CN1749371A - Process for producing liquefied petroleum gas - Google Patents

Abstract

The invention relates to a manufacturing method of liquefied petroleum gas, comprising the following steps that: alkene-contained gas, which takes propylene and/or butene as principal component and comprises ethylene and amylene, is made from at least one methanol and dimethyl enther; the obtained alkene-contained gas and alkene conversion reaction product gas obtained during following production process are separated into propylene/butene inclusion, ethylene inclusion and amylene inclusion; the alkene conversion reaction product gas taking propylene and/or butene as main component is made from the obtained ethylene inclusion and amylene inclusion and is conveyed to a separation production process; finally, the propylene/butene inclusion is reacted with hydrogen to make liquefied petroleum gas. The invention can provide an economic method to make liquefied petroleum gas (LPG) through adopting at least one methanol and dimethyl enther as raw material.

Description

The manufacture method of liquefied petroleum gas (LPG)

Technical field

At least a material manufacturing main component that the present invention relates to from methyl alcohol and dme is that propane is or/and the method for the liquefied petroleum gas (LPG) of butane.

Background technology

Liquefied petroleum gas (LPG) (LPG) is meant the hydrocarbon that is gasiform oil system or Sweet natural gas system at normal temperatures and pressures, compression or cool off simultaneously and form liquid material, and its main component is propane or butane.Can store and the LPG of transportation have the characteristics of easy transportation with liquid state, and need provide the Sweet natural gas of pipeline different when supplying with, can offer any place with the form of high-pressure gas cylinder.For this reason, be the LPG of principal constituent with propane, promptly propane gas is widely used as home-use, commerce fuel.At present, in Japan, to about 2,500 ten thousand families (more than 50% of all families) supply propane gas.In addition, LPG also can be used as fuel (being mainly butane gas), industrial fuel and automobile fuel that moving bodys such as boxlike bogey (cassette cooking stove), disposable lighter are used except using the fuel as home-use, commercial.

All the time, LPG can generate 1 by following method) method, 2 that reclaims from moist Sweet natural gas) method, 3 that reclaims from stable (vapour pressure adjustment) operation of crude oil) separate with method of extraction to the product of generation refining of petroleum operation etc. etc.

LPG, especially still having demand in the future as the home-use and commercial propane gas of using with fuel, and if can be in the enforceable and new manufacture method of industrial establishment, then very valuable.

As the manufacture method of LPG, in patent documentation 1, propose under the effect of mixed catalyst, the synthetic gas of being made up of hydrogen and carbon monoxide to be reacted, make the method for liquefied petroleum gas (LPG) or the composition hydrocarbon mixture close with it.Wherein, described mixed catalyst is that methanol synthesis catalysts such as Cu-Zn system, Cr-Zn system or Pd system (are specially CuO-ZnO-Al ₂O ₃Catalyzer, Pd/SiO ₂Catalyzer) and be roughly methanol conversion catalyst that the above zeolite (being specially y-type zeolite) of 10 (1nm) forms by mean pore size and carry out physical mixed and make.

In addition, as the manufacture method of LPG, the method for pointing out in non-patent literature 1 is to use by the 4wt%Pd/SiO as methanol synthesis catalyst ₂, BASF S3-85) and carry out the SiO of 1 hour steam-treated under 450 ℃ Cu-Zn-Al mixed oxide [Cu: Zn: Al=40: 23: 37 (atomic ratio)] or Cu be low pressure methanol synthetic catalyst (trade(brand)name: ₂/ Al ₂O ₃The mixed catalyst that=7.6 high silicon dioxide y-type zeolite is constituted, via methyl alcohol, dme, the selection rate with 69～85% is made the method for the paraffinic hydrocarbons of C2～C4 from synthetic gas.

On the other hand, as the manufacture method of LPG, proposition comprises the manufacture method of the liquefied petroleum gas (LPG) of operation as described below in patent documentation 2,

(1) manufacturing process of olefin-containing gas:

With at least a material in methyl alcohol and the dme and hydrogen is unstripped gas, by catalyst layer, is contained the reaction gas of olefines, water and hydrogen that main component is propylene or butylene at least.Wherein, described catalyst layer contains at least a material from methyl alcohol and dme employed olefin-containing gas synthetic catalyst when making olefin-containing gas, the part that the ratio (atomic ratio) that is specially Si and Al is below 100, the more preferably ZSM-5 below 70 more than 20, or the half of the Al of this skeleton is following is by the metal silicate of Fe metathetical MFI structure;

(2) olefin-containing gas hydrogenation process:

The reaction gas that in olefin-containing gas manufacturing process, obtains, pass through catalyst layer, making main component is the liquefied petroleum gas (LPG) of propane or butane, wherein, described catalyst layer contains the olefin-containing gas hydrogenation catalyst that uses when making paraffinic hydrocarbons in that alkene is carried out hydrogenation, is specially nickel catalyzator, palladium catalyst or platinum catalyst etc.

And then as the manufacture method of LPG, proposition comprises the manufacture method of the liquefied petroleum gas (LPG) of operation as described below in patent documentation 2,

(1) contain alkene appropriate hydrocarbon gas manufacturing process:

When at least a material from methyl alcohol and dme is made olefin-containing gas under the effect of employed olefin-containing gas synthetic catalyst, at least a material from methyl alcohol and dme and in separation circuit from olefin-containing gas isolated and ethene that in recirculation, be recycled use as the raw material of olefin-containing gas manufacturing process contain thing, the main component of making institute's hydrocarbonaceous is propylene or butylene and the olefin-containing gas that contains ethene;

(2) separation circuit:

From by the olefin-containing gas that obtains the olefin-containing gas manufacturing process, isolate the ethene that contains ethene and contain thing, contain thing thereby obtain propylene;

(3) recirculation operation:

Will be in separation circuit separated ethene part or all raw material of containing thing as olefin-containing gas manufacturing process carry out recirculation;

(4) olefin-containing gas hydrogenation process:

Under the effect of the olefin-containing gas hydrogenation catalyst that uses when making paraffinic hydrocarbons in that alkene is carried out hydrogenation, contain thing and hydrogen from the propylene that is obtained by separation circuit, making main component is the liquefied petroleum gas (LPG) of propane or butane.

In addition, as the manufacture method of LPG, proposition comprises the manufacture method of the liquefied petroleum gas (LPG) of operation as described below in patent documentation 3,

Synthetic gas manufacturing process: the synthetic gas that contains hydrogen and carbon monoxide from the carbon raw material manufacturing;

Methyl alcohol/dme manufacturing process: under the effect of catalyzer, make methyl alcohol and/or dme from synthetic gas;

Light alkene manufacturing process: under the effect of catalyzer, from methyl alcohol and/or the dme that this methyl alcohol/dme manufacturing process, obtains, make contain carbonatoms be 2,3 and 4 olefine mixing gas contain light alkene gas;

Liquefied petroleum gas (LPG) manufacturing process: under the effect of catalyzer, to contain the manufacturing of light alkene gas be the liquefied petroleum gas (LPG) of main component with propane with this.

And then, in patent documentation 3, proposed in above-mentioned method, preferably contain the composition that isolated boiling point the light alkene gas is lower than propylene from above-mentioned, be specially ethene etc., and offer above-mentioned synthetic gas manufacturing process and/or above-mentioned light alkene manufacturing process.In addition, also mentioned in the patent documentation 3 in above-mentioned method, from the reaction product of above-mentioned methyl alcohol/dme manufacturing process, preferentially isolated at least a portion its contained hydrogen and/or carbon monoxide, and offered above-mentioned liquefied petroleum gas (LPG) manufacturing process.

In addition, in non-patent literature 2, proposed to make as raw material the method for LPG with at least a material in methyl alcohol and the dme.Specifically being to be under the condition of 603K (330 ℃) in little pressurization and temperature of reaction, is being benchmark with methyl alcohol, and LHSV is 20H ^-1Condition under, make methyl alcohol: H ₂: N ₂=1: 1: 1 unstripped gas is that ZSM-5 and back segment are the 2 layers of catalyst layer (ZSM-5/Pt-C series) of Pt-C or the mixed catalyst layer (ZSM-5/Pt-C granular mixture) that is made of ZSM-5 and Pt-C by leading portion, carries out the LPG building-up reactions.

Patent documentation 1: the spy opens clear 61-23688 communique,

Patent documentation 2: international disclosing No. 2004/074411,

Patent documentation 3: international disclosing No. 2004/001798,

Non-patent literature 1: " Selective Synthesis of LPG from Synthesis Gas ", KaoruFujimoto et al., Bull.Chem.Soc.Jpn., 58, P.3059-3060 (1985),

Non-patent literature 2: " Methanol/Dimethyl Ether Conversion on ZeoliteCatalysts for Indirect Synthesis of LPG from Natural Gas ", Yingjie Jin et al., the 92nd catalyzer discussion discussion A preliminary draft collection, P.322, on September 18th, 2003.

Summary of the invention

The objective of the invention is to, provide a kind of with at least a material in methyl alcohol and the dme as raw material, less expensive ground manufacturing main component be propane and/or butane hydrocarbon, be the method for liquefied petroleum gas (LPG) (LPG).

According to the present invention, a kind of manufacture method (the LPG manufacture method of 1-1) of liquefied petroleum gas (LPG) can be provided, it is characterized in that, comprising:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and/or butylene and contain ethene and the olefin-containing gas of amylene;

(ii) separation circuit:

It is that to contain thing and main component be that the amylene of amylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propene/but-1-ene that is separated into main component at least and is propylene and/or butylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, react by making olefines, promptly contain thing and amylene and contain thing and react from the ethene that separation circuit, obtains, making main component is the olefin reaction product gas of propylene and/or butylene; With;

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propene/but-1-ene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane and/or butane.

In addition,, also can provide a kind of manufacture method (the LPG manufacture method of 1-2) of liquefied petroleum gas (LPG), it is characterized in that, comprise according to the present invention:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and contain ethene and the olefin-containing gas of butylene;

(ii) separation circuit:

It is that to contain thing and main component be that the butylene of butylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propylene that is separated into main component at least and is propylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, react by making olefines, promptly contain thing and butylene and contain thing and react from the ethene that separation circuit, obtains, making main component is the olefin reaction product gas of propylene; With

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propylene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane.

And then, according to the present invention, also can provide a kind of manufacture method (the LPG manufacture method of 2-1) of liquefied petroleum gas (LPG), it is characterized in that, comprising:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and/or butylene and contain ethene and the olefin-containing gas of amylene;

(ii) separation circuit:

It is that to contain thing and main component be that the amylene of amylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propene/but-1-ene that is separated into main component at least and is propylene and/or butylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, by at least a material in olefines and methyl alcohol and the dme is reacted, promptly contain thing, amylene from the ethene that obtains separation circuit and contain that at least a material reacts in thing and methyl alcohol and the dme, making main component is the olefin reaction product gas of propylene and/or butylene; With

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propene/but-1-ene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane and/or butane.

In addition,, also can provide a kind of manufacture method (the LPG manufacture method of 2-2) of liquefied petroleum gas (LPG), it is characterized in that, comprise according to the present invention:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and contain ethene and the olefin-containing gas of butylene;

(ii) separation circuit:

It is that to contain thing and main component be that the butylene of butylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propylene that is separated into main component at least and is propylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, by at least a material in olefines and methyl alcohol and the dme is reacted, promptly contain thing, butylene from the ethene that obtains separation circuit and contain that at least a material reacts in thing and methyl alcohol and the dme, making main component is the olefin reaction product gas of propylene; With

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propylene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane.

And then, according to the present invention, also can provide a kind of after above-mentioned alkene manufacturing process and before above-mentioned separation circuit, have the manufacture method of the liquefied petroleum gas (LPG) of the water sepn operation of from above-mentioned olefin-containing gas and/or above-mentioned olefin reaction product gas, separating water outlet.

In the present invention, at first, with at least a material in methyl alcohol and the dme, making main component is the olefines of propylene and/or butylene, and preferred main component is the olefin-containing gas of propylene.This olefin-containing gas also contains usually as the propylene of target component LPG carbonatoms and the olefines outside the butylene.

When making olefines with at least a material in methyl alcohol and the dme or during based on the hydrocarbon of olefines, by the dehydration reaction generation carbene (H of methyl alcohol ₂C :), the polyreaction by carbene generates alkene, so what obtain usually is not a kind of alkene, but has the olefines more than 2 kinds that definite composition distributes.When making with carbonatoms is that 3 propylene is the olefines of main component or during based on the hydrocarbon of such olefines, usually in reaction product except containing propylene, go back carbon atom quantity and be 2 ethene, carbonatoms and be 4 butylene and carbonatoms and be 5 amylene.

Thus, in the olefin-containing gas of manufacturing of the present invention,, usually also contain ethene or contain the alkene (being also referred to as higher alkene) that carbonatoms such as amylene is Duoed than target product as by product.Wherein, when making propane gas, butylene also belongs to higher alkene.

But, with regard to ethene, under the effect of zeolite catalyst, it is reacted, can convert it into propylene and butylene as LPG composition carbonatoms.But its yield might not be high, and have the trend of the yield of butylene greater than propylene.As the LPG composition, compare with butane, more preferably propane, preferred for this reason propene yield is high.

On the other hand, senior alkene such as amylene (except the butylene) is difficult to change into separately propylene and the butylene that contains LPG composition carbonatoms.Butylene also is difficult to change into separately propylene.

But, react with ethene by making senior alkene (except the butylene) such as amylene, just can change into propylene and butylene as LPG composition carbonatoms.Butylene also can change into propylene by reacting with ethene.This reaction is exactly many replacement(metathesis)reactions of knowing (intersection replacement(metathesis)reaction).

Therefore, by from the olefin-containing gas of manufacturing of the present invention, isolating ethene and higher alkene, and they are reacted, can improve the yield of propylene and/or butylene.Therefore, the present invention can be with higher yield, and at least a material from methyl alcohol and dme is made propylene and/or butylene, and then makes propane and/or butane (the LPG manufacture method of 1-1, the LPG manufacture method of 1-2).

And then, sometimes by in ethene and higher alkene, adding at least a material in methyl alcohol and the dme and it is reacted, thereby further improve the yield (the LPG manufacture method of 2-1, the LPG manufacture method of 2-2) of propylene and/or butylene.

In addition, according to the present invention, because separately carry out alkene manufacturing process and conversion of olefines operation, so can make each operation reach optimizing, and can make propylene and/or butylene, and then make propane and/or butane with at least a material of higher yield from methyl alcohol and dme.Specifically, for example, in alkene manufacturing process, use iron aluminosilicate (ferroalumino silicate), more preferably use iron aluminosilicate to react as catalyzer with MFI structure, in the conversion of olefines operation, by using Hydrogen ZSM-5 (H-ZSM-5) to react, can make propylene and/or butylene with at least a material of higher yield from methyl alcohol and dme, and then make propane and/or butane as catalyzer.In conversion of olefines operation of the present invention, compare as catalyzer with using Hydrogen ZSM-5, even use metathesis catalyst in the past to react, also be difficult to make propylene and/or butylene with high yield.

As mentioned above,, can make propane and/or butane with at least a material of high yield from methyl alcohol and dme according to the present invention, less expensive ground manufacturing main component be propane and/or butane hydrocarbon, be liquefied petroleum gas (LPG) (LPG).

Description of drawings

Fig. 1 is that LPG manufacturing installation (system) main composition of the of the present invention the 1st LPG manufacture method and one of them example of process flow sheet be fit to are implemented in expression.

Fig. 2 is that LPG manufacturing installation (system) main composition of the of the present invention the 2nd LPG manufacture method and one of them example of process flow sheet be fit to are implemented in expression.

Among the figure: 21-alkene is made reactor, 21a-alkene is made catalyzer, the 22-separator, the 23-olefin reactor, 23a-conversion of olefines catalyzer, 24-olefin hydrogenation reactor, 24a-olefin hydrogenation catalyzer, 210,211,212,213,214,215,216,217,218, the 219-pipeline, 31-alkene is made reactor, 31a-alkene is made catalyzer, 32-separator, 33-olefin reactor, 33a-conversion of olefines catalyzer, 34-olefin hydrogenation reactor, 34a-olefin hydrogenation catalyzer, 310,311,312,313,314,315,316,317,318,319, the 320-pipeline.

Embodiment

With reference to the accompanying drawings, an embodiment to LPG manufacture method of the present invention describes.

[the LPG manufacture method of 1-1 and the LPG manufacture method of 1-2]

Fig. 1 is an example of the LPG manufacturing installation (system) of expression LPG manufacture method (also both being called altogether the 1st LPG manufacture method sometimes) that be fit to implement the LPG manufacture method of 1-1 of the present invention and 1-2.Compare with the LPG manufacture method that with propane and butane is the 1-1 of target product, the LPG manufacture method of 1-2 is to be target product with propane, promptly makes propane gas.

At first, via pipeline 210, will offer alkene manufacturing reactor 21 as the methyl alcohol and/or the dme of reaction raw materials.Alkene is housed in alkene is made reactor 21 makes catalyzer 21a.In this alkene is made reactor 21, make at alkene under the effect of catalyzer, from methyl alcohol and/or dme, synthetic main component is propylene and/or butylene and contains ethene and the olefin-containing gas of amylene (the LPG manufacture method of 1-1) that perhaps synthetic main component is propylene and contains ethene and the olefin-containing gas of butylene (the LPG manufacture method of 1-2).This olefin-containing gas contains the water as by product usually.

The olefin-containing gas of manufacturing remove moisture etc. by operations such as gas-liquid separations after, offers separator 22 via pipeline 211 and 212.In addition, the olefin reaction product gas can be removed after moisture etc. as required, offers separator 22 from olefin reactor 23 via pipeline 216 and 212.In this separator 22, it is that to contain thing, main component be that to contain thing and main component be that the amylene of amylene contains thing (the LPG manufacture method of 1-1) for the ethene of ethene for the propene/but-1-ene of propylene and/or butylene that olefin-containing gas and olefin reaction product gas are separated into main component.Perhaps, being separated into main component is that to contain thing, main component be that to contain thing and main component be that the butylene of butylene contains thing (the LPG manufacture method of 1-2) for the ethene of ethene for the propylene of propylene.

Here separated ethene contains the part in the thing, also can circulate as required to offer alkene manufacturing reactor 21.

Separated ethene contains thing and offers olefin reactor 23 via pipeline 213 and 214.In addition, amylene contains thing (the LPG manufacture method of 1-1) or butylene contains thing (the LPG manufacture method of 1-2) also via pipeline 215 and 214, offers olefin reactor 23.In olefin reactor 23, conversion of olefines catalyzer 23a is housed.In this olefin reactor 23, under the effect of conversion of olefines catalyzer,, contain thing and amylene from ethene and contain thing to make main component be the olefin reaction product gas of propylene and/or butylene by the LPG manufacture method of 1-1.Perhaps, by the LPG manufacture method of 1-2, contain thing and butylene from ethene and contain thing to make main component be the olefin reaction product gas of propylene.

The olefin reaction product gas of manufacturing is transported in the separator 22 by pipeline 216 and 212.

On the other hand, isolating propene/but-1-ene contains thing (the LPG manufacture method of 1-1) or propylene contains thing (the LPG manufacture method of 1-2) in separator 22, offers olefin hydrogenation reactor 24 via pipeline 217.In addition, hydrogen also offers olefin hydrogenation reactor 24 via pipeline 218.In olefin hydrogenation reactor 24, olefin hydrogenation catalyzer 24a is housed.In this olefin hydrogenation reactor 24, under the effect of olefin hydrogenation catalyzer, by the LPG manufacture method of 1-1, containing the synthetic main component of thing and hydrogen from propene/but-1-ene is the hydrocarbon gas (containing the lower alkane appropriate hydrocarbon gas) of propane and/or butane.Perhaps, by the LPG manufacture method of 1-2, containing the synthetic main component of thing and hydrogen from propylene is the hydrocarbon gas (containing the lower alkane appropriate hydrocarbon gas) of propane.

After the method for knowing by the crowd was removed low boiling point component such as hydrogen and high boiling point is become to grade from institute's synthetic hydrocarbon gas as required, pressurization and cooling obtained product LPG from pipeline 219.

Not expression among the figure also has, though can be provided with compressor, heat exchanger, valve and power operation control device etc. as required on the LPG manufacturing installation.

[the LPG manufacture method of 2-1 and the LPG manufacture method of 2-2]

Fig. 2 is an example of the LPG manufacturing installation (system) of expression LPG manufacture method (also both being called altogether the 2nd LPG manufacture method sometimes) that be fit to implement the LPG manufacture method of 2-1 of the present invention and 2-2.Compare with the LPG manufacture method that with propane and butane is the 2-1 of target product, the LPG manufacture method of 2-2 is to be target product with propane, promptly makes propane gas.

At first, via pipeline 310, will offer alkene manufacturing reactor 31 as the methyl alcohol and/or the dme of reaction raw materials.In alkene is made reactor 31, alkene is housed makes catalyzer 31a.In this alkene is made reactor 31, make at alkene under the effect of catalyzer, from methyl alcohol and/or dme, synthetic main component is propylene and/or butylene and contains ethene and the olefin-containing gas of amylene (the LPG manufacture method of 2-1) that perhaps synthetic main component is propylene and contains ethene and the olefin-containing gas of butylene (the LPG manufacture method of 2-2).This olefin-containing gas contains the water as by product usually.

The olefin-containing gas of manufacturing remove moisture etc. by operations such as gas-liquid separations after, offers separator 32 via pipeline 311 and 312.In addition, the olefin reaction product gas is also removed after moisture etc. as required, offers separator 32 from olefin reactor 33 via pipeline 316 and 312.In this separator 32, it is that to contain thing, main component be that to contain thing and main component be that the amylene of amylene contains thing (the LPG manufacture method of 2-1) for the ethene of ethene for the propene/but-1-ene of propylene and/or butylene that olefin-containing gas and olefin reaction product gas are separated into main component.Perhaps, being separated into main component is that to contain thing, main component be that to contain thing and main component be that the butylene of butylene contains thing (the LPG manufacture method of 2-2) for the ethene of ethene for the propylene of propylene.

Here separated ethene contains the part in the thing, also can circulate as required to offer alkene manufacturing reactor 31.

Separated ethene contains thing and offers olefin reactor 33 via pipeline 313 and 314.In addition, amylene contains thing (the LPG manufacture method of 2-1) or butylene contains thing (the LPG manufacture method of 2-2) also via pipeline 315 and 314, offers olefin reactor 33.And then methyl alcohol and/or dme also offer olefin reactor 33 via pipeline 320 and 314.In olefin reactor 33, conversion of olefines catalyzer 33a is housed.In this olefin reactor 33, under the effect of conversion of olefines catalyzer, by the LPG manufacture method of 2-1, make ethene contain thing, amylene contains thing and methyl alcohol and/or dme and reacts, making main component is the olefin reaction product gas of propylene and/or butylene.Perhaps, by the LPG manufacture method of 2-2, make ethene contain thing, butylene contains thing and methyl alcohol and/or dme and reacts, making main component is the olefin reaction product gas of propylene.

The olefin reaction product gas of manufacturing is transported in the separator 32 by pipeline 316 and 312.

On the other hand, separated propene/but-1-ene contains thing (the LPG manufacture method of 2-1) or propylene contains thing (the LPG manufacture method of 2-2) in separator 32, offers olefin hydrogenation reactor 34 via pipeline 317.In addition, hydrogen also offers olefin hydrogenation reactor 34 via pipeline 318.In olefin hydrogenation reactor 34, olefin hydrogenation catalyzer 34a is housed.In this olefin hydrogenation reactor 34, under the effect of olefin hydrogenation catalyzer, by the LPG manufacture method of 2-1, containing the synthetic main component of thing and hydrogen from propene/but-1-ene is the hydrocarbon gas (containing the lower alkane appropriate hydrocarbon gas) of propane and/or butane.The perhaps LPG manufacture method by 2-2 contains thing and the synthetic main component of hydrogen is the hydrocarbon gas (containing the lower alkane appropriate hydrocarbon gas) of propane from propylene.

After the method for knowing by the crowd was removed low boiling point component such as hydrogen and high boiling point is become to grade from institute's synthetic hydrocarbon gas as required, pressurization and cooling obtained product LPG from pipeline 219.

Not expression among the figure also has, though can be provided with compressor, heat exchanger, valve and power operation control device etc. as required on the LPG manufacturing installation.

Below, each operation of the manufacture method of LPG of the present invention is described.

[alkene manufacturing process]

In alkene manufacturing process, make at alkene under the effect of catalyzer, react by making at least a material in methyl alcohol and the dme, making main component is the olefin-containing gas of propylene and/or butylene.By being target product with propane, promptly make the LPG manufacture method of 1-2 of propane gas and the LPG manufacture method of 2-2, making main component is the olefin-containing gas of propylene.

As previously mentioned, except propylene and butylene, also contain senior alkene such as ethene and amylene in the resulting olefin-containing gas.In addition, this olefin-containing gas except containing olefines gas, also contains the water as by product usually.And then, in alkene manufacturing process, carry out the hydrogenation of olefin reaction, thereby in resulting olefin-containing gas, contain paraffinics such as propane and butane.

As reaction raw materials, both can use methyl alcohol or dme separately, also can use the mixture of methyl alcohol and dme.When the mixture that uses methyl alcohol and dme during as reaction raw materials, be not particularly limited the ratio that contains of methyl alcohol and dme, just can as long as suitably determine.

In addition, as reaction raw materials, also can use aqueous unpurified methyl alcohol and aqueous unpurified dme.

In alkene manufacturing process, compare as reaction raw materials with using methyl alcohol, when using dme, can suppress thermal discharge usually as reaction raw materials, thus easier control reaction.

In alkene manufacturing process, be fed in the gas in the reactor, except methyl alcohol and/or dme, can also contain other compositions such as water and rare gas element.Particularly when reaction raw materials is dme, by making the gas that is fed in the reactor with dme: the ratio of water=1: 1 (mol ratio) contains water, can improve the transformation efficiency that dme transforms to propane and butane.In addition,, also can further increase the selectivity of LPG hydrocarbon (propylene, butylene, propane and butane) sometimes, and suppress the inactivation of catalyzer by diluting as the methyl alcohol of reaction raw materials and at least a material in the dme with hydrogen or rare gas element etc.

Make catalyzer as alkene, can enumerate in the condensation reaction that generates hydrocarbon from methyl alcohol and/or generate the zeolite that demonstrates katalysis the condensation reaction of hydrocarbon etc. from dme.

In this alkene manufacturing process, can think that according to described in the following formula (I) the synthetic main component of at least a material from methyl alcohol and dme is the olefines of propylene and/or butylene.Wherein, in the following formula (I), generating carbene (H ₂C :) time can generate water as by product.

[changing 1]

In the generative process of this alkene, at first, in the micropore of the zeolite by making catalyzer at alkene, under the acid point of in its space, arranging and the synergy of alkali point, through the dehydration reaction generation carbene (H of methyl alcohol ₂C :).Then, by the polyreaction of carbene, generating main component is the alkene of propylene and/or butylene.Illustrate further, the polymerization carbene generates ethene during as dimer, perhaps as tripolymer by generating propylene with ethylene reaction, perhaps as the tetramer by generating butylene with propylene reaction or the dimerization by ethene.

In addition, in the generative process of this alkene, also following reaction can take place, promptly the dehydration dimerization by methyl alcohol generates dme, hydration reaction by dme generates methyl alcohol, decomposition by ethene etc. generates carbene, and the polymerization by light alkene generates higher alkene, and the decomposition by higher alkene, the cyclisation of alkene and dehydrogenation generate aromatic hydrocarbons, conjugated hydrocarbons compound and stable hydrocarbon with reactions such as the tar of conjugated hydrocarbons compound with cyclopentadiene based structures etc. or coking.

Among the present invention, in the middle of above-mentioned reaction, to the alkene of the carbonatoms that is equivalent to target product LPG or the formation reaction of its precursor is the formation reaction of carbene and the reaction that generates lower hydrocarbon such as ethene, propylene, butylene by the polymerization of carbene, the reaction of carbene and ethene or propylene and the reaction of the dimerization of ethene, it is very important that the reaction beyond the decomposition of higher alkene is controlled.By the main component reaction controlled with the olefines that generates is that propylene and/or butylene are very important.

For this reason, it is very important using the zeolite with suitable strength of acid, acid amount (acid concentration) and micropore diameter to make catalyzer as alkene.

Make catalyzer as alkene, aluminosilicophosphate (SAPO), ZSM-34, ZSM-5 such as SAPO-34 can give an example, the ratio (atomic ratio) of preferred Si and Al is the high silicon dioxide ZSM-5 more than 20, part or all of Al in the zeolite framework preferably contained the iron aluminosilicate of iron atom etc. by other element (atom) displacement or displaced metal silicate in zeolite framework.In addition, also can enumerate metals such as containing Ni, Co, Fe, Pt, Pd, Cu or Ag or elements such as Mg, P or lanthanide, the above-mentioned zeolite that has perhaps carried out ion-exchange with these metallic elements or Ti and Nb etc.By making it contain metal or compound, perhaps by carrying out ion-exchange, make the coke deposition with metal or compound, can adjust the strength of acid or the acid amount of zeolite.And, do the strength of acid or the acid amount that not only can make zeolite like this and reach equalization, near for example also can be respectively outer, the micropore inlet to zeolite micropore, micropore is inner adjusts, and, also can or carry out fine adjustment to micropore diameter in addition in the adjustment of carrying out strength of acid or acid amount.Also have, when also can make it to contain metal or compound or carrying out ion-exchange with metal or compound, the deposition coke.

Make catalyzer as alkene, preferred SAPO-34, ZSM-5, replaced a part of Al in the zeolite framework, promptly replaced the part of Al and in zeolite framework, contain the iron aluminosilicate of iron atom with iron atom, optionally angle from catalyst activity and LPG hydrocarbon (propylene, butylene, propane or butane), more preferably high silicon dioxide ZSM-5, have the iron aluminosilicate of MFI structure, from the selectivity of propane and butane and the angle of catalyst life, especially preferably has the iron aluminosilicate of MFI structure.

The ratio (atomic ratio) of Si among the high silicon dioxide ZSM-5 and Al is preferably more than 20 below 100, and is preferred especially more than 20 below 80.When using methyl alcohol as reaction raw materials, generate the angle of the transformation efficiency of propane and butane from methyl alcohol, the ratio (atomic ratio) of the Si among the ZSM-5 and Al is further preferably more than 20 below 40.On the other hand, when using dme as reaction raw materials, particularly generate the angle of the transformation efficiency of propane and butane from dme, the ratio (atomic ratio) of the Si among the ZSM-5 and Al is further preferably more than 35 below 55.No matter be to use methyl alcohol also to be to use dme as reaction raw materials, along with the increase of the Si among the ZSM-5 with the ratio (atomic ratio) of Al, there is trend of rising in the selectivity of LPG hydrocarbon (propylene, butylene, propane or butane).

Make catalyzer as alkene, preferred ZSM-5, the iron aluminosilicate (iron aluminosilicate) of a part of Al in the preferred above-mentioned especially zeolite framework of having replaced high silicon dioxide ZSM-5 with Fe with MFI structure.By with a part of Al in the Fe displacement zeolite framework, can when keeping high activity of catalyst, further suppress the generation of higher alkene, ester ring type hydrocarbon and aromatic hydrocarbons, can improve the selectivity of LPG hydrocarbon (propylene, butylene, propane or butane).

Be not only iron aluminosilicate among the present invention with MFI structure, with the homotype zeolite facies ratio that does not contain the iron atom Al of Fe displacement zeolite framework (with), the selectivity of LPG hydrocarbon (propylene, butylene, propane or butane) that contains the iron aluminosilicate of iron atom in zeolite framework is also higher.As the alkene catalyst for producing, from the selectivity of LPG hydrocarbon, preferred iron aluminosilicate.Wherein, from the angle of catalyst activity, a part of Al in the zeolite framework of preferred especially ZSM-5 is promptly had the iron aluminosilicate of MFI structure by Fe metathetical iron aluminosilicate.

As the iron aluminosilicate, preferably in zeolite framework, contain the iron aluminosilicate catalyzer that iron atom and Fe/ (Al+Fe) are 0.05 than (atomic ratio) more than (Al 5% replaced by Fe).More preferably contain iron atom and Fe/ (Al+Fe) (Al 10% replaced by Fe) the above iron aluminosilicate catalyzer that is 0.10 than (atomic ratio).By making Fe/ (Al+Fe) than in above-mentioned scope, can further improve the selectivity of LPG hydrocarbon, promptly embody the effect that contains iron atom in the zeolite framework more fully.

As the iron aluminosilicate, preferably in zeolite framework, contain the iron aluminosilicate catalyzer that iron atom and Fe/ (Al+Fe) are 0.45 than (atomic ratio) below (Al 45% replaced by Fe).By making Fe/ (Al+Fe), can obtain higher catalyst activity than in above-mentioned scope.When Fe/ (Al+Fe) when excessive, for example Fe/ (Al+Fe) than be 1 (Al 100% replaced by Fe), be the ferrosilicate that the Al in the zeolite framework has all been replaced by Fe, its catalyst activity has a declining tendency.

In addition, the Si/ of iron aluminosilicate (Al+Fe) than (atomic ratio) more preferably more than 20 below 100.When using methyl alcohol as reaction raw materials, generate the angle of the transformation efficiency of propane and butane from methyl alcohol, the Si/ of iron aluminosilicate (Al+Fe) is than (atomic ratio) more preferably more than 20 below 70.On the other hand, when using dme as reaction raw materials, particularly generate the angle of the transformation efficiency of propane and butane from dme, the Si/ of iron aluminosilicate (Al+Fe) is than (atomic ratio) more preferably more than 25 below 80.

Make catalyzer as the alkene that uses in the present invention, the iron aluminosilicate with MFI structure of preferred Hydrogen.In addition, this iron aluminosilicate can contain the heteroatomss such as gallium beyond the deironing in zeolite framework, but does not preferably contain the heteroatomic iron aluminosilicate beyond the iron usually.

Also have, can use a kind of alkene to make catalyzer, also can use the alkene more than 2 kinds to make catalyzer simultaneously.In addition, alkene manufacturing catalyzer can contain other added ingredientss under the prerequisite of not damaging its required effect.For example, use after can using the above-mentioned catalyzer of dilution such as quartz sand, but usually preferably with using after the moulding such as alumina adhesive.

In addition, when reacting on fixed bed, the catalyst layer that contains alkene manufacturing catalyzer also can change its composition according to the flow direction of unstripped gas.

If the main component of the olefines that generates will be controlled to be propylene and/or butylene, importantly control reaction conditions, particularly control the duration of contact that unstripped gas and alkene are made catalyzer.The formation reaction of the polymerization of carbene, the alkene such as polymerization of alkene is a successive reaction, and it is long more that unstripped gas (in methyl alcohol and the dme at least a) and alkene are made duration of contact of catalyzer, might generate the many alkene of carbonatoms more.

Can obtain with propylene and/or butylene is the olefines of main component or the duration of contact of making catalyzer based on the unstripped gas and the alkene of the hydrocarbon of such olefines, different with the kind of the catalyzer that uses or other reaction conditionss etc.In the present invention, also can carry out the building-up reactions of alkene in advance, determine the duration of contact of unstripped gas and alkene manufacturing catalyzer.

Reaction also can be undertaken by fixed bed, thermopnore or moving-bed.But when catalyst layer is set more than 2 layers, preferably react with fixed bed.The reaction conditionss such as duration of contact of unstripped gas composition, temperature of reaction, reaction pressure and catalyzer can be made suitably decision according to kind, performance and the shape etc. of the catalyzer that uses.

For example, make catalyzer, when using the high silicon dioxide ZSM-5 zeolite of Hydrogen or having the iron aluminosilicate of MFI structure, can under condition as described below, react as alkene.

As mentioned above, be fed in the gas in the reactor except methyl alcohol and at least a material in the dme, can also contain for example other compositions such as water and rare gas element as reaction raw materials.In addition,, be not particularly limited the ratio that contains of methyl alcohol and dme, just can as long as suitably determine when the mixture that uses methyl alcohol and dme during as reaction raw materials.

From the angle of catalyst activity, temperature of reaction is preferably more than 320 ℃, and more preferably more than 360 ℃, in addition, from the angle of selectivity and catalyst life, temperature of reaction is preferably below 460 ℃, more preferably below 440 ℃.

From the angle of the operability of catalyst activity, selectivity and device, reaction pressure is preferably more than 0.1MPa, more preferably more than the 0.11MPa.In addition, from the angle of economy and security, reaction pressure is preferably below 2MPa, more preferably below the 0.99MPa.

From the angle of economy, space-time speed is preferably at 1000H ^-1More than, more preferably 2000H ^-1More than.In addition, from active and angle optionally, space-time speed is preferably 40000H ^-1Below, more preferably 20000H ^-1Below.

Be fed to the gas in the reactor, can be sent in the reactor in batches, thus can control reaction temperature.

Reaction can utilize fixed bed, thermopnore or moving-bed etc. to carry out, but preferably selectes from the control of temperature of reaction and two aspects of renovation process of catalyzer.For example, as fixed bed, can use quenching type reactor, row cast reactor, the inside of inner multistage quenching mode etc. to contain multi-stage type reactor, multistage cooling footpath stream mode or two sleeve pipe exchange type of a plurality of heat exchangers etc. or spiral coil cooling tube is built-in or other reactors such as mixed flow mode etc.

For controlled temperature, alkene is made catalyzer also can enough silicon-dioxide, aluminum oxide etc. or inertia and stable thermal conductor dilute and use.In addition, be purpose with the controlled temperature, alkene manufacturing catalyzer also can be coated on the heat-exchanger surface and use.

Usually with zeolite during as catalyzer and from the synthetic olefines of methyl alcohol and/or dme, zeolite catalyst can be easy to inactivation because of coking etc.For example, in the present invention, when H-ZSM-5 or alkene such as iron aluminosilicate with MFI structure are made catalyst deactivation, can make catalyst regeneration by under the high temperature about 500 ℃, carrying out roast.Particularly repeat to allow iron aluminosilicate carry out building-up reactions and aforesaid catalyst regeneration that methyl alcohol and/or dme generate alkene, stability that increases catalyzer and the tendency that reduces deactivation rate are arranged with MFI structure.From this point, alkene is made the iron aluminosilicate that the most suitable use of catalyzer has the MFI structure.

[water sepn operation]

In the olefin-containing gas that in above-mentioned alkene manufacturing process, obtains, except containing olefines, paraffinic, also contain water usually as by product.Therefore, preferably before following separation circuit, from the olefin-containing gas that alkene manufacturing process, obtains, separate water outlet.

In addition, in the olefin reaction product gas that from following conversion of olefines operation, obtains, also except containing olefines, paraffinic hydrocarbons, also contain water sometimes.Usually be sent in the 2nd the LPG manufacture method of olefin reactor at the gas that will add at least a material in methyl alcohol and/or the dme, contain water in the olefin reaction product gas that obtains as by product.At this moment, preferably before following separation circuit, from the olefin reaction product gas that the conversion of olefines operation, obtains, separate water outlet.

When branch is dried up from olefin-containing gas and olefin reaction product gas, can be dried up from wherein dividing respectively, but preferably in olefin-containing gas, add after the olefin reaction product gas, carry out water sepn once.

The method that the separation of water can separate by liquid liquid for example, know through crowds such as refrigerative gas-liquid separations is carried out.Separation condition can also can be made suitably decision according to the method that the crowd knows.

[separation circuit]

In separation circuit, for the olefin-containing gas that in above-mentioned alkene manufacturing process, obtains, preferably in above-mentioned water sepn operation, carried out the olefin-containing gas of water sepn, and the olefin reaction product gas that in following conversion of olefines operation, obtains, preferably in above-mentioned water sepn operation, carried out the olefin reaction product gas of water sepn, unreacted raw material such as the further separation of methanol of knowing by the crowd of method and/or dme as required, the propene/but-1-ene that is separated into main component at least and is propylene and/or butylene contains thing, main component is that to contain thing and main component be that the amylene of amylene contains thing (the LPG manufacture method of 1-1 and the LPG manufacture method of 2-1) to the ethene of ethene.Perhaps, it being separated at least main component is that to contain thing, main component be that to contain thing and main component be that the butylene of butylene contains thing (the LPG manufacture method of 1-2 and the LPG manufacture method of 2-2) for the ethene of ethene for the propylene of propylene.

Here, the propene/but-1-ene in the LPG manufacture method of 1-1 and the LPG manufacture method of 2-1 contains thing, and the propylene in the LPG manufacture method of 1-2 and the LPG manufacture method of 2-2 contains thing and is also referred to as the LPG hydrocarbon and contains thing.In addition, the amylene in the LPG manufacture method of the LPG manufacture method of 1-1 and 2-1 contains butylene in the LPG manufacture method of the LPG manufacture method of thing, 1-2 and 2-2 and contains thing and be also referred to as higher alkene and contain thing.

In the present invention, the part in the olefin reaction product gas that obtains in following conversion of olefines operation can be retracted to outside the system, and remainder is offered separator together with olefin-containing gas.

Also have, be fed in the olefin-containing gas and olefin reaction product gas in the separator, can contain moisture, methyl alcohol and/or dme, but preferred alkenes class or be the hydrocarbon of main component with the olefines.

In addition, also can suitably determine to add to the amount of the olefin reaction product gas in the olefin-containing gas, promptly be fed to the content of the olefin reaction product gas in the gas of separator.

In this separation circuit, can be as required from the olefin-containing gas that separated moisture, methyl alcohol and/or dme and olefin reaction product gas after separating ethene contains thing, separate higher alkene again and contain thing.Perhaps after the separation higher alkene contained thing, separating ethene contained thing again.

In addition, can use identical separator as required, will separate the olefin-containing gas and the olefin reaction product gas of moisture, methyl alcohol and/or dme, be separated into that the LPG hydrocarbon contains thing, ethene contains thing and higher alkene contains thing.

The separation that ethene contains thing contains separating of thing with higher alkene, can be undertaken by the method that crowds such as for example gas-liquid separation, distillation, extraction or extractive distillation know.More particularly, can carry out gas-liquid separation at normal temperatures or through cooling off laggard promoting the circulation of qi liquid separation etc. by pressurization.In addition, can pass through membrane sepn, also can be by separating after the combination of methods such as membrane sepn and gas-liquid separation, distillation, extraction or extractive distillation.

Here, being lower than the material propylene boiling point or that have sublimation point (low boiling point component) becomes ethene usually and contains thing.In addition, in the LPG manufacture method of the LPG of 1-1 of the present invention manufacture method and 2-1, the material (high boiling point composition) that is higher than the butane boiling point becomes higher alkene usually and contains thing (amylene contains thing).In the LPG manufacture method of the LPG of 1-2 of the present invention manufacture method and 2-2, the material (high boiling point composition) that is higher than the propylene boiling point becomes higher alkene usually and contains thing (butylene contains thing).

Wherein, separation condition can be made suitably decision according to the method that the crowd knows.

[conversion of olefines operation]

In the conversion of olefines operation of LPG manufacture method the 1st, under the effect of conversion of olefines catalyzer, by olefines is reacted [intersect replacement(metathesis)reaction (cross metathetical reation) or polymerization/decomposition reaction], promptly contain thing and higher alkene from the ethene that obtains above-mentioned separation circuit and contain thing (amylene contains thing or butylene contains thing) and react, making main component is the olefin reaction product gas of propylene and/or butylene.

In the conversion of olefines operation of LPG manufacture method the 2nd, under the effect of conversion of olefines catalyzer, by at least a material in olefines and methyl alcohol and the dme is reacted, promptly contain thing, higher alkene from the ethene that obtains above-mentioned separation circuit and contain that at least a material reacts in thing (amylene contains thing or butylene contains thing) and methyl alcohol and the dme, making main component is the olefin reaction product gas of propylene and/or butylene.

In the conversion of olefines operation, be fed to the gas in the reactor, can be to the ethene that in separation circuit, obtains contain thing, higher alkene contains the material that other compositions of at least a interpolation in thing or methyl alcohol and the dme form.In addition, being fed to the gas in the reactor in the conversion of olefines operation, also can be to contain that thing and/or higher alkene contain that thing is isolated predetermined component and the material that obtains from the ethene that obtains separation circuit.

In this conversion of olefines operation, the replacement(metathesis)reaction or the polymerization/decomposition reaction of the olefines shown in following formula (II) for example might take place.

[changing 2]

(II)

Wherein, above-mentioned formula (II) is the building-up reactions of propylene, but the building-up reactions of other alkene also can take place, and usually except propylene, also contains senior alkene such as butylene, ethene, amylene in the olefin reaction product gas that obtains.

In addition, in the conversion of olefines operation, also can carry out the hydrogenation of olefin reaction, and the olefin reaction product gas that obtains can contain paraffinics such as propane and butane.

As the conversion of olefines catalyzer, the metathesis catalyst that the crowd that can give an example knows is specially transistion metal compound of 4A～8A families such as the oxide compound of Mo, W and Re or carbonyl compound etc.In addition, can in carriers such as silicon-dioxide, aluminum oxide, silica/alumina or zeolite, use behind these catalyzer of load, perhaps also can use their mixture.And then as the conversion of olefines catalyzer, the alkene that also can give an example above-mentioned is made catalyzer.

As the conversion of olefines catalyzer, preferred above-mentioned alkene is made catalyzer, from the optionally angle of catalyst activity and LPG hydrocarbon (propylene, butylene, propane or butane), more preferably ZSM-5, the ratio (atomic ratio) of preferred especially Si and Al are the high silicon dioxide ZSM-5 more than 20.

The ratio (atomic ratio) of the Si of high silicon dioxide ZSM-5 and Al is more preferably more than 20 below 200.When using methyl alcohol as reaction raw materials, generate the angle of the transformation efficiency of propane and butane from methyl alcohol, the ratio (atomic ratio) of the Si of ZSM-5 and Al is further preferably more than 20 below 140.On the other hand, when using dme as reaction raw materials, particularly generate the angle of the transformation efficiency of propane and butane from dme, the ratio (atomic ratio) of the Si of ZSM-5 and Al is further preferably more than 25 below 160.In addition, no matter be to use methyl alcohol also to be to use dme as reaction raw materials, along with the increase of Si with the ratio (atomic ratio) of Al of ZSM-5, the selectivity of LPG hydrocarbon (propylene, butylene, propane or butane) has trend of rising.

The conversion of olefines catalyzer of Shi Yonging in the present invention, the high silicon dioxide ZSM-5 of preferred Hydrogen.

Also have, can use a kind of conversion of olefines catalyzer, also can use conversion of olefines catalyzer more than 2 kinds simultaneously.In addition, the conversion of olefines catalyzer can contain other added ingredientss under the prerequisite of not damaging its required effect.For example, can use the above-mentioned catalyzer of dilution such as quartz sand.

In addition, when reacting with fixed bed, the catalyst layer that contains the conversion of olefines catalyzer also relatively the flow direction of unstripped gas change its composition.

Reaction also can be undertaken by fixed bed, thermopnore or moving-bed.But when catalyst layer is set more than 2 layers, preferably carry out with fixed bed.The reaction conditionss such as duration of contact of unstripped gas composition, temperature of reaction, reaction pressure and catalyzer can suitably be determined according to kind, performance and the shape etc. of the catalyzer that uses.

For example, as the conversion of olefines catalyzer, when using the high silicon dioxide ZSM-5 zeolite of Hydrogen, can under condition as described below, react.

When the LPG manufacture method that adopts the 1st, be fed to gas in the reactor and contain that the ethene that obtains contains thing and higher alkene contains thing (amylene contains thing or butylene contains thing) in above-mentioned separation circuit.

Being fed to ethene in the gas in the reactor contains thing and higher alkene and contains containing ratio and can suitably determining of thing.

Usually, be fed to higher alkene in the gas in the reactor and contain thing and contain the ratio that contains of thing with respect to ethene, from the angle of conversion of ethylene, be benchmark with carbon, preferred more than 0.5, more preferably more than 1.In addition, be fed to higher alkene in the gas in the reactor and contain thing and contain the ratio that contains of thing with respect to ethene, from the angle of product selectivity, be benchmark with carbon, preferred below 10.

Be fed to gas in the reactor except containing ethene and contain thing and higher alkene containing the thing, can also contain for example water and rare gas element etc.

Also have, the ethene that obtains in separation circuit contains thing and higher alkene contains thing, both can offer reactor through mixing, also can offer reactor respectively.In addition, be fed to the gas of reactor, can send in the reactor in batches.

The ethene that obtains in separation circuit can be contained a part that thing and/or higher alkene contain thing is retracted to outside the system remainder is offered reactor.In addition, the part circulation that also ethene that obtains can be contained thing in separation circuit offers alkene manufacturing process.

When the LPG manufacture method that adopts the 2nd, be fed to gas in the reactor and contain that the ethene that obtains contains thing, higher alkene contains at least a material in thing (amylene contains thing or butylene contains thing) and methyl alcohol and the dme in above-mentioned separation circuit.

Being fed to ethene in the gas in the reactor contains thing, higher alkene and contains containing ratio and can suitably determining of at least a material in thing and methyl alcohol and the dme.

Usually, be fed to higher alkene in the gas in the reactor and contain thing and contain the ratio that contains of thing with respect to ethene, from the angle of conversion of ethylene, be benchmark with carbon, preferred more than 0.1, more preferably more than 0.2.In addition, be fed to higher alkene in the gas in the reactor and contain thing and contain the ratio that contains of thing with respect to ethene, from the angle of product selectivity, be benchmark with carbon, preferred below 10.

In addition, be fed to methyl alcohol in the gas in the reactor and/or dme and contain the ratio that contains of thing with respect to ethene, from the angle of conversion of ethylene, be benchmark with carbon, preferred more than 0.2, more preferably more than 0.3.In addition, be fed to methyl alcohol in the gas in the reactor and/or dme and contain the ratio that contains of thing with respect to ethene, from the angle of conversion of ethylene and product selectivity, be benchmark with carbon, preferred below 2, more preferably below 1.4.

Be fed to that gas in the reactor contains thing except containing ethene, higher alkene contains thing and methyl alcohol and/or the dme, can also contain for example water and rare gas element etc.

Also have, the ethene that obtains in separation circuit contains thing, higher alkene contains thing, methyl alcohol and dme, both can offer reactor through mixing, also can offer reactor respectively.In addition, be fed to the gas of reactor, can send in the reactor in batches.

The ethene that obtains in separation circuit can be contained a part that thing and/or higher alkene contain thing is retracted to outside the system remainder is offered reactor.In addition, the part circulation that also ethene that obtains can be contained thing in separation circuit offers alkene manufacturing process.

From catalyst activity and angle optionally, temperature of reaction is preferably more than 350 ℃, and more preferably more than 380 ℃, in addition, from the angle of catalyst life, temperature of reaction is preferably below 460 ℃, more preferably below 430 ℃.

From catalyst activity, optionally with the device operability angle, reaction pressure is preferably more than 0.1MPa, more preferably more than the 0.11MPa.In addition, from the angle of economy and security, reaction pressure is preferably below 2MPa, more preferably below the 0.99MPa.

From the angle of economy, space-time speed is preferably at 500H ^-1More than, more preferably 1000H ^-1More than.In addition, from catalyst activity and angle optionally, space-time speed is preferably 40000H ^-1Below, more preferably 20000H ^-1Below.

Be fed to the gas in the reactor, be sent in the reactor in batches, thus can control reaction temperature.

Reaction can be carried out on fixed bed, thermopnore or moving-bed etc., but preferably selectes from the control of temperature of reaction and two aspects of renovation process of catalyzer.For example, as fixed bed, can use quenching type reactor, row cast reactor, the inside of inner multistage quenching mode etc. to contain multi-stage type reactor, multistage cooling footpath stream mode or two sleeve pipe exchange type of a plurality of heat exchangers etc. or spiral coil cooling tube is built-in or other reactors such as mixed flow mode etc.

For controlled temperature, the conversion of olefines catalyzer also can enough silicon-dioxide, aluminum oxide etc. or inertia and stable thermal conductor dilute and use.In addition, be purpose with the controlled temperature, the conversion of olefines catalyzer also can be coated on the heat-exchanger surface and use.

Among the present invention, part or all circulation of the olefin reaction product gas that obtains is offered above-mentioned separation circuit or water sepn operation.Then, in separation circuit, isolate from the olefin reaction product gas (hydrocarbon that contains propylene and/or butylene) that obtains that ethene contains thing and higher alkene contains thing.Therefore, can make propylene and/or butylene with at least a material of higher yield from methyl alcohol and dme, and then make propane and/or butane.

The olefin reaction product gas can all circulate and offer separation circuit or water sepn operation, in addition, also a part can be retracted to outside the system, and the remainder circulation is offered separation circuit or water sepn operation.Also can from the olefin reaction product gas, only isolate the composition that needs and circulate and offer separation circuit or water sepn operation.

[olefin hydrogenation operation]

In the olefin hydrogenation operation, under the effect of olefin hydrogenation catalyzer, by alkene and hydrogen are reacted, utilize the LPG manufacture method of 1-1 and the LPG manufacture method of 2-1, make the propene/but-1-ene that obtains from above-mentioned separation circuit contain thing and hydrogen reacts, making main component is the liquefied petroleum gas (LPG) (LPG) of the hydrocarbon of propane and/or butane.Perhaps, utilize the LPG manufacture method of 1-2 and the LPG manufacture method of 2-2, make the propylene that obtains from above-mentioned separation circuit contain thing and hydrogen reacts, making main component is the liquefied petroleum gas (LPG) (LPG) of the hydrocarbon polymer of propane.

In this olefin hydrogenation operation, according to following formula (III), propylene and hydrogen are reacted, make propane, according to following formula (IV), butane and hydrogen are reacted, make butane.

[changing 3]

(III)

[changing 4]

(IV)

As the olefin hydrogenation catalyzer, the olefin hydrogenation catalyzer that the crowd that can give an example knows, specifically, metal or alloys such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu or Re are arranged, the oxide compound of metals such as Cu, Co, Ni, Cr, Zn, Re, Mo or W, the sulfide of metals such as Co, Re, Mo or W etc.In addition, the material of these catalyzer that can use in carriers such as carbon, silicon-dioxide, aluminum oxide, silica/alumina, zeolite load perhaps also can use their mixture.And then as the olefin hydrogenation catalyzer, the alkene that also can give an example above-mentioned is made catalyzer.

As the olefin hydrogenation catalyzer, preferred palladium catalyst or platinum catalyst.

Also have, can use a kind of olefin hydrogenation catalyzer, also can use olefin hydrogenation catalyzer more than 2 kinds simultaneously.In addition, the olefin hydrogenation catalyzer can contain other added ingredientss under the prerequisite of not damaging its required effect.For example, can use the above-mentioned catalyzer of dilution such as quartz sand.

In addition, when reacting with fixed bed, the catalyst layer that contains the olefin hydrogenation catalyzer also relatively the flow direction of unstripped gas change its composition.

Reaction also can utilize fixed bed, thermopnore or moving-bed to carry out.But when catalyst layer is set more than 2 layers, preferably carry out with fixed bed.The reaction conditionss such as duration of contact of unstripped gas composition, temperature of reaction, reaction pressure and catalyzer, the method that can adopt the crowd to know is suitably determined according to kind, performance and the shape etc. of the catalyzer that uses.

For example, when as the olefin hydrogenation catalyzer, when using Pd-aluminum oxide (supported palladium on aluminum oxide), can under condition as described below, react.

Be fed to and contain in the gas in the reactor that the propene/but-1-ene that obtains contains thing or propylene contains thing and hydrogen in above-mentioned separation circuit.

Being fed to propene/but-1-ene in the gas in the reactor contains thing or propylene and contains containing ratio and can suitably determining of thing and hydrogen.

Usually, be fed to hydrogen in the gas of reactor and contain ratio (H with respect to alkene (mainly being propylene, butylene) ₂/ C _nH _2nMol ratio), preferred more than 1.1 from alkene being carried out hydrogenant angle more fully, more preferably more than 1.5.In addition, be fed to hydrogen in the gas of reactor and contain ratio (H with respect to alkene (mainly being propylene, butylene) ₂/ C _nH _2nMol ratio), preferred below 10 from the angle of economy, more preferably below 5.

Be fed in the gas in the reactor, propene/but-1-ene contains thing or propylene contains thing and the hydrogen except containing, and can also contain for example water and rare gas element etc.

Also have, the propene/but-1-ene that obtains in separation circuit contains thing or propylene contains thing and hydrogen (gas of hydrogen), both can offer reactor through mixing, also can offer reactor respectively.In addition, be fed to the gas of reactor, can send in the reactor in batches.

From the angle of catalyst activity, temperature of reaction is preferably more than 120 ℃, and more preferably more than 140 ℃, in addition, from selectivity and the angle of removing reaction heat, temperature of reaction is preferably below 400 ℃, more preferably below 350 ℃.

From the angle of catalyst activity, reaction pressure is preferably more than 0.11MPa.In addition, from the angle of economy and security, reaction pressure is preferably below 3MPa, more preferably below the 2MPa.

From the angle of economy, space-time speed is preferably at 1000H ^-1More than, more preferably 1500H ^-1More than.In addition, from active angle, space-time speed is preferably 40000H ^-1Below, more preferably 20000H ^-1Below.

In the reaction product gas that so obtains (containing the lower alkane appropriate hydrocarbon gas), the main component of contained hydrocarbon is propane and/or butane.From the angle of liquefaction property, the content that contains propane in the lower alkane appropriate hydrocarbon gas and butane adds up to The more the better.

And then, from the angle of incendivity and vapour pressure characteristic, what containing of obtaining, preferably propane was Duoed than butane in the lower alkane appropriate hydrocarbon gas.

In addition, in containing in the lower alkane appropriate hydrocarbon gas of obtaining, the high boiling point composition that contain unreacted raw materials such as hydrogen sometimes, is lower than the low boiling point component propane boiling point or that have sublimation point and is higher than the butane boiling point.For this reason, isolate low boiling point component or high boiling point composition the lower alkane appropriate hydrocarbon gas from containing of obtaining as required, thereby to obtain with propane or butane be the liquefied petroleum gas (LPG) (LPG) of main component.

In addition, in order to obtain liquefied petroleum gas (LPG), can pressurize as required and/or cool off.

When using fuel,, for example preferably the content of the low boiling point component among the LPG is dropped to below 5% and (also contain 0%) by separation from the angle of safe handling as life.

According to the manufacture method of LPG of the present invention, can make the LPG that main component is propane and/or butane, the content that is specially propane and butane adds up to more than 90%, further is the LPG that (also contains 100%) more than 95%.

In addition, according to the manufacture method of LPG of the present invention, can make the LPG that main component is a propane, the content that is specially propane is more than 70%, further is the LPG that (also contains 100%) more than 80%.According to the manufacture method of LPG of the present invention, can make LPG with the composition that is suitable for being widely used as home-use, commercial propane gas with fuel.

In addition, methyl alcohol and the dme that uses as raw material in the present invention at present can be in industrial manufacturing.

Methyl alcohol can be by method manufacturing as described below, promptly, will be by the water vapor upgrading method of Sweet natural gas (methane), compound upgrading method or the water-based gas of making from the synthetic gas of thermal upgrading manufactured or from coal tar carbon etc. as raw material, under the effect of methanol synthesis catalyst, carbon monoxide and hydrogen are reacted, make methyl alcohol.In the product that obtains (unpurified methyl alcohol), contain water usually and as dme of by product etc.Usually this unpurified methyl alcohol converts refining methyl alcohol to and need consume lot of energy.In the present invention, a very big advantage is to use this unpurified methyl alcohol as reaction raw materials.

On the other hand, for example, dme can use solid acid catalysts such as aluminum phosphate and make by the dehydration reaction of methyl alcohol.And then, just be to use the mixed catalyst of methanol synthesis catalyst and methanol dehydration catalyst in the method for practicability, directly do not make the method for dme from synthetic gas via methyl alcohol.In the product that obtains (unpurified dme), contain water usually and as methyl alcohol of by product etc.Usually this unpurified dme converts refining dimethyl ether to and need consume lot of energy.In the present invention, a very big advantage is to use this unpurified dme as reaction raw materials.

[embodiment]

Below, further describe the present invention by embodiment.And the present invention has more than and is limited to these embodiment.

(reference example 1)

Use LPG manufacturing installation (system) shown in Figure 1 to make LPG.

Make catalyzer 21a as alkene, using ratio (atomic ratio) by the Si of 65% (wt) and Al is the catalyzer that the alumina adhesive of 45 Hydrogen ZSM-5 and 35% (wt) is made.As conversion of olefines catalyzer 23a, use identical catalyzer with alkene manufacturing catalyzer 21a, be the catalyzer that the alumina adhesive of 45 Hydrogen ZSM-5 and 35% (wt) is made promptly by the ratio (atomic ratio) of the Si of 65% (wt) and Al.As olefin hydrogenation catalyzer 24a, use the Pd-aluminum oxide of 0.5% (wt).

At first, at 400 ℃ of temperature of reaction, reaction pressure 0.12MPa, H ₂GHSV 20000H ^-1Under the condition of methyl alcohol dividing potential drop 0.04MPa, make methyl alcohol make reactor 21 by alkene, described alkene is made and has been filled the alkene manufacturing catalyzer 21a that is made by the alumina adhesive of the Hydrogen ZSM-5 of 65% (wt) (Si with Al ratio (atomic ratio)=45) and 35% (wt) in the reactor 21.As a result, the transformation efficiency that generates hydrocarbon from methyl alcohol is 94.1%, is benchmark in carbon, consisting of of hydrocarbon in the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 23.7%, it is 45.1% that propylene contains thing, remaining is that main component is that the butylene of butylene contains thing.

Then, from the reaction product gas that obtains, remove moisture etc. by gas-liquid separation, in separator 22, by multistage distillation this has been removed the reaction product gas of moisture etc. and the reaction product gas of carrying from olefin reactor 23, be separated into propylene contain thing, be lower than the propylene boiling point and main component is that the ethene of ethene contains thing and is higher than the propylene boiling point and main component is that the butylene of butylene contains thing.

At 420 ℃ of temperature of reaction, reaction pressure 0.12MPa and GHSV 8000H ^-1Condition under, make separated ethene contain thing and butylene and contain thing, filled the conversion of olefines catalyzer 23a that makes by the alumina adhesive of the Hydrogen ZSM-5 that accounts for total amount 65% (wt) (Si with Al ratio (atomic ratio)=45) and 35% (wt) in the described olefin reactor 23 by olefin reactor 23.In carbon is benchmark, the consisting of of the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 22.0%, it is 40.5% that propylene contains thing, remaining is that main component is that the butylene of butylene contains thing.This reaction product gas that obtains is all offered separator 22.

On the other hand, at 330 ℃ of temperature of reaction, reaction pressure 0.12MPa, GHSV 20000H ^-1And H ₂Under the condition of/hydrocarbon (mol ratio)=4, make the propylene that obtains in separator 22 contain thing and hydrogen by olefin hydrogenation reactor 24, having filled 0.5% (wt) Pd-aluminum oxide in the described olefin hydrogenation reactor 24 is olefin hydrogenation catalyzer 24a.Adopt gas chromatography to analyze part hydrocarbon product from pipeline 219, the composition of result product is, propane is 92% (wt), and butane is 8% (wt).In addition, the accurate yield of the carbon back of the material benzenemethanol of this product is 63.3%.

[embodiment 1]

Use LPG manufacturing installation (system) shown in Figure 1 to make LPG.

Make catalyzer 21a as alkene, having used by Fe/ (Al+Fe) be 0.35 than (atomic ratio) (Al 35% replaced by Fe) and Si/ (Al+Fe) is the catalyzer that 50 Hydrogen iron aluminosilicate 65% (wt) with MFI structure and alumina adhesive 35% (wt) are made than (atomic ratio).As conversion of olefines catalyzer 23a, using ratio (atomic ratio) by the Si of 65% (wt) and Al is the catalyzer that the alumina adhesive of 45 Hydrogen ZSM-5 and 35% (wt) is made.As olefin hydrogenation catalyzer 24a, use the Pd-aluminum oxide of 0.5% (wt).

At first, at 400 ℃ of temperature of reaction, reaction pressure 0.12MPa, H ₂GHSV 20000H ^-1Under the condition of methyl alcohol dividing potential drop 0.04MPa, make methyl alcohol make reactor 21 by alkene, described alkene is made and has been filled the alkene manufacturing catalyzer 21a that is made by the alumina adhesive of the Hydrogen iron aluminosilicate with MFI structure of 65% (wt) (Fe/ (Al+Fe) is 0.35 than (atomic ratio), and (Al 35% replaced by Fe) and Si/ (Al+Fe) are 50 than (atomic ratio)) and 35% (wt) in the reactor 21.As a result, the transformation efficiency that generates hydrocarbon from methyl alcohol is 94.0%, is benchmark in carbon, consisting of of hydrocarbon in the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 7.3%, it is 54.1% that propylene contains thing, remaining is that main component is that the butylene of butylene contains thing.

Then, from the reaction product gas that obtains, remove moisture etc. by gas-liquid separation, in separator 22, by multistage distillation this is removed the reaction product gas of moisture etc. and the reaction product gas of carrying from olefin reactor 23, be separated into propylene contain thing, be lower than the propylene boiling point and main component is that the ethene of ethene contains thing and is higher than the propylene boiling point and main component is that the butylene of butylene contains thing.

At 420 ℃ of temperature of reaction, reaction pressure 0.12MPa and GHSV 8000H ^-1Condition under, make separated ethene contain thing and butylene and contain thing, filled the conversion of olefines catalyzer 23a that makes by the alumina adhesive of the Hydrogen ZSM-5 that accounts for total amount 65% (wt) (Si/Al is than (atomic ratio)=45) and 35% (wt) in the described olefin reactor 23 by olefin reactor 23.In carbon is benchmark, the consisting of of the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 22.0%, it is 40.3% that propylene contains thing, remaining is that main component is that the butylene of butylene contains thing.This reaction product gas that obtains is all offered separator 22.

On the other hand, at 330 ℃ of temperature of reaction, reaction pressure 0.12MPa, GHSV 20000H ^-1And H ₂Under the condition of/hydrocarbon (mol ratio)=4, make the propylene that obtains in separator 22 contain thing and hydrogen by olefin hydrogenation reactor 24, having filled 0.5% (wt) Pd-aluminum oxide in the described olefin hydrogenation reactor 24 is olefin hydrogenation catalyzer 24a.Adopt gas chromatography to analyze part hydrocarbon product from pipeline 219, the composition of result product is, propane is 95% (wt), and butane is 5% (wt).In addition, the accurate yield of the carbon back of the material benzenemethanol of this product is 68.3%.

[embodiment 2]

On the basis of embodiment 1, other conditions are all identical with embodiment 1, only changed the condition in the separator 22, to make reaction product gas that reactor 21 carries and the reaction product gas of carrying from olefin reactor 23 from alkene by multistage distillation, be separated into propylene and butylene contain thing, be lower than the propylene boiling point and main component is that the ethene of ethene contains thing and is higher than the butylene boiling point and main component is that the amylene of amylene contains thing.Make isolated ethene contain thing and amylene contains thing all by olefin reactor 23.In carbon is benchmark, in the composition of the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 22.0%, it is 73.0% that propylene and butylene contain thing, remaining is that main component is that the amylene of amylene contains thing.This reaction product gas that obtains is all offered separator 22.

Its result, when adopting the gas chromatography analysis from the part hydrocarbon product of pipeline 219, to be that 99% (wt) is above be propane and butane to the composition of product.In addition, the accurate yield of the carbon back of the material benzenemethanol of this product is 90.5%.

[embodiment 3]

Use LPG manufacturing installation (system) shown in Figure 2 to make LPG.

Make catalyzer 31a as alkene, using by Fe/ (Al+Fe) be 0.35 than (atomic ratio) (Al 35% replaced by Fe) and Si/ (Al+Fe) is the catalyzer that 50 Hydrogen iron aluminosilicate 65% (wt) with MFI structure and alumina adhesive 35% (wt) are made than (atomic ratio).As conversion of olefines catalyzer 33a, using ratio (atomic ratio) by the Si of 65% (wt) and Al is the catalyzer that the alumina adhesive of 45 Hydrogen ZSM-5 and 35% (wt) is made.As olefin hydrogenation catalyzer 34a, use the Pd-aluminum oxide of 0.5% (wt).

At first, at 400 ℃ of temperature of reaction, reaction pressure 0.12MPa, H ₂GHSV 20000H ^-1Under the condition of methyl alcohol dividing potential drop 0.04MPa, make methyl alcohol make reactor 31 by alkene, described alkene is made and has been filled the alkene manufacturing catalyzer 31a that is made by the alumina adhesive of the Hydrogen iron aluminosilicate with MFI structure of 65% (wt) [Fe/ (Al+Fe) is 0.35 than (atomic ratio), and (Al 35% replaced by Fe) and Si/ (Al+Fe) are 50 than (atomic ratio)] and 35% (wt) in the reactor 31.As a result, the transformation efficiency that generates hydrocarbon from methyl alcohol is 94.0%, is benchmark in carbon, consisting of of hydrocarbon in the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 7.3%, it is 54.1% that propylene contains thing, remaining is that main component is that the butylene of butylene contains thing.

Then, from the reaction product gas that obtains, remove moisture etc. by gas-liquid separation, in separator 32, by multistage distillation this is removed the reaction product gas of moisture etc. and the reaction product gas of carrying from olefin reactor 33, be separated into propylene contain thing, be lower than the propylene boiling point and main component is that the ethene of ethene contains thing and is higher than the propylene boiling point and main component is that the butylene of butylene contains thing.

At 410 ℃ of temperature of reaction, reaction pressure 0.12MPa and GHSV 10000H ^-1Condition under, make separated ethene contain thing and butylene contains the whole of thing and when being benchmark with carbon and ethene contain thing with the methyl alcohol of amount by olefin reactor 33, filled the conversion of olefines catalyzer 33a that makes by the alumina adhesive of the Hydrogen ZSM-5 (Si/Al is than (atomic ratio)=45) of 65% (wt) and 35% (wt) in the described olefin reactor 33.In carbon is benchmark, the consisting of of the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 16.0%, it is 45.2% that propylene contains thing, remaining is that main component is that the butylene of butylene contains thing.This reaction product gas that obtains is all offered separator 32.

On the other hand, at 330 ℃ of temperature of reaction, reaction pressure 0.12MPa, GHSV 20000H ^-1And H ₂Under the condition of/hydrocarbon (mol ratio)=4, make the propylene that obtains in separator 32 contain thing and hydrogen by olefin hydrogenation reactor 34,34 to have filled 0.5% (wt) Pd-aluminum oxide be olefin hydrogenation catalyzer 34a in the described olefin hydrogenation reactor.Adopt the part hydrocarbon product of gas chromatography analysis from pipeline 319, the composition of result product is, propane is 95% (wt), and butane is 5% (wt).In addition, the accurate yield of the carbon back of the material benzenemethanol of this product is 68.9%.

[embodiment 4]

On the basis of embodiment 3, other conditions are all identical with embodiment 3, only changed the condition of separator 32, to make reaction product gas that reactor 31 carries and the reaction product gas of carrying from olefin reactor 33 from alkene by multistage distillation, be separated into propylene and butylene contain thing, be lower than the propylene boiling point and main component is that the ethene of ethene contains thing and is higher than the butylene boiling point and main component is that the amylene of amylene contains thing.Make separated ethene contain thing and amylene contains thing all by olefin reactor 33.In carbon is benchmark, the consisting of of the reaction product gas that obtains, main component be the ethene of ethene to contain thing be 16.0%, it is 81.3% that propylene and butylene contain thing, remaining is that main component is that the amylene of amylene contains thing.This reaction product gas that obtains is all offered separator 32.

Its result, when adopting the gas chromatography analysis from the part hydrocarbon product of pipeline 319, to be that 99% (wt) is above be propane and butane to the composition of product.In addition, the accurate yield of the carbon back of the material benzenemethanol of this product is 90.8%.

As mentioned above, according to the present invention, as raw material, can less expensive ground making main component be the hydrocarbon of propane and/or butane, i.e. liquefied petroleum gas (LPG) (LPG) with at least a material in methyl alcohol and the dme.

Claims (12)

1, a kind of manufacture method of liquefied petroleum gas (LPG) is characterized in that, comprising:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and/or butylene and contain ethene and the olefin-containing gas of amylene;

(ii) separation circuit:

It is that to contain thing and main component be that the amylene of amylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propene/but-1-ene that is separated into main component at least and is propylene and/or butylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, react by making olefines, promptly contain thing and amylene and contain thing and react from the ethene that separation circuit, obtains, making main component is the olefin reaction product gas of propylene and/or butylene; With;

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propene/but-1-ene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane and/or butane.

2, a kind of manufacture method of liquefied petroleum gas (LPG) is characterized in that, comprising:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and contain ethene and the olefin-containing gas of butylene;

(ii) separation circuit:

It is that to contain thing and main component be that the butylene of butylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propylene that is separated into main component at least and is propylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, react by making olefines, promptly contain thing and butylene and contain thing and react from the ethene that separation circuit, obtains, making main component is the olefin reaction product gas of propylene; With

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propylene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane.

3, a kind of manufacture method of liquefied petroleum gas (LPG) is characterized in that, comprising:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and/or butylene and contain ethene and the olefin-containing gas of amylene;

(ii) separation circuit:

It is that to contain thing and main component be that the amylene of amylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propene/but-1-ene that is separated into main component at least and is propylene and/or butylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, by at least a material in olefines and methyl alcohol and the dme is reacted, promptly contain thing, amylene from the ethene that obtains separation circuit and contain that at least a material reacts in thing and methyl alcohol and the dme, making main component is the olefin reaction product gas of propylene and/or butylene; With

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propene/but-1-ene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane and/or butane.

4, a kind of manufacture method of liquefied petroleum gas (LPG) is characterized in that, comprising:

(i) alkene manufacturing process:

Make at alkene under the effect of catalyzer, at least a material in methyl alcohol and the dme is reacted, make main component and be propylene and contain ethene and the olefin-containing gas of butylene;

(ii) separation circuit:

It is that to contain thing and main component be that the butylene of butylene contains thing for the ethene of ethene that olefin-containing gas that will obtain in alkene manufacturing process and the olefin reaction product gas that obtains in the conversion of olefines operation, the propylene that is separated into main component at least and is propylene contain thing, main component;

(iii) conversion of olefines operation:

Under the effect of conversion of olefines catalyzer, by at least a material in olefines and methyl alcohol and the dme is reacted, promptly contain thing, butylene from the ethene that obtains separation circuit and contain that at least a material reacts in thing and methyl alcohol and the dme, making main component is the olefin reaction product gas of propylene; With

(iv) olefin hydrogenation operation:

Under the effect of olefin hydrogenation catalyzer, alkene and hydrogen are reacted, promptly contain thing and hydrogen reacts from the propylene that separation circuit, obtains, making main component is the liquefied petroleum gas (LPG) of the hydrocarbon of propane.

5, as the manufacture method of any described liquefied petroleum gas (LPG) in the claim 1～4, it is characterized in that, after alkene manufacturing process and before separation circuit, also has the dried up water sepn operation of branch from olefin-containing gas and/or olefin reaction product gas.

As the manufacture method of any described liquefied petroleum gas (LPG) in the claim 1～5, it is characterized in that 6, alkene is made catalyzer, is the iron aluminosilicate that contains iron atom in zeolite framework.

7, the manufacture method of the liquefied petroleum gas (LPG) described in claim 6 is characterized in that, alkene is made catalyzer, is the iron aluminosilicate with MFI structure.

8, the manufacture method of the liquefied petroleum gas (LPG) described in claim 7 is characterized in that, alkene is made catalyzer, is the iron aluminosilicate with MFI structure of Hydrogen.

As the manufacture method of any described liquefied petroleum gas (LPG) in the claim 6～8, it is characterized in that 9, alkene is made catalyzer, is during with atomic ratio measuring, and the ratio of Fe/ (Al+Fe) is the iron aluminosilicate more than 0.05, below 0.45.

As the manufacture method of any described liquefied petroleum gas (LPG) in the claim 6～9, it is characterized in that 10, alkene is made catalyzer, is during with atomic ratio measuring, and the ratio of Si/ (Al+Fe) is the iron aluminosilicate more than 20, below 100.

As the manufacture method of any described liquefied petroleum gas (LPG) in the claim 1～10, it is characterized in that 11, the conversion of olefines catalyzer is a Hydrogen ZSM-5 zeolite.

12, the manufacture method of the liquefied petroleum gas (LPG) described in claim 11 is characterized in that, the conversion of olefines catalyzer is during with atomic ratio measuring, and Si is the Hydrogen ZSM-5 zeolite below 200 more than 20 with the ratio of Al.

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