, the reaction is performed. Prior to the start, a reduction treatment can be performed to activate the methanol synthesis catalyst component. The treatment conditions of this reduction treatment can be appropriately determined according to the type of the methanol synthesis catalyst component and the like.

[0123] The lower paraffin-producing catalyst is produced by uniformly mixing the methanol synthesis catalyst component and the zeolite catalyst component, and then molding as necessary. The method of mixing and molding the two catalyst components is not particularly limited, but a dry method is preferred. Mixing of both catalyst components by wet method • When molding, transfer of compound between both catalyst components, such as methanol synthesis catalyst The migration of the basic component in the component to the acid site in the zeolite catalyst component 'neutralization' may change the properties and the like optimized for the respective functions of both catalyst components. Examples of the method for forming the catalyst include an extrusion molding method and a tablet molding method.

[0124] In the present invention, the methanol synthesis catalyst component and the zeolite catalyst component to be mixed are preferably in the form of granules, rather than in the form of powder, which preferably have a somewhat large particle diameter.

[0125] Here, the powder refers to a powder having an average particle diameter of 10 / zm or less, and the granule refers to a powder having an average particle diameter of 100m or more.

[0126] Granular, ie, a methanol synthesis catalyst component having an average particle diameter of 100 µm or more, and zeolite catalyst component, which is similarly condyle, ie, an average particle diameter of 100 m or more, are mixed and molded as necessary. By producing a catalyst for producing lower paraffin, it is possible to obtain a catalyst having a longer catalyst life and less deterioration. The average particle size of the methanol synthesis catalyst component and the average particle size of the zeolite catalyst component to be mixed are more preferably 200 m or more, particularly preferably 500 μm or more.

On the other hand, from the viewpoint of maintaining the excellent performance of the mixed catalyst, the average particle diameter of the methanol synthesis catalyst component and the average particle diameter of the zeolite catalyst component to be mixed are preferably 5 mm or less, more preferably 2 mm or less.

[0128] The average particle diameter of the methanol synthesis catalyst component to be mixed and the average particle diameter of the zeolite catalyst component are preferably the same.

[0129] In the case of producing a mixed catalyst, usually, each catalyst component is mechanically pulverized as necessary, and the average particle size is adjusted to, for example, about 0.5 to 2 m, and then uniformly mixed. Mold as needed. Alternatively, all the desired catalyst components are added, mixed until uniform while mechanically pulverizing, and the average particle size is adjusted to, for example, about 0.5 to 2 m, and then molded if necessary.

[0130] On the other hand, when a catalyst for producing lower paraffin is produced by mixing a granular methanol synthesis catalyst component and a granular zeolite catalyst component, each catalyst component is usually prepared in advance by a tableting method and an extrusion method. It is molded by a known molding method such as a molding method, and is mechanically pulverized if necessary, and the average particle diameter is preferably adjusted to about 100 m to 5 mm, and then both are uniformly mixed. Then, if necessary, the mixture is molded again, and the lower To manufacture a catalyst for the production of

[0131] The lower paraffin-producing catalyst may contain other additive components as needed as long as the desired effect is not impaired.

[0132] In the liquid production petroleum gas production step of the first LPG production method or the lower paraffin production step of the second LPG production method, carbon monoxide and hydrogen are produced in the presence of the above-mentioned catalyst. And are reacted to produce paraffins whose main component is propane or butane, preferably paraffins whose main component is propane.

[0133] The gas fed into the reactor, that is, the raw material gas, was separated from the synthesis gas and carbon dioxide obtained in the above-described synthesis gas production step, or from the lower paraffin-containing gas in the separation step described below. Gas containing carbon dioxide.

[0134] The content of carbon monoxide in the gas fed into the reactor is determined in consideration of securing a pressure (partial pressure) of carbon monoxide suitable for the reaction and improving the unit consumption of raw materials. It is preferably at least 3 mol%, more preferably at least 3.3 mol%, based on the total amount of carbon oxide, carbon dioxide and hydrogen. In addition, the content of carbon monoxide in the gas fed into the reactor is such that the conversion rate of carbon monoxide becomes sufficiently higher, so that carbon monoxide, Is preferably 30 mol% or less, more preferably 28 mol% or less, based on the total amount of

[0135] The content of carbon dioxide in the gas fed into the reactor is determined based on the total amount of mono-orientated carbon, di-orientated carbon and hydrogen from the viewpoint of improving the CO unit consumption. 5 mol% or more is preferable 7 mol% or more is more preferable 8 mol% or more is particularly preferable. In addition, the content of carbon dioxide in the gas sent into the reactor is controlled by carbon monoxide and carbon dioxide in order to reduce the amount of CO generated.

2

35 mol% or less is preferable, and 30 mol% or less is more preferable, and 17 mol% or less is especially preferable with respect to the total amount of carbon and hydrogen.

[0136] The content of carbon dioxide in the gas fed into the reactor is preferably 0.2 mol or more per 1 mol of carbon dioxide from the viewpoint of suppressing the amount of carbon dioxide generated. The magus is more preferably at least 0.3 mol. Further, the content of carbon dioxide in the gas fed into the reactor is preferably 1 mol or less, more preferably 0.7 mol or less, based on 1 mol of carbon dioxide from the viewpoint of productivity. preferable.

[0137] When the content of carbon dioxide in the gas fed into the reactor increases, the by-product The amount of carbon decreases. On the other hand, if the content of carbon dioxide in the gas sent to the reactor becomes too large, the amount of circulation (circulation) of unnecessary gas increases.

[0138] The content of hydrogen in the gas fed into the reactor is preferably 1.2 mol or more per 1 mol of carbon monoxide from the viewpoint that carbon monoxide reacts more sufficiently. 1. More than 5 moles is more preferred. Further, the content of hydrogen in the gas fed into the reactor is more preferably 3.5 mol or less, more preferably 3 mol or less, per 1 mol of carbon monoxide from the viewpoint of economy.

[0139] In the second method for producing LPG, the content of the carbon dioxide-containing gas in the gas fed into the reactor is such that the composition of the gas fed into the reactor is preferably within the above range. It can be determined as appropriate.

[0140] The gas fed into the reactor may include, for example, water, methane, ethane, ethylene, an inert gas, and the like, in addition to carbon monoxide, hydrogen, and carbon dioxide. The gas sent to the reactor may be the synthesis gas and carbon dioxide obtained in the above-mentioned synthesis gas production process, or the carbon dioxide-containing gas in which the lower paraffin-containing gas power is also separated in the separation process described below. The gas may contain other components as necessary. Further, the gas fed into the reactor is the synthesis gas obtained in the above-described synthesis gas production step, and the dioxin-containing carbon-containing gas separated from the lower paraffin-containing gas in the separation step described below. If necessary, predetermined components may be separated.

[0141] The reaction temperature is preferably 270 ° C or higher, more preferably 300 ° C or higher, since the methanol synthesis catalyst component and the zeolite catalyst component each show sufficiently higher activities. Further, the reaction temperature is preferably 420 ° C or lower, more preferably 400 ° C or lower, in view of the limit temperature for use of the catalyst and the ease of removing and recovering the reaction heat.

[0142] Further, by raising the reaction temperature to a high temperature, it is also possible to react dihydrogen carbon and hydrogen to produce a olefin. In that case, the reaction temperature is preferably 310 ° C or higher, more preferably 330 ° C or higher. Also in this case, the reaction temperature is preferably 420 ° C or lower, more preferably 400 ° C or lower.

[0143] A suitable reaction temperature depends on the type of the catalyst to be used. When a Cu—Zn-based methanol synthesis catalyst is used as the methanol synthesis catalyst component, the reaction temperature is too high! /, More preferably, specifically, 340 ° C. or lower. On the other hand, as a methanol synthesis catalyst component In the case of using a Pd-based methanol synthesis catalyst or a catalyst in which the olefin hydrogenation catalyst component is supported on a Zn—Cr-based methanol synthesis catalyst, the reaction temperature is particularly preferably 340 ° C. or higher.

[0144] The reaction pressure is more preferably 2 MPa or more, which is preferably IMPa or more, since the methanol synthesis catalyst component exhibits a sufficiently high activity. The reaction pressure is 10

MPa or less is preferred. 7 MPa or less is more preferred.

[0145] Gas hourly space velocity, in terms of economic efficiency, or 500 hr ^_1 is preferable instrument 2000Hr- ¹ or more is more preferable. In addition, the gas space velocity depends on the methanol synthesis catalyst component and the zeolite catalyst component.

, Respectively, from the viewpoint of giving a contact time indicating a more sufficiently high Utati匕率, LOOOOhr- ¹ hereinafter is preferably tool 5000Hr- ¹ or less is more preferable.

[0146] The gas fed into the reactor is split and fed into the reactor, thereby controlling the reaction temperature.

[0147] The reaction can be carried out in a fixed bed, a fluidized bed, a moving bed, or the like. For example, as fixed beds, there are a multi-stage reactor such as an internal multi-stage reactor, a multi-tube reactor, a multi-stage reactor including multiple heat exchanges, a multi-stage cooling radial flow system, a double-tube heat system, and the like. Other reactors such as an exchange system, a built-in cooling coil system, and a mixed flow system can be used.

[0148] The catalyst for producing lower paraffin can be used after being diluted with an inert and stable heat conductor, such as silica or alumina, for the purpose of controlling the temperature. Further, the catalyst for producing lower paraffin can be used by coating it on the heat exchange surface for the purpose of controlling the temperature.

[0149] The liquid-shape petroleum gas obtained in the liquid-shape petroleum gas production process and the lower paraffin-containing gas before separation of water and the like, or the lower paraffin-containing gas obtained in the lower paraffin-producing process are included. The main component of the hydrocarbons used is propane or butane. From the viewpoint of the liquid-riding properties, the larger the total content of propane and butane in the liquid-riding petroleum gas or the lower paraffin-containing gas, the better. According to the present invention, it is possible to obtain a liquid crystal gas or a lower paraffin-containing gas having a total content of propane and butane of 75% or more, more preferably 80% or more (including 100%) based on carbon.

[0150] Furthermore, the liquid paraffin-containing gas obtained in the liquid paraffin production process and the lower paraffin-containing gas before separation of water and the like, or in the lower paraffin production process The obtained lower paraffin-containing gas preferably contains more propane than butane from the viewpoint of flammability and vapor pressure characteristics. In the present invention, it is possible to obtain a liquid gas or a liquid containing lower paraffin having a propane content of 57% or more, more preferably 62% or more (including 100%) based on carbon.

[0151] In the first method for producing LPG, as described above, a lower paraffin-containing gas in which the main component of the hydrocarbon contained is propane or butane is produced, and if necessary, water or propane is produced. Liquefied petroleum gas (LPG) is produced by separating low boiling components that are substances having a boiling point or sublimation point lower than the boiling point, and high boiling components that are substances having a boiling point higher than that of butane. Separation of water, low-boiling components and high-boiling components can be performed by a known method. In addition, pressurization and / or cooling may be performed as necessary in order to obtain liquid gas.

[0152] For consumer use, from the viewpoint of safety during use, for example, it is preferable that the content of low boiling components in LPG is reduced to 5 mol% or less (including 0 mol%) by separation.

[0153] The total content of propane and butane in the LPG thus produced can be 95 mol% or more, and further 98 mol% or more (including 100 mol%). The content of propane in the LPG produced is 60 mol% or more, further it can be 65 mol% or more (including 100 mol ^_0/0).

According to the first method for producing an LPG of the present invention, it is possible to produce an LPG having a composition suitable for propane gas widely used as a fuel for home and business use.

[Separation Step]

In the separation step of the second LPG production method, in the above-mentioned lower paraffin production step, water and the like are separated from the lower paraffin-containing gas obtained as necessary, and then the carbon dioxide is removed. Is separated to obtain a liquefied petroleum gas (LPG) containing propane or butane as a main component. Pressurization and Z or cooling may be performed as necessary in order to obtain a liquid oil gas.

[0156] The lower paraffin-containing gas obtained in the lower paraffin production step includes, in addition to carbon dioxide, unreacted raw materials such as hydrogen and carbon monoxide, and by-products such as ethane, methane, and ethylene. Contains low boiling components with low boiling points or sublimation points Be turned. These low-boiling components may also be separated at the same time as carbon dioxide-containing gas.

[0157] Separation of the carbon dioxide-containing gas can be performed by a known method such as gas-liquid separation, absorption separation, and distillation. More specifically, the separation can be performed by gas-liquid separation or absorption separation at normal temperature under pressure, gas-liquid separation or absorption separation by cooling, or a combination thereof. Further, it can be carried out by membrane separation or adsorption separation, and can also be carried out by combining these with gas-liquid separation, absorption separation, and distillation.

[0158] Lower paraffin-containing gas power [0158] From the separated carbon dioxide-containing gas, components other than carbon dioxide, for example, the above-mentioned low-boiling components can be separated as necessary. Separation of low-boiling components and the like can be performed by a known method.

[0159] Before separating the carbon dioxide-containing gas or after separating the carbon dioxide-containing gas, the lower paraffin-containing gas is converted into a substance having a boiling point higher than that of butane, such as a high boiling point component, for example, a high boiling point component. Paraffin gas or the like may be separated. Separation of the high boiling component can be performed by a known method such as gas-liquid separation, absorption separation, and distillation.

[0160] For consumer use, from the viewpoint of safety during use, for example, the content of low boiling components in LPG is preferably 5 mol% or less (including 0 mol%) by separation.

[0161] The total content of propane and butane in the LPG thus produced is 95 mol

% Or more, and 98% or more (including 100% by mole). The content of propane in the LPG produced is 60 mol% or more, further it can be 65 mol% or more (including 100 mol ^_0/0).

According to the second LPG production method of the present invention, it is possible to produce LPG having a composition suitable for propane gas which is widely used as a fuel for home and business use.

[0163] [Recycling process]

In the recycling process of the second LPG production method, the carbon dioxide-containing gas separated from the lower paraffin-containing gas in the above separation process is recycled to the lower paraffin production process.

[0164] All of the carbon dioxide-containing gas separated from the lower paraffin-containing gas may be recycled to the lower-paraffin production process, or part of the gas may be extracted to the outside of the system or recycled to the synthesis gas production process. The rest may be recycled to the lower paraffin manufacturing process. The carbon dioxide-containing gas can be separated into only a desired component, that is, carbon dioxide, and recycled to the lower paraffin production process.

[0165] In order to recycle the carbon dioxide-containing gas, a known technique such as appropriately providing a pressure increasing means in a recycle line can be adopted.

[Method of Manufacturing LPG]

Next, an embodiment of an LPG manufacturing method of the present invention will be described with reference to the drawings.

FIG. 1 shows an example of an LPG production apparatus suitable for carrying out the first LPG production method of the present invention.

[0168] First, methane is supplied to the reformer 11 via the line 13 as a carbon-containing raw material. Although not shown, steam is supplied to the line 13 to perform steam reforming. The reformer 11 includes a reforming catalyst 11a. Further, the reformer 11 includes a heating means (not shown) for supplying heat required for reforming. In the reformer 11, methane is reformed in the presence of the reforming catalyst 11a, and a synthesis gas containing hydrogen, carbon monoxide, carbon dioxide, and water vapor is obtained.

[0169] The synthesis gas thus obtained is supplied to the reactor 12 via the lines 14 and 15. Also, carbon dioxide is supplied to the line 15 via the line 16. The reactor 12 is provided with a lower paraffin production catalyst 12a. In this reactor 12, a lower paraffin-containing gas containing propane and butane is synthesized from a raw material gas containing synthesis gas and carbon dioxide in the presence of a lower paraffin-producing catalyst 12a.

[0170] The synthesized lower paraffin-containing gas is subjected to pressurization and cooling after removing water and the like as necessary, and LPG as a product is obtained from line 17. LPG may remove hydrogen and the like by gas-liquid separation or the like.

[0171] Although not shown, the LPG manufacturing apparatus is provided with a booster, a heat exchange, a valve, an instrumentation control device, and the like as necessary.

FIG. 2 shows an example of an LPG production apparatus suitable for carrying out the second LPG production method of the present invention.

[0173] First, methane is supplied to the reformer 21 via the line 24 as a carbon-containing raw material. Also, Although not shown, steam is supplied to the line 24 for performing steam reforming. In the reformer 21, a reforming catalyst 21a is provided. Further, the reformer 21 includes a heating means (not shown) for supplying heat required for reforming. In the reformer 21, methane is reformed in the presence of the reforming catalyst 21a, and a synthesis gas containing hydrogen, carbon monoxide, carbon dioxide, and water vapor is obtained.

[0174] The synthesis gas thus obtained is supplied to the reactor 22 via the lines 25 and 26. Further, a carbon dioxide-containing gas containing carbon dioxide is supplied from a separator 23 to a line 26 via a recycling line 29. The reactor 22 is provided with a lower paraffin production catalyst 22a. In the reactor 22, in the presence of the lower paraffin production catalyst 22a, a raw paraffin containing propane and butane, and a lower paraffin-containing gas containing butane are synthesized.

[0175] The synthesized lower-paraffin-containing gas is supplied to a separator 23, which is a distillation column, through a line 27 after removing water and the like as necessary. Then, a substance having a boiling point equal to or higher than the boiling point of propane, that is, LPG as a product, is obtained by pressure distillation at room temperature, and a substance having a boiling point or sublimation point lower than the boiling point of propane, that is, a low boiling point. The components are obtained as residual gas. In this way, a product LPG is obtained from the line 28. On the other hand, the residual gas (low-boiling point component) obtained from the top is recycled to the reactor 22 through the recycling line 29 as a carbon dioxide-containing gas containing carbon dioxide.

[0176] Although not shown, the LPG manufacturing apparatus is provided with a booster, a heat exchange, a valve, an instrumentation control device, and the like as necessary.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. Note that the present invention is not limited to these examples.

[Example 1]

LPG was manufactured using the LPG manufacturing apparatus shown in FIG. As the reforming catalyst (catalyst for producing synthesis gas) and the catalyst for producing lower paraffin, those prepared as follows were used.

(Preparation of Reforming Catalyst)

Magnesium oxide fired in air at 920 ° C for 2 hours is sized to 0.27-0.75mm After that, Ru was loaded by the impregnation method. The Ru-impregnated body was obtained by repeatedly dropping an aqueous solution of ruthenium (III) chloride hydrate (Ru content: 1.0% by weight) into calcined MgO little by little and shaking. Then, the Ru-impregnated body was dried in air at 120 ° C. for 2.5 hours, and then calcined in air at 920 ° C. for 2 hours to obtain a reforming catalyst (Ru-supported MgO catalyst). The resulting R u supporting MgO catalyst, the supported amount of Ru is 0. 0 6 mol% with 1. 5 X 10- ³ g, mol in terms relative to MgO lg, surface area of 9. 6 m ² Zg .

(Preparation of Catalyst for Production of Lower Paraffin)

As the methanol synthesis catalyst component, a commercially available Cu—Zn methanol synthesis catalyst (manufactured by Nippon Zoohemie Co., Ltd.) that was mechanically powdered was used. As a zeolite catalyst component, a separately prepared proton type ZSM-5 zeolite having a SiO / AlO molar ratio of 14.5 (pore diameter: short

2 2 3

0.53 mm diameter, 0.556 mm long diameter) powder was used.

[0181] This methanol synthesis catalyst component and a zeolite catalyst component of the same weight are uniformly mixed, press-molded and sized, and then reduced in a hydrogen stream at 300 ° C for 3 hours to produce lower paraffin. A catalyst was obtained.

[0182] (Syngas production process)

After filling the above-mentioned reforming catalyst into an externally heated reaction tube type apparatus, prior to the reaction, the catalyst was subjected to a reduction treatment in a hydrogen stream at 900 ° C. for 1 hour.

[0183] Natural gas 46.5 mole ^_0/0, a steam 47.3 mole ^_0/0, carbon dioxide 6.2 mole ^_0/0 becomes raw material gas force, was passed through the reforming catalyst layer. The reaction conditions were as follows: reaction temperature 870 ° C, reaction pressure 2.1

MPa ゝ GHSV (gas hourly space velocity) 2000 hr- ¹ .

[0184] The product (syngas) was analyzed by gas chromatography to find that the composition was hydrogen.

61 mole ^_0/0, the carbon monoxide 30 mol ^_0/0, CO 2 mole ^_0/0, methane 7 mole ⁰ /. Met.

[Liquefied petroleum gas production process]

Synthesis was added 18Z 100 fold volume of the secondary Sani匕carbon gas to a synthesis gas obtained gas production step Te Contactヽ, hydrogen 52.6 mole ^_0/0, carbon monoxide 25.9 mole ⁰ / ₀ , carbon dioxide 1

A gas consisting of 5.5 mol% and methane 6.0 mol% was passed through the lower paraffin production catalyst layer. The reaction conditions were as follows: reaction temperature 325 ° C, reaction pressure 2.0MPa, GHSV3000hr- ^1. [0186] The product (lower paraffin-containing gas) was analyzed by gas chromatography to find that the conversion of carbon monoxide to hydrocarbons was 50%, and the conversion of carbon monoxide to carbon dioxide was a shift reaction. 0%. The generated hydrocarbons were propane and butane in 75% on a carbon basis, with propane and butane being 56% propane and 4% butane power on a carbon basis.

[0187] After gas-liquid separation of the obtained lower paraffin-containing gas, it was dried with a molecular sieve, and bubbled into an octane solution maintained at about 0 ° C. Monore ^_0/0, Etan and ethylene 2.2 Monore ^_0/0, carbon dioxide 25.9 mole. / ₀ , a gas consisting of 21.9 mol% of unreacted carbon monoxide and 37.3 mol% of hydrogen was separated as a low-boiling component to produce LPG.

[Comparative Example 1]

LPG was produced in the same manner as in Example 1 except that a gas containing lower paraffin was produced without supplying carbon dioxide from the line 16.

[0189] As a result, the gas containing lower paraffin before the separation of the low-boiling components was analyzed by gas chromatography. As a result, the conversion of carbon monoxide was 70%, and the shift reaction of carbon monoxide to carbon dioxide was confirmed. The conversion ratio was 35%, and the conversion ratio to hydrocarbon was 35%. In the hydrocarbons produced, 76% was propane and butane on a carbon basis, and the breakdown of propane and butane was 55% for propane and 45% for butane on a carbon basis.

[0190] In Comparative Example 1, the amounts of propane and butane contained in the lower paraffin-containing gas produced from the synthesis gas were smaller than in Example 1.

[Example 2]

LPG was manufactured using the LPG manufacturing apparatus shown in FIG. As the reforming catalyst (catalyst for producing synthesis gas) and the catalyst for producing lower paraffin, those prepared in the same manner as in Example 1 were used.

[Syngas Production Process]

[0193] Natural gas 45 mole ^_0/0, steam 45 mole ^_0/0, the carbon dioxide 10 mole ^_0/0 force becomes the raw material gas Was passed through the reforming catalyst layer. The reaction conditions were a reaction temperature of 870 ° C., a reaction pressure of 2. lMPa, and a GHSV (gas hourly space velocity) of 2000 hr- ¹ .

[0194] The product (synthesis gas) was analyzed by gas chromatography to find that the composition was 62 mol% of hydrogen, 31 mol% of carbon monoxide, 4.8 mol% of carbon dioxide, and 2.2 mol% of methane. I

[0195] (Lower paraffin production process)

To the synthesis gas obtained in the synthesis gas production process, added a gas containing carbon dioxide, which was recycled as a raw material in the lower-grade production process of 8Z10 times the volume of the synthesis gas. A gas consisting of 26.9% of carbon, 14.2% of carbon dioxide, 6.9% of methane, and 1.0% of others was passed through a catalyst layer for producing lower paraffin. The reaction conditions were a reaction temperature of 325 ° C, a reaction pressure of 2. OMPa, and GHSV of 3000 hr- ¹ .

[0196] When the product (lower paraffin-containing gas) was analyzed by gas chromatography, the conversion of carbon monoxide to hydrocarbons was 50%, and the shift conversion of carbon monoxide to carbon dioxide was 50%. 0%. The generated hydrocarbons were propane and butane in 75% on a carbon basis, with propane and butane being 56% propane and 4% butane power on a carbon basis.

[0197] (Separation / recycling process)

After gas-liquid separation of the gas containing lower paraffin obtained in the process of producing lower paraffin, it is dried over molecular sieves and bubbled into an octane solution maintained at about 0 ° C to convert methane from lower paraffin-containing gas into methane. . 8 mole ^_0/0, Etan and Echire emissions 2.2 mole%, carbon dioxide 25.9 mole%, the gas containing carbon dioxide and comprising carbon monoxide 21.9 mole%, and hydrogen 37.3 mole% of unreacted Separated as gas (low boiling point component) to produce LPG.

[0198] The separated carbon dioxide-containing gas was pressurized to 2.5MPa by a compressor, and then recycled as a raw material in a low-grade paraffin production process.

[Comparative Example 2]

Example 2 except that the gas containing carbon dioxide separated from the gas containing lower paraffin was not recycled to the reactor 22 by the recycling line 29 and the gas containing lower paraffin was produced. LPG was produced in the same manner as in 2.

[0200] As a result, when the lower paraffin-containing gas before the separation of the carbon dioxide-containing gas was analyzed by gas chromatography, the conversion of carbon monoxide was 53%, indicating that the conversion of carbon monoxide was 53%. The conversion ratio to hydrocarbons was 10%, and the conversion ratio to hydrocarbons was 43%. Propane and butane accounted for 72% of the generated hydrocarbons on a carbon basis. The proportion of propane and butane was 54% for propane and 46% for butane on a carbon basis.

[0201] In addition, lower-paraffin-containing gas forces in the separation 'recycling process the composition of the separated two-Sani匕carbon-containing gas, methane 10.3 mol ^_0/0, Etan and ethylene 1.9 mole ^_0/0, two 28.0 mol% of carbon oxide, 21.3 mol% of unreacted carbon monoxide and 38.5 mol% of hydrogen.

[0202] In Comparative Example 2, the amounts of propane and butane contained in the lower paraffin-containing gas produced from the synthesis gas column were smaller than in Example 2.

[Example 3]

(Production of catalyst)

As a methanol synthesis catalyst component, a catalyst (also referred to as “PdZZn—Cr”) prepared as follows, in which 1% by weight of Pd was supported on a Zn—Cr-based methanol synthesis catalyst, was mechanically powdered. (Average particle size: 0.7 m) was used.

[0204] As a Zn—Cr-based methanol synthesis catalyst, a product name: K manufactured by Sudo Chemie Catalysts, Inc.

MA (average particle size: about lmm) was used. The composition of this Zn-Cr methanol synthesis catalyst is Zn

ZCr = 2 (atomic ratio).

[0205] First, Pd (NH) (NO) aqueous solution (Pd content: 4.558 wt ^_0/0) 4. Ion exchange 4ml

3 2 3 2

A Pd-containing solution was prepared by adding 1 ml of water. The prepared Pd-containing solution was charged with 20 g of a Zn—Cr-based methanol synthesis catalyst, and impregnated with the Pd-containing solution. Then, the Zn-Cr-based methanol synthesis catalyst impregnated with the Pd-containing solution was dried in a dryer at 120 ° C for 12 hours, and further calcined in air at 450 ° C for 2 hours. Into a methanol synthesis catalyst component.

[0206] As the zeolite catalyst component, a commercially available proton type 13-having a molar ratio of SiO ZA1 O of 37.1 was used. Zeolite (manufactured by Tosoichi Co., Ltd.) mechanically powdered (average particle size: 0.7 m) was used.

The prepared methanol synthesis catalyst component and zeolite catalyst component were uniformly mixed with Pd / Zn-Cr: β-zeolite = 2: 1 (weight ratio). Then, this was subjected to tablet molding and sizing to obtain a granular molding catalyst having an average particle diameter of lmm.

[0208] (Manufacture of LPG)

After filling the prepared catalyst lg into a reaction tube having an inner diameter of 6 mm, the catalyst was reduced in a hydrogen stream at 400 ° C. for 3 hours before the reaction.

[0209] After reducing the catalyst, a raw material gas (HZCO = 2 (on a molar basis)) consisting of 66.7 mol% of hydrogen and 33.3 mol% of carbon monoxide was reacted at a reaction temperature of 375 ° C and a reaction pressure of 5%. . IMPa, gas

2

LPG synthesis reaction was performed by flowing through the catalyst layer at a space velocity of 2000 hr— ^ WZF: ^ Og'hZmol).

[0210] Three hours after the start of the reaction, the raw material gas (HZCO = 2 (on a molar basis)) was added to the gas containing carbon dioxide.

2

Gas (H / CO = 2 (mole basis)) as raw material gas: carbon dioxide-containing gas = 3: 1 (flow ratio)

twenty two

After the addition, an LPG synthesis reaction was performed. Gas composition was passed through the catalyst layer, hydrogen 66.7 mole ^_0/0, carbon monoxide 25.0 mole ^_0/0, and carbon dioxide 8.3 mol ^_0/0 (H / CO /

2

CO = 8Z3Zl (mol

2 criteria)).

[0211] The results (yield of hydrocarbons and carbon dioxide and time course of the composition distribution of generated hydrocarbons) are shown in FIG. The product was analyzed by gas chromatography.

[0212] As is evident from Fig. 3, the addition of carbon dioxide to the raw material gas significantly reduced the production of carbon dioxide without significantly reducing the yield of hydrocarbons and the yields of propane and butane. Could be suppressed.

[Example 4]

(Manufacture of LPG)

An LPG synthesis reaction was performed in the same manner as in Example 3 except that the reaction temperature was changed to 400 ° C.

[0214] Fig. 4 shows the results (yields of hydrocarbons and carbon dioxide and changes over time in the composition distribution of generated hydrocarbons). [0215] As is clear from FIG. 4, as in Example 3, the addition of diacid carbon to the raw material gas did not significantly reduce the yields of hydrocarbons and propane and butane. The production of carbon was significantly suppressed.

[0216] [Example 5]

(Production of catalyst)

[0217] As a Zn-Cr-based methanol synthesis catalyst, a product name: K manufactured by Sued Chemie Catalysts Co., Ltd.

ZCr = 2 (atomic ratio).

[0218] First, Pd (NH) (NO) aqueous solution (Pd content: 4.558 wt ^_0/0) 4. Ion exchange 4ml

3 2 3 2

[0219] As a zeolite catalyst component, a commercially available proton type 13-having a molar ratio of SiO ZA1 O of 37.1 was used.

2 2 3

Zeolite (manufactured by Tosoichi Co., Ltd.) loaded with 1% by weight of Pd and mechanically powdered (average particle size: 0.7 m) was used.

[0220] Pd was supported on a / 3-zeolite as follows.

[0221] 0.0825 g of PdCl (purity> 99 wt%) was added to 40-50. 12.5wt% ammonia water in C

2

The solution was dissolved in 10 ml. Further, 150 ml of ion-exchanged water was added to this solution to prepare a solution to be used for ion exchange.

[0222] The ion exchange was carried out using 10 g of 13-zeolite by heating and stirring at 60 to 70 ° C for 6 hours. The ion-exchanged sample was repeatedly filtered and washed with ion-exchanged water until chlorine ions were no longer observed in the filtrate, dried at 120 ° C for 12 hours, and calcined in air at 500 ° C for 2 hours. [0223] The prepared methanol synthesis catalyst component and zeolite catalyst component were uniformly mixed with Pd / Zn-Cr: β-zeolite = 2: 1 (weight ratio). Then, this was subjected to tablet molding and sizing to obtain a granular molding catalyst having an average particle diameter of lmm.

[0224] (Manufacture of LPG)

[0225] After reduction treatment of the catalyst, a raw material gas consisting of hydrogen, carbon monoxide and carbon dioxide was passed through the catalyst layer at a reaction temperature of 400 ° C and a reaction pressure of 5. IMPa to perform an LPG synthesis reaction. The composition of the source gas and WZF were changed as follows during the reaction.

[0226] (Raw material gas composition and WZF)

From the start of the reaction to 2 hours:

Raw gas composition: H / CO / CO

2 2 = 8Z3Zl (molar basis); WZF = 6.7 g-h / mol

From 2 hours to 4 hours:

Source gas composition: H / CO / CO = 6Z2Zl (on a molar basis); WZF = 5.9 g-h / mol

twenty two

From 4 hours to the end of the reaction:

Source gas composition: H / CO / CO = 10Z3Z2 (on a molar basis); WZF = 5.3g-h / mo

twenty two

[0227] The results (changes in the yield of hydrocarbons and carbon dioxide and the composition distribution of the generated hydrocarbons over time) are shown in FIG.

[0228] As is clear from Fig. 5, when the content of carbon dioxide in the source gas increases, the amount of by-produced carbon dioxide decreases, while the yield of hydrocarbons, and further, the propane and Butane yield tends to decrease.

Industrial applicability

[0229] As described above, according to the present invention, LPG having a high propane and / or butane concentration can be produced more easily and more economically from a carbon-containing raw material such as natural gas or a synthesis gas. Can be.

Claims

The scope of the claims

[1] (a synthesis gas production process of producing a synthesis gas from a carbon-containing raw material,

A method for producing a liquid gas comprising propane or butane as a main component.

[2] In the production process of liquid and petroleum gas,

The method for producing a liquefied petroleum gas according to claim 1, wherein the content of carbon monoxide in the raw material gas is 3 to 30 mol% based on the total amount of carbon monoxide, carbon dioxide, and hydrogen.

[3] (i) a synthesis gas production process for producing a synthesis gas from a carbon-containing raw material,

[4] In the production process of liquid oil

4. The production of a liquid gas according to claim 3, wherein the content of the carbon monoxide in the raw material gas is 3 to 30 mol% based on the total amount of carbon monoxide, carbon dioxide and hydrogen. Method.

[5] (i) a synthesis gas production process for producing a synthesis gas from a carbon-containing raw material,

(iii) In the process of producing lower paraffin, the gas power containing lower paraffin obtained in Separating a carbon dioxide-containing gas containing carbon to obtain a liquefied petroleum gas containing propane or butane as a main component,

[6] In the lower paraffin production process,

6. The method according to claim 5, wherein the content of carbon dioxide in the raw material gas is 5 to 35 mol% based on the total amount of carbon monoxide, carbon dioxide, and hydrogen.

[7] In the lower paraffin production process,

7. The production of a liquid gas according to claim 6, wherein the content of carbon monoxide in the raw material gas is 3 to 30 mol% based on the total amount of carbon monoxide, carbon dioxide and hydrogen. Method.

[8] In the production process of liquid oil and gas,

6. The method for producing liquid Iridani petroleum gas according to claim 5, wherein the content of carbon dioxide in the raw material gas is 0.2-1 mol per 1 mol of carbon monoxide.

[9] In the lower paraffin production process,

9. The production of a liquid gas according to claim 8, wherein the content of carbon monoxide in the raw material gas is 3 to 30 mol% based on the total amount of carbon monoxide, carbon dioxide and hydrogen. Method.

[10] (i) In the presence of a catalyst, containing carbon monoxide, hydrogen and carbon dioxide, the content of carbon dioxide is based on the total amount of carbon monoxide, carbon dioxide and hydrogen. Liquid gas production process for producing liquid gas containing propane or butane as a main component from a raw gas of 5 to 35 mol%

[11] In the production process of liquid oil and gas,

The production of a liquid gas according to claim 10, wherein the content of carbon monoxide in the raw material gas is 3 to 30 mol% based on the total amount of carbon monoxide, carbon dioxide and hydrogen. Method.

[12] (i) In the presence of a catalyst, containing carbon monoxide, hydrogen, and carbon dioxide, and having a carbon dioxide content of 0.2 to 1 mole of the source gas per mole of carbon monoxide, propane Or Liquefied petroleum gas production process to produce liquefied petroleum gas containing butane as the main component

[13] In the manufacturing process of liquid oil and gas,

The production of a liquid gas according to claim 12, wherein the content of carbon monoxide in the raw material gas is 3 to 30 mol% based on the total amount of carbon monoxide, carbon dioxide and hydrogen. Method.