CN102766010B

CN102766010B - The preparation method of propylene

Info

Publication number: CN102766010B
Application number: CN201210241616.9A
Authority: CN
Inventors: 山口正志; 瀬户山亨; 中川佳午人; 内海史尊; 岩出慎二
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Chemical Corp; Mitsubishi Rayon Co Ltd
Priority date: 2006-09-21
Filing date: 2007-09-20
Publication date: 2015-08-19
Anticipated expiration: 2027-09-20
Also published as: WO2008035743A1; KR101435230B1; TWI405750B; CN102766010A; TW200831453A; KR20090059123A

Abstract

The invention provides one in the presence of a catalyst, make the olefin feedstock of at least one in methyl alcohol and dme and carbonatoms more than 4 react to prepare the method for propylene, the method can use a small amount of raw material prepare propylene with high yield and inhibit the deterioration of catalyzer.

Description

The preparation method of propylene

The divisional application that the application is the applying date is on September 20th, 2007, application number is 200780035328.5, denomination of invention is the application of " preparation method of propylene ".

Technical field

The present invention relates to by the raw mixture of the alkene containing at least one in methyl alcohol and dme and carbonatoms more than 4 to prepare the method for propylene.

Background technology

As the preparation method of propylene, usually adopted petroleum naphtha and the steam splitting process of ethane, the FCC process of vacuum gas in the past, in recent years, with ethene and 2-butylene for raw material carry out replacement(metathesis)reaction method, have the alkene of more than 4 carbon atoms catalystic pyrolysis and also receive much concern with the MTO technical process that at least one in methyl alcohol and dme is carried out for raw material.On the other hand, also to there will be a known with carbonatoms be more than 4, and the oxygenatedchemicals such as alkene and methyl alcohol prepares the method (patent documentation 1) of light alkene for raw material.

Patent documentation 1: No. 6888038th, United States Patent (USP)

Summary of the invention

The problem that invention will solve

So far, propose the method preparing propylene in a large number, it is wherein the method about reaction and purifying disclosed in the overwhelming majority, and about with oxygenatedchemicalss such as the alkene of carbonatoms more than 4 and methyl alcohol for the method for propylene prepared by raw material, although its reaction is disclosed itself, there is no the technical process proposing to comprise the purification system of reactor downstream side.

Therefore, the 1st object of the present invention is to provide a kind of novel and technical process of economy, and it is for by making the olefine reaction of at least one in methyl alcohol and dme and carbonatoms more than 4 prepare propylene.

On the other hand, with regard to now as the main flow preparation method of ethene, propylene steam cracking process flow process with regard to, there is not large change in the ethene of preparation and the ratio of propylene, and by technical process of the present invention and steam cracking process flow process being combined, significantly can change the ratio of ethene and propylene.And, due to by two kinds of technical process are merged, can effectively to utilize in technical process each other the fluid discard, expect by the more efficient technical process of its synergy structure.

Therefore, the 2nd object of the present invention is to provide a kind of this technical process and steam cracking process flow process are combined novel and the technical process of economy.

The method of dealing with problems

For the olefine reaction of at least one made in methyl alcohol and dme and carbonatoms more than 4 to prepare the reaction of propylene, when the present inventor etc. study it, obtain following discovery.

If the amount of alkene that reaction consumes is too much, then the amount that side reaction generates the less desirable compound such as aromatics or paraffinic hydrocarbons obviously increases, and if the amount of alkene that reaction consumes is very few, then propene yield is too low.By reaction conditionss such as suitable design temperature, pressure, dividing potential drop, space velocities, the amount of alkene of consumption is controlled in specified range, can with high selectivity and high yield obtains propylene.When reacting in such a situa-tion, due in reactor outlet fluid containing the alkene with more than 4 carbon atoms that to can be used as reaction raw materials in a large number, therefore preferred these compounds to be recycled in reactor.

On the other hand, in the reaction of the alkene of at least one in methyl alcohol and dme and carbonatoms more than 4, also produce aromatics and the paraffinic hydrocarbons of trace, it is included in reactor outlet fluid.Particularly when the olefin feedstock using the raw material containing paraffinic hydrocarbons as carbonatoms more than 4, the paraffin concentration in reactor outlet fluid increases.Because paraffinic does not substantially react in reactor, when being recycled in reactor together with the alkene of carbonatoms more than 4, paraffinic hydrocarbons concentrates and accumulates in system.Therefore, preferably the fluid of part containing paraffinic is taken out in system.Now, preferably make the fluid of taking-up become and there is the fluid that effectively can utilize composition.

In addition, in the olefin stream of the carbonatoms more than 4 be recycled, when there is the aromatics of more than certain concentration, at least one in the reaction of the alkene of these aromatics and carbonatoms more than 4 and methyl alcohol and dme and the reaction of aromatics become remarkable, the consumption of at least one in the methyl alcohol supplied and dme and the alkene of carbonatoms more than 4 more than necessary consumption, not preferably.

In addition, when aromatics is supplied in reactor, the compound that the olefine reaction of aromatics and above-mentioned carbonatoms more than 4 generates makes the hole plug of catalyzer, thus facilitate the deterioration of catalyzer, therefore preferably the aromatics existed in reactor outlet fluid is taken out by system as far as possible as far as possible, reduce the concentration of the aromatics in the fluid be recycled in reactor.Now, the fluid still preferably taken out is have the fluid that effectively can utilize composition.

Like this, with the alkene of at least one in methyl alcohol and dme and carbonatoms more than 4 for raw material is prepared in the method for propylene, the present inventor etc. have found various problems, by building the technical process that can address these problems, a small amount of raw material can be used to suppress catalyst degradation and to prepare propylene with high yield.

Find in addition, by the fluid taken out by this technical process is supplied to steam cracking process flow process, and the fluid of steam cracking process flow process is supplied in this technical process, can effectively utilize cheap fluid, realize efficient technical process.

Based on above-mentioned discovery, complete the present invention, the present invention includes following main points.

[1] preparation method for propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and raw material containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, wherein,

By the taking-up at least partially of aromatics contained in this reactor outlet eluting gas (reactor outlet gas), and make the alkene of carbonatoms more than 4 contained in this reactor outlet eluting gas (reactor outlet gas) at least partially again in the reactor with catalyst exposure.

The preparation method of the propylene [2] Gen Ju [1], wherein, the olefin feedstock of above-mentioned carbonatoms more than 4 contains the paraffinic that carbonatoms is more than 4.

The preparation method of the propylene [3] Gen Ju [2], wherein, above-mentioned paraffinic comprises at least one in normal butane and Trimethylmethane.

[4] according to the preparation method of the propylene according to any one of [1] ~ [3], wherein, be supplied in the raw material of above-mentioned reactor containing divinyl.

[5] according to the preparation method of the propylene according to any one of [1] ~ [4], wherein, the mol ratio of the total amount of the alkene of the carbonatoms more than 4 contained by the total amount of contained in the above-mentioned whole raw materials be supplied in reactor aromatics and this whole raw material is less than 0.05.

[6] according to the preparation method of the propylene according to any one of [1] ~ [5], wherein, relative to 2 times of the dme mole number be supplied in reactor with the total amount of moles of methanol, the amount of the alkene of the above-mentioned carbonatoms more than 4 be supplied in reactor is less than more than 0.2 10 with molar ratio computing.

[7] according to the preparation method of the propylene according to any one of [1] ~ [6], wherein, the total concn (substrate concn) of the alkene of the carbonatoms more than 4 contained in the above-mentioned whole raw materials be supplied in reactor, methyl alcohol and dimethyl ether is controlled at 20 more than volume % 80 volume below %.

[8] a kind of preparation method of propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and raw material containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1), the technical process of (2) and (3A) forms

Step (1): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (D) by step (3A) recirculation are supplied in reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 90%, under the reaction conditions, make itself and above-mentioned catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the gas (reactor outlet gas) of aromatics and water,

Step (2): the fluid reactor outlet gas from above-mentioned steps (1) being separated into the hydrocarbon being rich in carbonatoms less than 3, the fluid (A) being rich in the hydrocarbon of carbonatoms more than 4 and be rich in the fluid of water;

Step (3A): the fluid at least partially (C) of fluid (A) in above-mentioned steps (2) is separated into fluid (D) and fluid (E), and above-mentioned fluid (D) is recycled in reactor, above-mentioned fluid (E) takes out from this technical process, in wherein said fluid (D), aromatic concentrations is than low in fluid (C), and in described fluid (E), carbonatoms is low in the hydrocarbon concentration ratio fluid (C) of 4.

[9] a kind of preparation method of propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and raw material containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1), the technical process of (2) and (3A) forms

Step (1): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (D) by step (3A) recirculation are supplied in reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 90%, under the reaction conditions, make above-mentionedly to be supplied to material in reactor and above-mentioned catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the gas (reactor outlet gas) of aromatics and water,

Step (3A) a: part (B) for fluid (A) in above-mentioned steps (2) is taken out from this technical process, and residual fluid (C) is separated into fluid (D) and fluid (E), and above-mentioned fluid (D) is recycled in reactor, above-mentioned fluid (E) takes out by this technical process, in wherein said fluid (D), aromatic concentrations is than low in fluid (C), and in described fluid (E), carbonatoms is low in the hydrocarbon concentration ratio fluid (C) of 4.

[10] preparation method of basis [8] or the propylene described in [9], wherein, above-mentioned reactor comprises the plural reacting part be connected in series, and at least one segmentation in the hydrocarbon-containifluids fluids (D) of at least one in the olefin feedstock of the above-mentioned carbonatoms more than 4 be supplied in reactor, methyl alcohol and dme and recirculation is supplied to the 1st section of reacting part and the 2nd section or later reacting part.

[11] according to the preparation method of the propylene according to any one of [8] ~ [10], wherein, above-mentioned fluid (B) is supplied in steam cracking process flow process, uses as cracking stock.

The preparation method of the propylene [12] Gen Ju [11], wherein, makes contacting with hydrogenation catalyst at least partially of above-mentioned fluid (B), is then supplied in steam cracking process flow process.

[13] according to the preparation method of the propylene according to any one of [8] ~ [12], wherein, the total concn of contained in above-mentioned fluid (B) aromatics is less than 5.0 volume %.

[14] according to the preparation method of the propylene according to any one of [8] ~ [13], wherein, above-mentioned fluid (E) is mixed with the cracked naphtha of steam cracking process flow process.

[15] according to the preparation method of the propylene according to any one of [8] ~ [14], wherein, contained in above-mentioned fluid (E) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

[16] according to the preparation method of the propylene according to any one of [8] ~ [15], wherein, by controlling the flow of above-mentioned fluid (B) and above-mentioned fluid (E), the total concn (substrate concn) of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

[17] a kind of preparation method of propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and mixture containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, it comprises the following steps (1), (2) and (3B)

Step (1): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (I) from step (3B) recirculation are supplied to reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 90%, under the reaction conditions, make above-mentionedly to be supplied to material in reactor and catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the gas (reactor outlet gas) of aromatics and water,

Step (3B): the fluid (A) in above-mentioned steps (2) is separated into fluid (G) and fluid (F), and (I) at least partially of above-mentioned fluid (G) is recycled in reactor, remaining fluid (H) takes out from this technical process, in wherein said fluid (G), aromatic concentrations is than low in fluid (A), and in described fluid (F), carbonatoms is low in the hydrocarbon concentration ratio fluid (A) of 4.

[18] a kind of preparation method of propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and mixture containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1), the technical process of (2) and (3B) forms

Step (1): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (I) by step (3B) recirculation are supplied in reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 90%, under the reaction conditions, make above-mentionedly to be supplied to material in reactor and catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the gas (reactor outlet gas) of aromatics and water,

Step (3B): the fluid (A) in above-mentioned steps (2) is separated into fluid (G) and fluid (F), above-mentioned fluid (F) is taken out by this technical process, and a part (I) of above-mentioned fluid (G) is recycled in reactor, remaining fluid (H) takes out from this technical process, in wherein said fluid (G), aromatic concentrations is than low in fluid (A), and in described fluid (F), carbonatoms is low in the hydrocarbon concentration ratio fluid (A) of 4.

[19] according to the preparation method of [17] or [18] described propylene, wherein, described reactor comprises the plural reacting part be connected in series, and at least one segmentation in the hydrocarbon-containifluids fluids (I) of at least one in the olefin feedstock of the above-mentioned carbonatoms more than 4 be supplied in reactor, methyl alcohol and dme and recirculation is supplied to the 1st section of reacting part and the 2nd section or later reacting part.

[20] according to the preparation method of the propylene according to any one of [17] ~ [19], wherein, described fluid (H) is supplied in steam cracking process flow process, uses as cracking stock.

The preparation method of the propylene [21] Gen Ju [20], wherein, makes contacting with hydrogenation catalyst at least partially of described fluid (H), is then supplied in steam cracking process flow process.

[22] according to the preparation method of the propylene according to any one of [17] ~ [21], wherein, the summation of contained in described fluid (H) aromatic concentrations is less than 5.0 volume %.

[23] according to the preparation method of the propylene according to any one of [17] ~ [22], wherein, described fluid (F) is mixed with the cracked naphtha of steam cracking process flow process.

[24] according to the preparation method of the propylene according to any one of [17] ~ [23], wherein, contained in described fluid (F) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

[25] according to the preparation method of the propylene according to any one of [17] ~ [24], wherein, by controlling the flow of described fluid (F) and described fluid (H), the total concn (substrate concn) of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

[26] according to the preparation method of the propylene according to any one of [8] ~ [25], wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, then be isolated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and be rich in the fluid of hydrocarbon of carbonatoms more than 3, the more described fluid being rich in the hydrocarbon of carbonatoms more than 3 being separated into the fluid of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

[27] according to the preparation method of the propylene according to any one of [8] ~ [25], wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, then be isolated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and be rich in the fluid of hydrocarbon of carbonatoms more than 4, the more described fluid being rich in the hydrocarbon of carbonatoms less than 3 be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and be rich in the fluid that carbonatoms is the hydrocarbon of 3.

[28] according to the preparation method of the propylene according to any one of [8] ~ [25], wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, then by distilling the fluid that the hydrocarbon that is isolated into containing carbonatoms less than 2 and carbonatoms are the hydrocarbon of 3, and be rich in the fluid of hydrocarbon of carbonatoms more than 3, by distillation the described fluid being rich in the hydrocarbon of carbonatoms more than 3 is separated into the fluid of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 again.

[29] according to the preparation method of the propylene according to any one of [8] ~ [25], wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, then by distilling the fluid of the fluid being isolated into the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon being rich in carbonatoms more than 4, the described fluid being rich in the hydrocarbon of carbonatoms less than 3 is separated into by distillation the fluid that hydrocarbon containing carbonatoms less than 2 and carbonatoms are the hydrocarbon of 3 again, and be rich in the fluid that carbonatoms is the hydrocarbon of 3.

[30] according to the preparation method of the propylene according to any one of [8] ~ [29], wherein, the olefin feedstock of described carbonatoms more than 4 contains the paraffinic of carbonatoms more than 4.

The preparation method of the propylene [31] Gen Ju [30], wherein, described paraffinic contains at least one in normal butane and Trimethylmethane.

[32] according to the preparation method of the propylene according to any one of [8] ~ [31], wherein, be supplied in the raw material of reactor containing divinyl described.

[33] according to the preparation method of the propylene according to any one of [8] ~ [32], wherein, the mol ratio of the alkene total amount of contained in the total amount and this whole raw material of the aromatics contained by described being supplied in whole raw materials of reactor carbonatoms more than 4 is less than 0.05.

[34] according to the preparation method of the propylene according to any one of [8] ~ [33], wherein, the amount being supplied to the alkene of the carbonatoms more than 4 in reactor described in is less than more than 0.2 10 with the mol ratio of 2 times of dme mole number that are supplied in this reactor and the total amount of moles of methanol.

[35] according to the preparation method of propylene according to any one of [8] ~ [34], wherein, it is the hydrocarbon fluid of 4 that the olefin feedstock of the carbonatoms more than 4 be supplied in reactor described in contains the carbonatoms that steam cracking process flow process obtains.

[36] a kind of preparation method of propylene, the method is in the presence of a catalyst, make containing at least one in methyl alcohol and dme and containing carbonatoms more than 4 alkene mixture in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1C), (2C), the technical process of (3C) and (4C) forms

Step (1C): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4, the hydrocarbon fluid (Q) come from step (4C) recirculation is supplied to reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 90%, under the reaction conditions, make above-mentionedly to be supplied to material in reactor and catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the gas (reactor outlet gas) of aromatics and water,

Step (2C): will cool from the reactor outlet gas of above-mentioned steps (1C), and be separated into gaseous fluid (L), and be rich in the hydrocarbon of carbonatoms more than 4 and contain the fluid liquid (M) of aromatics and be rich in the fluid of water;

Step (3C): the fluid (N) of the fluid gaseous fluid (L) in above-mentioned steps (2C) being separated into the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon that is rich in carbonatoms more than 4;

Step (4C): the fluid at least partially (Q) of above-mentioned fluid (N) is recycled in reactor.

[37]. a kind of preparation method of propylene, the method is in the presence of a catalyst, make containing at least one in methyl alcohol and dme and containing carbonatoms more than 4 alkene mixture in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1C), (2C), the technical process of (3C) and (4C) forms

Step (2C): will cool from the reactor outlet gas of above-mentioned steps (1C), by being separated into gaseous fluid (L) to cooled gaseous fluid (K) compression, being rich in the hydrocarbon of carbonatoms more than 4 and containing the fluid liquid (M) of aromatics and be rich in the fluid of water;

Step (4C) a: part (P) of above-mentioned fluid (N) is taken out from this technical process, and remaining fluid (Q) is recycled in reactor.

[38] preparation method of basis [36] or the propylene described in [37], wherein, by distillation, above-mentioned fluid liquid (M) is separated into fluid (R) and fluid (S), aromatic concentrations in wherein said fluid (R) is than low in fluid liquid (M), and the carbonatoms in described fluid (S) is low in the hydrocarbon concentration ratio fluid liquid (M) of 4.

The preparation method of the propylene [39] Gen Ju [38], wherein, described fluid (R) is turned back to the circulation position of any one kind or two or more fluid be selected from above-mentioned fluid (K), (L), (M), (P) and (Q).

[40] according to the preparation method of the propylene according to any one of [36] ~ [39], wherein, above-mentioned steps (3C) comprises the steps: described gaseous fluid (L) to be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and to be rich in the fluid of hydrocarbon of carbonatoms more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (N) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

[41] according to the preparation method of the propylene according to any one of [36] ~ [39], wherein, above-mentioned steps (3C) comprises the steps: described gaseous fluid (L) to be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and to be rich in the fluid (N) of hydrocarbon of carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

[42] according to the preparation method of the propylene according to any one of [36] ~ [39], wherein, above-mentioned steps (3C) comprises the steps: the fluid of the hydrocarbon described gaseous fluid (L) being separated into by distillation fluid that the hydrocarbon that comprises carbonatoms less than 2 and carbonatoms are the hydrocarbon of 3 and being rich in carbonatoms more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (N) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

[43] according to the preparation method of the propylene according to any one of [36] ~ [39], wherein, above-mentioned steps (3C) comprises the steps: described gaseous fluid (L) to be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and to be rich in the fluid (N) of hydrocarbon of carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into by distillation the hydrocarbon that comprises carbonatoms less than 2 and carbonatoms is the fluid of the hydrocarbon of 3 and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

[44] according to the preparation method of the propylene according to any one of [36] ~ [43], wherein, described reactor comprises the plural reacting part be connected in series, and at least one segmentation in the hydrocarbon-containifluids fluids of at least one in the olefin feedstock of the above-mentioned carbonatoms more than 4 be supplied in reactor, methyl alcohol and dme and recirculation is supplied to the 1st section of reacting part and the 2nd section or later reacting part.

[45] according to the preparation method of the propylene according to any one of [36] ~ [44], wherein, the olefin feedstock of described carbonatoms more than 4 contains the paraffinic of carbonatoms more than 4.

The preparation method of the propylene [46] Gen Ju [45], wherein, described paraffinic contains at least one in normal butane and Trimethylmethane.

[47] according to the preparation method of the propylene according to any one of [36] ~ [46], wherein, be supplied in the raw material of described reactor containing divinyl.

[48] according to the preparation method of the propylene according to any one of [36] ~ [47], wherein, the mol ratio of the total amount of the alkene of the carbonatoms more than 4 contained by the total amount being supplied in whole raw materials of described reactor contained aromatics and this whole raw material is less than 0.05.

[49] according to the preparation method of the propylene according to any one of [36] ~ [48], wherein, at least one in described fluid (M) and described fluid (P) is supplied in steam cracking process flow process, uses as cracking stock.

The preparation method of the propylene [50] Gen Ju [49], wherein, makes contacting with hydrogenation catalyst at least partially of at least one in described fluid (M) and described fluid (P), is then supplied in steam cracking process flow process.

[51] according to the preparation method of the propylene according to any one of [36] ~ [50], wherein, the total concn of contained at least one of described fluid (M) and described fluid (P) aromatics is less than 5.0 volume %.

[52] according to the preparation method of the propylene according to any one of [36] ~ [51], wherein, described fluid (M) is mixed with the cracked naphtha of steam cracking process flow process.

[53] according to the preparation method of the propylene according to any one of [36] ~ [52], wherein, the carbonatoms contained in described fluid (M) is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

[54] according to the preparation method of the propylene according to any one of [36] ~ [53], wherein, by controlling the flow of described fluid (M) and described fluid (P), the total concn (substrate concn) of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

[55] according to the preparation method of the propylene according to any one of [38] ~ [54], wherein, described fluid (R) is supplied in steam cracking process flow process, uses as cracking stock.

The preparation method of the propylene [56] Gen Ju [55], wherein, makes contacting with hydrogenation catalyst at least partially of described fluid (R), is then supplied in steam cracking process flow process.

[57] according to the preparation method of the propylene according to any one of [38] ~ [56], wherein, the total concn of contained in described fluid (R) aromatics is less than 5.0 volume %.

[58] according to the preparation method of the propylene according to any one of [38] ~ [57], wherein, described fluid (S) is mixed with the cracked naphtha of steam cracking process flow process.

[59] according to the preparation method of the propylene according to any one of [38] ~ [58], wherein, contained in described fluid (S) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

[60] according to the preparation method of the propylene according to any one of [38] ~ [59], wherein, by controlling the flow of described fluid (P), fluid (R) and fluid (S), the total concn (substrate concn) of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

[61] according to the preparation method of the propylene according to any one of [38] ~ [60], wherein, when described fluid (R) being turned back to the position at any one or two or more the fluid place be selected from described fluid (K), (L), (N), (P) and (Q), by controlling position that described fluid (R) returns and flow thereof, the total concn (substrate concn) of the above-mentioned alkene, methyl alcohol and the dme that are supplied to carbonatoms more than 4 contained in whole raw materials of reactor is controlled at 20 more than volume % 80 volume below %.

[62] according to the preparation method of the propylene according to any one of [36] ~ [61], wherein, the amount of the alkene of the above-mentioned carbonatoms more than 4 be supplied in reactor is less than more than 0.2 10 with the mol ratio of 2 times of dme mole number that are supplied in this reactor and the total amount of moles of methanol.

[63] according to the preparation method of the propylene according to any one of [38] ~ [62], wherein, the olefin feedstock of the above-mentioned carbonatoms more than 4 be supplied in reactor contains the hydrocarbon fluid of the carbonatoms more than 4 of steam cracking process flow process gained.

The effect of invention

According to the present invention, by the presence of a catalyst, make the olefine reaction of at least one in methyl alcohol and dme and carbonatoms more than 4 to prepare the method for propylene, raw material can be made full use of, suppress the deterioration of catalyzer and prepare propylene with high yield.

In addition, method of the present invention can be combined with steam cracking process flow process the technical process providing low cost.

Accompanying drawing explanation

[Fig. 1] is the system diagram of an example of the embodiment that propylene production of the present invention is shown.

[Fig. 2] is the system diagram of another example of the embodiment that propylene production of the present invention is shown.

[Fig. 3] is the system diagram of an example again of the embodiment that propylene production of the present invention is shown.

Nomenclature

10 reactors

20 the 1st separation and purification systems

30A, 30B the 2nd separation and purification system

13 reactors

23 compressors

33 separating tanks

43 oil-water separators

53 the 1st separation and purification systems

63 the 2nd separation and purification systems

Embodiment

Below, be specifically described for implementing the embodiment that represents of the present invention, but only otherwise exceed purport of the present invention, the present invention is not limited to following embodiment.

Propylene production of the present invention is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and raw material containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, wherein, by the taking-up at least partially of aromatics contained in this reactor outlet eluting gas, make simultaneously the alkene of carbonatoms more than 4 contained in this reactor outlet eluting gas at least partially this reactor again with catalyst exposure.

As first, second embodiment more specifically, comprise 3 steps (1) as above, (2), (3A) or (1), (2), (3B), in addition, 3rd embodiment comprises 4 steps (1C) as above, (2C), (3C) and (4C), but if the object solving problem of the present invention can be realized, do not get rid of and there is other step, other step can be there is before and after 4 steps, between each step, also can there is other step.

It should be noted that, the present invention's said " being rich in " refers to that target compound purity is more than 50 % by mole, is preferably more than 70 % by mole, is more preferably more than 90 % by mole, more preferably more than 95 % by mole.Such as, described " being rich in the fluid (N) of the hydrocarbon of carbonatoms more than 4 " refer to " containing more than 50 % by mole, preferably containing more than 70 % by mole, more preferably containing more than 90 % by mole, the further preferred fluid containing " hydrocarbon of carbonatoms more than 4 " of more than 95 % by mole.

[catalyzer]

First, the catalyzer used in the present invention is described.

As the catalyzer for reaction of the present invention, as long as have the solid matter of broensted acidity, be then not particularly limited, known catalyzer can be used, such as, following catalyzer can be enumerated: the clay minerals such as kaolin; In the carrier of clay mineral etc., flood/be supported with the material of the acid such as sulfuric acid, phosphoric acid; Acidic ion exchange resin; Zeolites; Aluminum phosphate class; The solid acid catalysts such as mesopore pure aluminium silicate such as Al-MCM41.

In above-mentioned solid acid catalyst, preferably there is the catalyzer of molecular sieve effect, in addition, the catalyzer that preferred acid intensity is not too high.

In above-mentioned solid acid catalyst, as the structure of the zeolites or aluminum phosphate class catalyzer with molecular sieve effect, if with the coded representation of International Zeolite Association (IZA) defined, then such as AEI, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON etc. can be enumerated.Wherein, the skeletal density of preferred catalyst is the catalyzer of below 18.0T/nm3, as this kind of catalyzer, and preferred MFI, MEL, MOR, MWW, FAU, BEA, CHA, more preferably MFI, MEL, MOR, MWW, CHA, particularly preferably is MFI, MEL, MWW, CHA.

Wherein, described skeletal density (unit: T/nm ³) refer to per unit volume (1nm ³) T atom (forming the atom beyond the oxygen in the atom of the zeolite framework) number that exists in zeolite, this value is by zeolite structured decision.

In addition, as described solid acid catalyst, being more preferably micropore, the BET specific surface area with fine pore 0.3 ~ 0.9nm is 200 ~ 700m ²/ g, pore volume are crystallinity aluminosilicate-type, the metal metasilicate salt or crystallinity aluminum phosphate class etc. of 0.1 ~ 0.5g/ml.In addition, described fine pore wherein represents the channel diameter (Crystallographic freediameter of the channels) in the crystallography that InternationalZeolite Association (IZA) specifies, when the shape of pore (duct) is positive circle, described fine pore refers to its diameter, when pore shape is oval, described fine pore refers to its minor axis.

In addition, preferred SiO in pure aluminium silicate ₂/ Al ₂o ₃mol ratio be more than 10.If SiO ₂/ Al ₂o ₃mol ratio too low, then catalyzer weather resistance reduce, therefore not preferred.SiO ₂/ Al ₂o ₃the upper limit of mol ratio is generally less than 10000.If SiO ₂/ Al ₂o ₃mol ratio higher than 10000, then catalyst activity reduce, therefore not preferred.Above-mentioned mol ratio can be obtained by the common method such as fluorescent X-ray or chemical analysis.

The aluminium content in catalyzer can be controlled by the feeding quantity of raw material during adjustment Kaolinite Preparation of Catalyst, in addition, Al content can also be reduced by steaming etc. after the production.In addition, part Al can also be replaced to other element such as boron or potassium, particularly preferably replace with boron.

Above-mentioned catalyzer can be used alone a kind, also can combine two or more and use.

In the present invention, above-mentioned catalyst active component directly can be used for reaction as catalyzer, can also use and carry out granulation, shaping to the inactive material of reaction or tackiness agent, or their mixing is used in reaction.As to the inactive material of this reaction or tackiness agent, aluminum oxide, alumina sol, silicon-dioxide, silica gel, quartz and their mixture etc. can be enumerated.

In addition, the composition of above-mentioned catalyzer is only the composition of catalyst active component, and it does not comprise above-mentioned to reaction inactive material and tackiness agent etc.But, catalyzer of the present invention, when containing above-mentioned to reaction inactive material or tackiness agent etc. time, above-mentioned catalyst active component and these are combined are called catalyzer to reacting inactive material or tackiness agent etc.; Above-mentioned to when reacting inactive material or tackiness agent etc. when not containing, only catalyst active component is called catalyzer.

The particle diameter of the catalyst active component used in the present invention is different according to condition difference during synthesis, but its median size is 0.01 μm ~ 500 μm usually.If the particle diameter of catalyzer is excessive, then the surface-area showing catalyst activity diminishes, if particle diameter is too small, its operability will be caused to be deteriorated, and is no matter that excessive or too small situation is all not preferred.This median size is tried to achieve by SEM observation etc.

For the preparation method of the catalyzer used in the present invention, be not particularly limited, the known method being called as Hydrothermal Synthesis usually can be adopted to prepare.In addition, can by carrying out ion-exchange, dealumination treatment after Hydrothermal Synthesis, flood or the composition that modification changes catalyzer such as supporting.

As long as the catalyzer used in the present invention has the catalyzer of above-mentioned physical property or composition when participating in reaction, prepare by any means.

< reaction raw materials >

Then, be described with regard to the alkene as the carbonatoms more than 4 of reaction raw materials in the present invention, methyl alcohol, dme.

< olefin feedstock >

As the alkene of the carbonatoms more than 4 as reaction raw materials, be not particularly limited.Such as, the carbonatoms more than 4 obtained by various known method can be used arbitrarily, the particularly alkene of carbonatoms 4 ~ 10, such as, alkene (the BB cut of the carbonatoms more than 4 prepared by oil base feed by catalytic cracking method or steam cracking etc., C4 raffinate-1, C4 raffinate-2 etc.), the hydrogen obtained by gasification of coal/CO gas mixture is the alkene that raw material carries out FT (Fischer-Tropsch (Fischer-Tropsch)) and synthesizes the carbonatoms more than 4 obtained, the oligomerization of dimerization is comprised and the alkene of obtained carbonatoms more than 4 by ethene, the alkene of the carbonatoms more than 4 that the paraffinic hydrocarbons of carbonatoms more than 4 is obtained through dehydriding or oxydehydro process, reacted by MTO and the alkene of obtained carbonatoms more than 4, the alkene of the carbonatoms more than 4 obtained by the dehydration reaction of alcohol, the alkene etc. of obtained carbonatoms more than 4 by the hydrogenation of the diolefin of carbonatoms more than 4, now, directly can use the alkene of the carbonatoms more than 4 under these states being mixed with arbitrarily the compound beyond the alkene of the carbonatoms more than 4 produced due to manufacture method, also purified alkene can be used.

Wherein, when using the olefin feedstock of the paraffinic containing carbonatoms more than 4, because paraffinic hydrocarbons plays the effect of diluent gas, therefore easily control temperature of reaction, and the raw material containing paraffinic hydrocarbons cheaply can obtain, therefore preferably.More preferably the olefin feedstock containing at least one in normal butane and Trimethylmethane.

As these preferred raw materials, can enumerate, above-mentioned BB cut, C4 raffinate-1, C4 raffinate-2.Usually containing divinyl in these raw materials.Because divinyl is easily converted into aromatics by reacting, therefore, as the present invention, the aromatics that generates at least partially is taken out, and be not that to be recycled in reactor be very important.In addition, because BB cut contains a large amount of divinyl, therefore preferably make it contact with hydrogenation catalyst and reduce butadiene concentration, and the fluid be minimized by this butadiene concentration is as raw material.

< methyl alcohol, dme >

As at least one be used as in the methyl alcohol of reaction raw materials and dme, prepared by source to it and is not particularly limited.Include, for example the mixed gas generation hydrogenation by making to come from by product in coal and Sweet natural gas and iron industry processed and hydrogen/CO and the product obtained; Modified-reaction is carried out and obtained product by making the alcohols coming from plant; By the product that fermentation method obtains; The product etc. obtained by organism such as recycled plastic, city wastes.Now, when producing the compound beyond methyl alcohol and dme in above-mentioned each preparation method, directly can use the product under these states being mixed with arbitrarily the compound beyond methyl alcohol and dme, also can use at least one in purified methyl alcohol and dme.

[operation, condition: step (1) (1C) in 1st ~ 3 embodiments]

Below, just use the operation of the propylene preparation feedback of the present invention of above-mentioned catalyzer and reaction raw materials, condition is described.

< reactor >

The reaction of the alkene of the methyl alcohol in the present invention and at least one in dme and carbonatoms more than 4 is gas-phase reaction.Form for this Gas-phase reactor is not particularly limited, and usually can select from the fixed-bed reactor of continous way or flowing bed reactor.Preferred fixed-bed reactor.

In addition, when being filled with above-mentioned catalyzer in fixed-bed reactor, in order to the temperature distribution of catalyst layer being controlled more among a small circle, can also filled stone sand, aluminum oxide, silicon-dioxide, pure aluminium silicate etc. to the mixture of reaction inactive saccharoid and catalyzer etc.Now, quartz sand etc. is not particularly limited the usage quantity of the inactive saccharoid of reaction.In addition, in order to make itself and catalyzer have uniform Combination, this saccharoid and catalyzer is preferably made to have the particle diameter of equal extent.

It should be noted that, reactor can comprise the plural reacting part be connected in series.Now, multiple reaction chamber can be divided into by a reactor, also plural reactors in series can be connected.

When two or more reactors in series being connected, heat exchanger can be set between reactor and reactor, for removing the heat of releasing with reaction.

In addition, in order to make heat release disperse, can by response matrix (reaction raw materials) segmentation supply.Preferably at least one segmentation in methyl alcohol and dme is supplied to reacting part (reactor or reaction chamber) and the 2nd section or the later reacting part (reactor or reaction chamber) of the 1st section.

Under the reaction conditions that the present invention uses, the little coking of catalyzer, catalyst degradation speed is slow, when carrying out the continuous running of more than 1 year, is necessary the on-stream regeneration carrying out catalyzer.

Such as, when selecting fixed-bed reactor, it is desirable at least to be set up in parallel plural reactor, running limit, limit switches reaction and regeneration.As the form of fixed-bed reactor, multi-tubular reactor or heat insulation type reactor can be selected.

On the other hand, during selective flow bed bioreactor, preferably catalyzer is sent in regeneration tank continuously, reacts while make the catalyzer regenerated in regeneration tank turn back to limit in reactor continuously.

Here, as the regenerative operation of catalyzer, can enumerate, the catalyzer that deterioration occurs because of coking be carried out the method regenerated with process such as the nitrogen containing oxygen or water vapour.As the regenerative operation in fixed-bed reactor, preferably with nitrogen removing attachment volatile organic compounds on a catalyst, then with the nitrogen combustion removing coking composition containing lower concentration oxygen, subsequently by the method with the molecular oxygen contained in nitrogen treatment removing catalyst layer.

< is supplied to the concentration ratio > of at least one in alkene in reactor and methyl alcohol and dme

In the present invention, the amount of alkene being supplied to the carbonatoms more than 4 of reactor is more than 0.2 with the mol ratio of 2 times of dme mole number that are supplied in reactor and the total amount of moles of methanol, is preferably more than 0.5, and is less than 10, preferably less than 5.

That is, the supply molar weight of the alkene of carbonatoms more than 4 is set to Mc4, the supply molar weight of methyl alcohol is set to Mm, when the supply molar weight of dme is set to Mdm, Mc4 is (Mm+2Mdm) 0.2 ~ 10 times, be preferably 0.5 ~ 5 times.

Too low or the too high reaction of all slowing down of this supply concentration ratio, not preferably, when particularly this supply concentration ratio is too low, the consumption of raw material olefin reduces, therefore not preferred.

Here, supplying concentration ratio can adopt the common analytical procedures such as vapor-phase chromatography to learn by carrying out quantitatively the composition of each fluid be supplied in reactor or mixed fluid.

In addition, when the alkene of at least one in methyl alcohol and dme and carbonatoms more than 4 is supplied in reactor, it can be supplied respectively, also can by wherein part or all resupplies after being pre-mixed.

< is supplied to the substrate concn > in reactor

In the present invention, the total concn (substrate concn) being supplied to the alkene of the carbonatoms more than 4 in whole base feeds of reactor, methyl alcohol and dme is preferably 20 more than volume % 80 volume below %, is more preferably 30 more than volume % 70 volume below %.

Here, substrate concn can adopt the common analytical procedures such as vapor-phase chromatography to learn by carrying out quantitatively the composition of each fluid be supplied in reactor or mixed fluid.

If substrate concn is too high, then the generation of aromatics or paraffinic becomes more remarkable, and the selection rate of propylene is on a declining curve.On the contrary, if described substrate concn is too low, speed of response will be caused slack-off, need a large amount of catalyzer, being increased by the cost of erection of the cost for purification and conversion unit that cause resultant further, is uneconomic.

In the present invention, in order to make substrate concn in above-mentioned scope, diluent gas described later is used to dilute response matrix.In this case, as the method controlling substrate concn, the method that the flow of the fluid be fetched into outside technical process is controlled can be enumerated.That is, by changing the fluid flow rate taken out from technical process, changing the flow of the diluent gas be recycled in reactor, thus can substrate concn be changed.

< is supplied to the impurity concentration > in the gas of reactor

In the present invention, although carbonatoms more than 4 alkene and/or be recycled use hydrocarbon-containifluids fluids described later in sometimes containing divinyl, supply to the concentration of the divinyl in whole base feeds of reactor, be preferably 2.0 below volume %.If the concentration of the divinyl in raw material is high, then aromatics growing amount increases, and the deterioration that catalyst coking causes accelerates, therefore not preferred.

Here, the concentration of divinyl can adopt the common analytical procedures such as vapor-phase chromatography to learn by carrying out quantitatively the composition of each fluid be supplied in reactor or mixed fluid.

As the method for the butadiene concentration reduced in raw material, can enumerate and make this fluid contact with hydrogenation catalyst and divinyl is converted into the partial hydrogenation method of olefines.

In addition, to be recycled in the aftermentioned hydrocarbon-containifluids fluids in reactor sometimes containing aromatics, but the total amount being preferably supplied to aromatics contained in whole raw materials of reactor is less than 0.05 with the mol ratio of total amount of the alkene being supplied to carbonatoms more than 4 contained in whole raw materials of reactor.If aromatic concentrations is high in raw material, then in the reaction of the alkene of aromatics and carbonatoms more than 4 in reactor, aromatics and methyl alcohol and dme, the reaction of at least one becomes more remarkable, cause the alkene consuming the methyl alcohol of more than necessary amount and at least one in dme and carbonatoms more than 4, therefore not preferred.

And, when aromatics is supplied in reactor, the olefine reaction of aromatics and above-mentioned carbonatoms more than 4, the hole of the compound blocking catalyst generated, thus can the deterioration of accelerator activator, therefore, preferably the aromatics existed in reactor outlet fluid is taken out in system as far as possible, thus reduce the concentration of the aromatics be recycled in the fluid of reactor.

Here, the total amount of above-mentioned aromatics can adopt the common analytical procedures such as vapor-phase chromatography to learn by carrying out quantitatively the composition of each fluid be supplied in reactor or mixed fluid with the ratio of the total amount of the alkene of carbonatoms more than 4.

As the method for the aromatic concentrations reduced in raw material, can enumerate and adopt distillation to carry out the method be separated.

< diluent gas >

In the reactor, except the alkene of at least one in methyl alcohol and dme and carbonatoms more than 4, can also there is other to the inactive gas of reaction, described other comprises the mixture etc. of paraffinic, the fragrant same clan, water vapour, carbonic acid gas, carbon monoxide, nitrogen, argon gas, helium and mentioned component to the inactive gas of reaction.In addition, in above-mentioned diluent gas, different according to reaction conditions, described paraffinic and the fragrant same clan have some reaction sometimes, but due to reacting weight less, still can be defined as diluent gas.

As above-mentioned diluent gas, the impurity comprised in reaction raw materials can be directly used, also the diluent gas otherwise prepared and reaction raw materials use can be mixed.

In addition, diluent gas can mix with reaction raw materials before joining reactor, also diluent gas and reaction raw materials can be supplied in reactor respectively.

Preferred diluent gas is the paraffinic of carbonatoms more than 4.More preferably at least one in normal butane and Trimethylmethane.About these paraffinics, the paraffinic contained in olefin feedstock can be utilized, and be the compound that thermal capacity is larger due to it, therefore easily can control temperature of reaction.

< space velocity >

Space velocity mentioned here, refer to the flow of the alkene of reaction raw materials corresponding to per unit weight catalyzer (catalyst active component) and carbonatoms more than 4, wherein, the weight of described catalyzer refers to the weight not containing the catalyst active component for the granulation of catalyzer, shaping non-active ingredient and tackiness agent.In addition, described flow refers to the flow (weight/hour) of the alkene of carbonatoms more than 4.

Space velocity is preferably at 0.1Hr ^-1to 500Hr ^-1between, more preferably at 1.0Hr ^-1to 100Hr ^-1between.If space velocity is too high, then at least one in material benzenemethanol and dme and conversion of olefines rate low, and sufficient propylene selectivity cannot be obtained.In addition, if space velocity is too low, then obtaining the necessary catalytic amount of certain output increases, and not only makes reactor become excessive, and generate the not preferred by product such as aromatics or paraffinic hydrocarbons, propylene selectivity reduces, therefore not preferred simultaneously.

< temperature of reaction >

As the lower limit of temperature of reaction, the gas temperature at reactor inlet place is typically about more than 300 DEG C, is preferably more than 400 DEG C; As the upper limit of temperature of reaction, be generally less than 700 DEG C, be preferably less than 600 DEG C.If temperature of reaction is too low, then speed of response is lower, and may remain a large amount of unreacting material, propene yield reduces further.On the other hand, if temperature of reaction is too high, then the yield of propylene significantly declines.

< reaction pressure >

The upper limit of reaction pressure is generally 2MPa (absolute pressure, identical below) below, is preferably below 1MPa, is more preferably below 0.7MPa.In addition, the lower limit of reaction pressure is not particularly limited, but is generally more than 1kPa, is preferably more than 50kPa.If reaction pressure is too high, then the growing amount of the by product that paraffinic hydrocarbons and aromatics etc. are not preferred increases, and the yield of propylene has the trend of reduction.If reaction pressure is too low, then speed of response has the tendency slowed down.

< reacts the consumption > of the raw material caused

Relative to the summation of the molar flow of the molar flow of the methyl alcohol be supplied in reactor and the dme of 2 times, be preferably less than 1% in the summation of the molar flow of the molar flow of the methyl alcohol of reactor exit and the dme of 2 times.Preferably be less than 0.1% further.

If the consumption of methyl alcohol and dme is few and the amount of the methyl alcohol of reactor exit or dme excessively increases in reactor, then the purifying of goods alkene is made to become difficulty.

As the method for consumption increasing methyl alcohol and dme, the method improving temperature of reaction or reduce space velocity can be enumerated.

In addition, in the present invention, relative to the molar flow of the alkene of the carbonatoms more than 4 be supplied in reactor, the molar flow of the alkene of the carbonatoms more than 4 of reactor exit is more than 20% and is less than 90%.This molar flow ratio is preferably more than 20% and is less than 70%, and more preferably more than 25% and be less than 60%.If the consumption of the alkene of carbonatoms more than 4 is very few in reactor, then unreacted alkene increases, and the flow being recycled to the fluid in reactor excessively increases, therefore not preferred.On the contrary, if consumption is too much, by-product is gone out the compound of the non-expectation such as paraffinic hydrocarbons or aromatics, propene yield reduces, therefore not preferred.

As the method for the alkene consumption of adjustment carbonatoms more than 4, the method for suitably setting temperature of reaction or space velocity etc. can be enumerated.

Wherein, the analytical procedure that the flow being supplied to the alkene of the methyl alcohol in reactor, dme and carbonatoms more than 4 can adopt vapor-phase chromatography etc. conventional by carrying out quantitatively the composition of the various fluid be supplied in reactor or mixed fluid thus measuring the flow of various fluid and learn, the method that vapor-phase chromatography etc. can be adopted conventional at the flow of the alkene of the methyl alcohol of reactor exit, dme and carbonatoms more than 4 by the composition of reactor exit fluid is carried out quantitatively thus measure or calculating reactor exit fluid flow and learn.

< reaction product >

As reactor outlet gas (reactor effluent), the mixed gas containing reaction product and propylene, unreacting material, by product and thinner can be obtained.Density of propylene in this mixed gas is generally 5 ~ 95 % by weight.

Unreacting material is generally the alkene of carbonatoms more than 4.According to the difference of reaction conditions, containing at least one in methyl alcohol and dme, but react under the reaction conditions of at least one preferably in not residual methanol and dme.Like this, being separated of reaction product and unreacting material is easily carried out.

As by product, ethene, the olefines of carbonatoms more than 4, paraffinic, aromatics and water can be enumerated.

[separating step]

Separating step in 1st and the 2nd embodiment

The hydrocarbon of < carbonatoms less than 3 and being separated of water: step (2) >

Reactor outlet gas by cooling, compression and the common separating step such as distillation be separated into the hydrocarbon being rich in carbonatoms less than 3 fluid, be rich in the fluid (A) of the hydrocarbon of carbonatoms more than 4 and be rich in the fluid of water.

As the 1st embodiment of above-mentioned common separating step, the method comprised the steps can be used, described step is: after cooling and compression step condensation removing moisture, the fluid of the fluid being separated by distillation into the hydrocarbon being rich in carbonatoms less than 2 and the hydrocarbon being rich in carbonatoms more than 3, then the fluid (A) by distillation the fluid of the hydrocarbon being rich in carbonatoms more than 3 being separated into the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4.

As the 2nd embodiment of common separating step, the method comprised the steps can be used, described step is: after cooling and compression step condensation removing moisture, the fluid (A) of the fluid being separated by distillation into the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon being rich in carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and be rich in the fluid that carbonatoms is the hydrocarbon of 3.

As the 3rd embodiment of common separating step, the method comprised the steps can be used, described step is: after cooling and compression step condensation removing moisture, be separated by distillation into fluid that hydrocarbon containing carbonatoms less than 2 and carbonatoms are the hydrocarbon of 3 and be rich in the fluid of hydrocarbon of carbonatoms more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (A) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

As the 4th embodiment of common separating step, the method comprised the steps can be used, described step is: after cooling and compression step condensation removing moisture, the fluid (A) of the fluid being separated by distillation into the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon being rich in carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into hydrocarbon containing carbonatoms less than 2 by distillation and carbonatoms is the fluid of the hydrocarbon of 3 and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

In the 1st ~ 4th embodiment of above-mentioned common separating step, preferably carry out the process such as termination reaction (quench), alkali cleaning, dehydration if desired.Time in reactor outlet gas containing oxygenatedchemicals, by termination reaction step, remove oxygenatedchemicals at least partially.Time in reactor outlet gas containing sour gas such as carbonic acid gas, remove sour gas at least partially by alkali cleaning.

Water mainly can adopt and carries out condensation with cooling by compressing and be separated.Preferably with the moisture that the sorbent material removings such as molecular sieve are remaining.The water removed by condensation and/or absorption can be used to the waste water treatment step of active sludge etc., also can be used to process water etc.

When technical process of the present invention (following, to be sometimes referred to as " this technical process ") is close to steam cracking process flow process, the water preferably reclaimed by reactor outlet gas uses as cracking vapour source.In addition, can also be recycled in the reactor of this technical process and use as diluent gas.

In addition, by the hydrocarbon of the carbonatoms less than 2 by reactor outlet gas gained, carbonatoms be preferably 3 hydrocarbon obtain the high ethene of purity and propylene respectively further by purification steps such as distillations.The purity of ethene is more than 95%, is preferably more than 99%, is more preferably more than 99.9%.The purity of propylene is more than 95%, is preferably more than 99%, is more preferably more than 99.9%.

The ethene of such gained and propylene, even if from the viewpoint of qualities such as impurity levels, also the ethene and the propylene derived raw material that can be used as preparation usually use, and ethene can be used for following preparation: such as, prepares oxyethane, ethylene glycol, thanomin, glycol ether etc. by oxidizing reaction; Vinyl chloride monomer, 1，1，1-trichloroethane, vinyl chloride resin, vinylidene chloride is prepared by chlorination; Or prepare alpha-olefin, low density or high density polyethylene(HDPE) by the polymerization of ethene; Ethylbenzene etc. is prepared by the ethylization of benzene.

Polyethylene terephthalate can be prepared for raw material further with the ethylene glycol by ethylene making, and can be that raw material prepares higher alcohols by carbongl group synthesis reaction and hydrogenation subsequently with alpha-olefin, can also be that raw material prepares styrene monomer, ABS resin etc. with ethylbenzene.In addition, by preparing vinyl-acetic ester with the reaction of acetic acid, prepare acetaldehyde and the ethyl acetate etc. as its derivative by watt gram reacting (wacker reaction).

In addition, propylene is applicable to following preparation: such as, prepares vinyl cyanide by ammonia oxidation; Propenal, vinylformic acid and acrylate is prepared by selective oxidation; The oxo alcohol such as propyl carbinol, 2-Ethylhexyl Alcohol is prepared by carbongl group synthesis reaction; Polypropylene is prepared by the polymerization of propylene; Propylene oxide and propylene glycol etc. is prepared by the selective oxidation of propylene.In addition, watt gram reaction can be utilized to prepare acetone, acetone can be utilized further to prepare methyl iso-butyl ketone (MIBK).Further, can prepare acetone cyanohydrin by acetone, described cyanalcohol finally can be converted into methyl methacrylate.In addition, Virahol can also be prepared by propylene hydration.In addition, make benzene generation alkylation obtain isopropyl benzene, it can be used as raw material, phenol, dihydroxyphenyl propane, polycarbonate resin can be prepared.

In addition, the fluid being preferably the hydrocarbon of 3 by the hydrocarbon containing carbonatoms less than 2 obtained in the 3rd embodiment and the 4th embodiment of above-mentioned common separating step and carbonatoms is supplied to and carries out purifying preparing in the technical process of ethene and propylene except this technical process.As the technical process preparing ethene and propylene except this technical process, the steam cracking process flow process of petroleum naphtha or ethane etc. can be enumerated.Obviously can reduce the investment of equipment in this technical process thus.

On the other hand, this technical process can not be generated containing the fluid of ethene be supplied to except this technical process prepare the technical process of ethene and propylene time, owing to being necessary the purifying carrying out ethene in this technical process, therefore preferably adopt above-mentioned 1st embodiment or the 2nd embodiment in this case.

Separating step in 3rd embodiment

[separating step]

< gaseous constituent, liquid component are separated with water: step (2C), (3C) >

In the present invention, reactor outlet gas is cooled, cooled gaseous fluid (K) be separated into gaseous fluid (L) by compression, be rich in the fluid of the hydrocarbon of carbonatoms more than 4, fluid liquid (M) containing aromatics and be rich in the fluid (step (2C)) of water, subsequently, gaseous fluid (L) be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by common separating steps such as distillations and be rich in the fluid (N) (step (3C)) of hydrocarbon of carbonatoms more than 4.

In step (2C), reactor outlet gas is generally the temperature of about 300 ~ 600 DEG C, and this reactor outlet gas is cooled to about 20 ~ 200 DEG C.This cooling is undertaken by heat exchanger usually, also can by directly cooling with the fluid chemical field lower than this gas temperature.Use compressor, separating tank or water-and-oil separator etc. by compression cooled fluid (K) is separated into the hydrocarbon being rich in carbonatoms less than 6 gaseous fluid (L), be rich in carbonatoms and be the hydrocarbon of more than 4 and the fluid liquid (M) containing aromatics and be rich in the fluid of water.In addition, in above-mentioned heat exchanger, the fluid carrying out heat exchange with reactor outlet gas is not particularly limited, but is preferably supplied to one or more fluids in reactor.

The gaseous fluid (L) that be rich in the hydrocarbon of carbonatoms less than 6 separated through this reactions steps (2C) is hydrocarbon-containifluids fluids, in step (3C), it is separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by common separating steps such as distillations and is rich in the fluid (N) of hydrocarbon of carbonatoms more than 4.

As the 1st embodiment of above-mentioned common separating step, the method comprised the steps can be adopted, described step is: be isolated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and be rich in the fluid of hydrocarbon of carbonatoms more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (N) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

As the 2nd embodiment of separating step, the method comprised the steps can be adopted, described step is: be isolated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and be rich in the fluid (N) of hydrocarbon of carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

As the 3rd embodiment of common separating step, the method comprised the steps can be used, described step is: by distilling the hydrocarbon that is isolated into containing carbonatoms less than 2 and carbonatoms is the fluid of the hydrocarbon of 3 and is rich in the fluid that carbonatoms is the hydrocarbon of more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (N) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

As the 4th embodiment of common separating step, the method comprised the steps can be used, described step is: be isolated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and be rich in the fluid (N) of hydrocarbon of carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into hydrocarbon containing carbonatoms less than 2 by distillation and carbonatoms is the fluid of the hydrocarbon of 3 and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

In above-mentioned technical process, preferably carry out the process such as termination reaction, alkali cleaning, dehydration if desired.Time in reactor outlet gas containing oxygenatedchemicals, by termination reaction step, remove oxygenatedchemicals at least partially.Time in reactor outlet gas containing sour gas such as carbonic acid gas, remove sour gas at least partially by alkali cleaning.

The ethene of such gained and propylene all can be used as ethene and the acryloyl derivative use of preparation usually, and ethene can be used for following preparation: such as, prepares oxyethane, ethylene glycol, thanomin, glycol ether etc. by oxidizing reaction; Vinyl chloride monomer, 1，1，1-trichloroethane, vinyl chloride resin, vinylidene chloride is prepared by chlorination; Or prepare alpha-olefin, low density or high density polyethylene(HDPE) by the polymerization of ethene; Ethylbenzene etc. is prepared by the ethylization of benzene.

Polyethylene terephthalate can be prepared for raw material further with the ethylene glycol by ethylene making, and can be that raw material prepares higher alcohols by carbongl group synthesis reaction and hydrogenation subsequently with alpha-olefin, can also be that raw material prepares styrene monomer, ABS resin etc. with ethylbenzene.In addition, by preparing vinyl-acetic ester with the reaction of acetic acid, prepare acetaldehyde and the ethyl acetate etc. as its derivative by a watt gram reaction.

In addition, the fluid being preferably the hydrocarbon of 3 by the hydrocarbon containing carbonatoms less than 2 obtained in the 3rd embodiment and the 4th embodiment of above-mentioned separating step and carbonatoms is supplied to and carries out purifying preparing in the technical process of ethene and propylene except this technical process.As the technical process preparing ethene and propylene except this technical process, the steam cracking process flow process of petroleum naphtha or ethane etc. can be enumerated.Obviously can reduce the investment of equipment in this technical process thus.

1st and the 2nd embodiment

The separation of the hydrocarbon of < carbonatoms more than 4 and recirculation: step (3A), (3B) >

By (following for the fluid (A) being rich in the hydrocarbon of carbonatoms more than 4 be separated by reactor outlet gas at least partially, be called the hydrocarbon fluid (A) of carbonatoms more than 4) be recycled in reactor, residual fluid is taken out from this technical process.

" taking out from this technical process " mentioned here refers to and is not recycled in the reactor of this technical process, directly can be supplied in other technical process via pipe arrangement, also can be supplied to again in other technical process afterwards in a reservoir via pipe arrangement temporary storage.In addition, also can not be supplied in other technical process and use as fuel.

As the 1st embodiment hydrocarbon fluid (A) of carbonatoms more than 4 being recycled to the method in reactor, the method comprised the steps can be adopted, described step is: a part (B) for the hydrocarbon fluid (A) of carbonatoms more than 4 taken out from this technical process, by common separation methods such as distillations, the fluid (C) of remnants is separated into fluid (D) and fluid (E), and fluid (D) is recycled in reactor, fluid (E) is taken out from this technical process, in wherein said fluid (D), aromatic concentrations (% by weight) is than low in fluid (C), in described fluid (E), carbonatoms is low in the hydrocarbon concentration ratio fluid (C) of 4.

As the 2nd embodiment, the method comprised the steps can be adopted, described step is: by common separation methods such as distillations, the hydrocarbon fluid (A) of carbonatoms more than 4 is separated into fluid (G) and fluid (F), and will take out from this technical process by fluid (F) at least partially, the fluid (I) at least partially of fluid (G) is recycled in reactor, again the fluid (H) of remnants is taken out from this technical process, in wherein said fluid (G), aromatic concentrations (% by weight) is than low in fluid (A), in described fluid (F), carbonatoms is low in the hydrocarbon concentration ratio fluid (A) of 4.

When using olefin feedstock as carbonatoms more than 4 of the raw material of paraffinic hydrocarbons containing carbonatoms more than 4, due to the composition fluid that the fluid (B) in above-mentioned 1st embodiment or the fluid (H) in the 2nd embodiment are containing a large amount of paraffinic hydrocarbons, be therefore difficult to the effective constituents such as separation and purification butylene.Therefore, when this technical process is close to steam cracking process flow process, is preferably supplied in steam cracking process flow process, is effectively utilized as cracking stock.

Thus, these fluids (B), (H) can be used as the raw material for the preparation of ethene or propylene in steam cracking process flow process.Now, preferably make contacting with hydrogenation catalyst at least partially in fluid (B) or fluid (H), the fluid of paraffin concentration higher than fluid (B) or fluid (H) is supplied in steam cracking process flow process.When fluid high for concentration of olefin being supplied in the cracking unit of steam cracking process flow process, in cracking unit, easily producing carbon separate out, therefore not preferred.

In addition, now, the total concn of aromatics contained in preferably fluid (B) or fluid (H) is less than 5.0 volume %, is more preferably less than 3.0 volume %.If aromatic concentrations is high, then when being supplied in cracking unit, not only carbon is separated out many, and there is the trend of yield of ethene reduction, therefore not preferred.

In addition, the fluid (E) preferably in above-mentioned 1st embodiment or the fluid (F) in the 2nd embodiment mix with the cracked naphtha of steam cracking process flow process etc.Like this, fluid (E) or fluid (F) can effectively be utilized.

Pressure gasoline mentioned here refers to the fluid of main paraffinic hydrocarbons containing carbonatoms less than more than 5 10, alkene, diene, aromatics, as required, can reclaim effective constituent from pressure gasoline.As effective constituent, such as, can enumerate the aromatics such as hydrocarbon or benzene,toluene,xylene that carbonatoms is 5.

When being the hydrocarbon of 4 containing carbonatoms in pressure gasoline, the carbonatoms reclaimed from pressure gasoline is be mixed with the hydrocarbon that carbonatoms is 4 in the hydrocarbon fluid of 5, thus not preferred.Therefore, in the fluid (E) preferably mixed with cracked naphtha or fluid (F) carbonatoms be 4 hydrocarbon be less than 5 % by weight, be more preferably less than 2 % by weight.

As the feature of the 1st embodiment, owing to can reduce the burden of the separating steps such as distillation by taking out fluid (B), therefore favourable than the 2nd embodiment in auxiliary materials expense and facility investment expense two.But fluid (B) forms identical fluid with fluid (A), and compared with the fluid (H) obtained with the 2nd embodiment, the concentration of aromatics uprises.Therefore, technical process is selected according to the purposes being removed fluid.

3rd embodiment

The circulation of the hydrocarbon of < carbonatoms more than 4: step (4C) >

The fluid (N) being rich in the hydrocarbon of carbonatoms more than 4 that will be separated through step (3C) is (following, be called " hydrocarbon fluid (N) of carbonatoms more than 4 ") a part (P) take out from this technical process, remaining fluid (Q) is recycled in reactor.In addition, fluid liquid (M) by the hydrocarbon being rich in carbonatoms more than 4 of condensation in compression step and containing aromatics takes out at least partially from this technical process.

Fluid liquid (M) can be separated by distillation into fluid (R) and fluid (S), aromatic concentrations (% by weight) in wherein said fluid (R) is than low in fluid liquid (M), and in described fluid (S), carbonatoms is low in the hydrocarbon concentration ratio fluid liquid (M) of 4.Now, preferably make fluid (R) turn back to be selected from the circulation position of any one kind or two or more fluid in above-mentioned fluid (K), (L), (M), (P) and (Q).When containing the hydrocarbon of a large amount of carbonatoms less than 4 in fluid liquid (M), particularly preferably carry out this distillation procedure.

When using olefin feedstock as carbonatoms more than 4 of the raw material of paraffinic hydrocarbons containing carbonatoms more than 4, due to the composition fluid that above-mentioned fluid (M), (P), (R) are containing a large amount of paraffinic hydrocarbons, be therefore difficult to the effective constituents such as separation and purification butylene.Therefore, when this technical process is close to steam cracking process flow process, preferably more than a kind fluid in these fluids (M), (P), (R) is supplied in steam cracking process flow process, effectively utilizes as cracking stock.

Thus, these fluids can be used as the raw material for the preparation of ethene or propylene in steam cracking.Now, preferably make contacting with hydrogenation catalyst at least partially in fluid (M), (P), (R), the fluid of paraffin concentration higher than fluid (M), (P), (R) is supplied in steam cracking process flow process.When fluid high for concentration of olefin being supplied in the cracking unit of steam cracking process flow process, in cracking unit, easily producing carbon separate out, therefore not preferred.

In addition, now, the total concn of aromatics contained in preferably fluid (M), (P), (R) is less than 5.0 volume %, is more preferably less than 3.0 volume %.If aromatic concentrations is high, then when being supplied in cracking unit, not only carbon is separated out many, and there is the trend of yield of ethene reduction, therefore not preferred.

In addition, preferred above-mentioned fluid (S) mixes with the cracked naphtha of steam cracking process flow process etc.Like this, fluid (S) can effectively be utilized.In addition, when the hydrocarbon concentration of the carbonatoms less than 4 in fluid (S) is low, also can directly fluid (M) be mixed with cracked naphtha.

When being the hydrocarbon of 4 containing carbonatoms in pressure gasoline, the carbonatoms reclaimed from pressure gasoline is be mixed with the hydrocarbon that carbonatoms is 4 in the hydrocarbon fluid of 5, thus not preferred.Therefore, in the fluid (M) preferably mixed with cracked naphtha or fluid (S) carbonatoms be 4 hydrocarbon be less than 5 % by weight, be more preferably less than 2 % by weight.

The control > of the substrate concn of < reactor inlet

In above-mentioned 1st embodiment, by controlling the flow of fluid (B) and fluid (E), can control to be recycled to the diluting gas flows such as paraffinic hydrocarbons contained in the fluid (D) of reactor.

In addition, in the 2nd embodiment, by controlling the flow of fluid (F) and fluid (H), can control to be recycled to the diluting gas flows such as paraffinic hydrocarbons contained in the fluid (I) of reactor.

In above-mentioned 3rd embodiment, by controlling the flow of fluid (M) and fluid (P) or the flow by controlling fluid (P), fluid (R) and fluid (S), and then control the flow of fluid (R) again or it returns to position, can control to be recycled to the diluting gas flows such as paraffinic hydrocarbons contained in the fluid (Q) of reactor, wherein said fluid (R) is the fluid at the circulation position turning back to any one kind or two or more fluid be selected from fluid (K), (L), (M), (P) and (Q).

Like this, preferably the total concn (substrate concn) of the alkene of the carbonatoms more than 4 be supplied in whole base feeds of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

[with combining of steam cracking process flow process]

In steam cracking process flow process, be mostly from the carbonatoms obtained be the required composition of removing the hydrocarbon fluid (BB cut) of 4, and fluid (being mainly C4 raffinate-2) low for the value obtained like this is carried out hydrogenation, then return it in cracking unit.

In this technical process, can with the low fluid of described value for raw material, and then unwanted for this technical process fluid can be used in steam cracking process flow process, from this viewpoint, this technical process is the technical process very efficiently that low value fluid each other effectively can be utilized.

[embodiment of technical process]

Below, be described with reference to the embodiment of accompanying drawing to present invention process flow process.

Fig. 1 illustrates the 1st embodiment of present invention process flow process, and Fig. 2 illustrates the 2nd embodiment.

In Fig. 1,2,10 is reactors, and 20 is the 1st separation and purification systems, and 30A, 30B are the 2nd separation and purification systems.101 ~ 114 represent pipe arrangement respectively.

The explanation > of < the 1st embodiment (Fig. 1)

At least one in the raw material of carbonatoms more than 4, hydrocarbon fluid (D), methyl alcohol and dme from the carbonatoms more than 4 of the 2nd separation and purification system 30A is supplied in reactor 10 via pipe arrangement 101,102,103 and pipe arrangement 104 respectively.Be supplied to the paraffinic that can contain carbonatoms more than 4 in the olefin feedstock of the carbonatoms more than 4 of reactor 10, such as normal butane or Trimethylmethane etc.In addition, be supplied to via pipe arrangement 104 in the material flow of reactor 10 and can also contain divinyl or aromatics.As mentioned above, the butadiene concentration in material flow is generally 2.0 below volume %, and the mol ratio of the total amount of the alkene of carbonatoms more than 4 contained in the total amount of aromatics and the material flow of pipe arrangement 104 is less than 0.05 usually.It should be noted that, material flow refers to the total amount of the fluid of the supply via pipe arrangement 101,102 and 103, and these fluids not necessarily will collaborate before entering reactor 10, also can be supplied in reactor 10 respectively.Be supplied to unstripped gas in reactor 10 in reactor 10 with catalyst exposure and reacting, obtain the reactor outlet gas containing propylene, other alkene, paraffinic, aromatics and water.

Reactor outlet gas is sent to through pipe arrangement 105 in the common separation and purification systems 20 such as cooling, compression, distillation, the fluid being separated into the hydrocarbon being rich in carbonatoms less than 3 in this separation and purification system 20, the fluid (A) being rich in the hydrocarbon of carbonatoms more than 4 and the fluid being rich in water, be removed via pipe arrangement 106,108,107 respectively.Wherein, the fluid being rich in the hydrocarbon of carbonatoms less than 3 represents more than one fluid.Such as, can be a kind of fluid of the hydrocarbon containing carbonatoms less than 3, also can be the fluid of the hydrocarbon being rich in carbonatoms less than 2 and to be rich in fluid that fluid that carbonatoms is the hydrocarbon of 3 or the hydrocarbon containing atomicity less than 2 and carbonatoms are the hydrocarbon of 3 and to be rich in carbonatoms be the such two kinds of fluids of the fluid of the hydrocarbon of 3.It can also be the fluid of more than three kinds.

A part for the fluid (A) being rich in the hydrocarbon of carbonatoms more than 4 is fetched into outside technical process via pipe arrangement 109, and the fluid (C) of remnants is supplied in the common separation and purification system 30A such as distillation via pipe arrangement 110.A part of fluid (B) of fluid (A) can be fetched into outside technical process.Now, the fluid (B) of taking-up can use as the cracking stock of steam cracking process flow process.In this case, preferably make the fluid of taking-up (B) contact with hydrogenation catalyst, become fluid that paraffin concentration is improved and be supplied in steam cracking process flow process.In the fluid (B) now taken out, the total concn of aromatics is less than 5.0 volume %.

In separation and purification system 30A, fluid (C) is separated into fluid (D) and fluid (E), and fluid (D) be recycled in reactor 10 via pipe arrangement 102 at least partially, and fluid (E) takes out from this technical process via pipe arrangement 111, in wherein said fluid (D), aromatic concentrations is than low in fluid (C), low in the hydrocarbon concentration ratio fluid (C) of the middle carbonatoms more than 4 of described fluid (E).The fluid (E) taken out can mix with the cracked naphtha of steam cracking process flow process etc.Now, contained in preferably fluid (E) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

A part of fluid (hereinafter referred to as " fluid (X) ") of fluid (D) can be fetched into outside technical process.Now, the cracking stock use that fluid (X) can be used as steam cracking process flow process is taken out.In this case, preferably make taking-up fluid (X) contact with hydrogenation catalyst, become the fluid that paraffin concentration is improved and be supplied in steam cracking process flow process.In taking-up fluid (X) now, the total concn of aromatics is less than 5.0 volume %.

Above-mentioned fluid (D) and fluid (X) are not must take out from technical process, but in order to prevent the accumulation of paraffinic, preferably will at least take out from technical process by any one fluid.

The explanation > of < the 2nd embodiment (Fig. 2)

At least one in the raw material of carbonatoms more than 4, hydrocarbon fluid (I), methyl alcohol and dme from the carbonatoms more than 4 of the 2nd separation and purification system 30B is supplied in reactor 10 via pipe arrangement 101,102,103 and pipe arrangement 104 respectively.Then, in the 1st separation and purification system 20, due to from reactor 10 exit gas, the step to the fluid being separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3, the hydrocarbon fluid (A) of carbonatoms more than 4 and being rich in water, all identical with Fig. 1, therefore explanation is omitted.

The hydrocarbon fluid (A) of carbonatoms more than 4 is supplied to the common separation and purification system 30B such as distillation by pipe arrangement 108.In separation and purification system 30B, be separated into aromatic concentrations lower than the fluid (G) of fluid (A) and the hydrocarbon concentration of carbonatoms more than 4 fluid (F) lower than fluid (A), fluid (F) takes out from this technical process via pipe arrangement 112.Take out fluid (F) to mix with the cracked naphtha of steam cracking process flow process etc.Now, contained in preferably fluid (F) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

Fluid (G) is removed via pipe arrangement 113, its part (H) is taken out from this technical process via pipe arrangement 114, and remaining fluid (I) is recycled in reactor 10 via pipe arrangement 102.Take out the cracking stock use that fluid (H) can be used as steam cracking process flow process.In this case, preferably make fluid (H) contact with hydrogenation catalyst, become fluid that paraffin concentration is improved and be supplied in steam cracking process flow process.In fluid (H) now, the total concn of aromatics is less than 5.0 volume %.

It is not required for being fetched into outside technical process by above-mentioned fluid (H), but in order to prevent the accumulation of paraffinic, preferably a part at least any one fluid is taken out from technical process.

[embodiment of technical process]

< the 3rd embodiment (Fig. 3) >

Fig. 3 illustrates an embodiment of present invention process flow process.

In figure 3,13 be reactor, 23 be compressor, 33 be separating tank, 43 for oil-water separator, 53 be the 1st separation and purification system, 63 be the 2nd separation and purification system.301 ~ 315 represent pipe arrangement respectively.

At least one in the olefin feedstock of carbonatoms more than 4, hydrocarbon fluid (Q), methyl alcohol and dme from the carbonatoms more than 4 of the 1st separation and purification system 53 is supplied in reactor 13 via pipe arrangement 301,302,303 and pipe arrangement 304 respectively.Be supplied to the paraffinic that can contain carbonatoms more than 4 in the olefin feedstock of the carbonatoms more than 4 of reactor 13, such as normal butane, Trimethylmethane etc.In addition, be supplied to via pipe arrangement 304 in the material flow of reactor 13 and can also contain divinyl or aromatics.As mentioned above, the butadiene concentration in material flow is generally 2.0 below volume %, and the mol ratio of the total amount of the alkene of carbonatoms more than 4 contained in the total amount of aromatics and the material flow of pipe arrangement 304 is less than 0.05 usually.It should be noted that, material flow refers to the total amount of the fluid of the supply via pipe arrangement 301,302 and 303, and these fluids not necessarily will collaborate before entering reactor 13, also can be supplied in reactor 13 respectively.Be supplied to unstripped gas in reactor 13 in reactor 10 with catalyst exposure and reacting, obtain the reactor outlet gas containing propylene, other alkene, paraffinic, aromatics and water.

Reactor outlet gas is cooled by such as heat exchanger, and cooled gaseous fluid (K) is boosted by compressor 23 through pipe arrangement 305.Compressor 23 can be 1, but preferred multiple stage.Heat exchanger and separating tank 33 are set after each compressor 23, after being cooled by the gas after compression, are separated into gaseous fluid (L) and condensation composition.Be condensed into and point be sent in water-and-oil separator 43 via pipe arrangement 308, be separated into the fluid (M) of the hydrocarbon being rich in carbonatoms more than 4 and be rich in the fluid of water; The fluid being rich in water is removed through pipe arrangement 310, and the fluid (M) being rich in the hydrocarbon of carbonatoms more than 4 is sent in the 2nd separation and purification system 63 via pipe arrangement 309.

The gaseous fluid (L) be separated through separating tank 33 is sent in the common 1st separation and purification systems 53 such as distillation via pipe arrangement 307, be separated into the fluid (N) of the fluid richness of the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon of carbon atom quantity more than 4, be removed via pipe arrangement 313,314 respectively.Wherein, the fluid being rich in the hydrocarbon of carbonatoms less than 3 represents more than one fluid.Such as, can be a kind of fluid of the hydrocarbon containing carbonatoms less than 3, also can be the fluid of the hydrocarbon being rich in carbonatoms less than 2 and to be rich in fluid that fluid that carbonatoms is the hydrocarbon of 3 or the hydrocarbon containing atomicity less than 2 and carbonatoms are the hydrocarbon of 3 and to be rich in carbonatoms be the such two kinds of fluids of the fluid of the hydrocarbon of 3.It can also be the fluid of more than three kinds.

The part (P) being rich in the fluid (N) of the hydrocarbon of carbonatoms more than 4 is fetched to outside technical process via pipe arrangement 315, and remaining fluid (Q) is recycled in reactor 13 via pipe arrangement 302.The cracking stock that fluid (P) can be used as steam cracking process flow process uses.In this case, preferably make fluid (P) contact with hydrogenation catalyst, become fluid that paraffin concentration is improved and be supplied in steam cracking process flow process.Now, in preferably fluid (P), the total concn of aromatics is less than 5.0 volume %.

On the other hand, the fluid liquid (M) be separated through oil-water separator 43 is rich in the hydrocarbon of carbonatoms more than 4 and the liquid parts containing aromatics, directly fluid liquid (M) can be taken out from this technical process, now, fluid liquid (M) can be used as the cracking stock use of steam cracking process flow process.In this case, preferably make fluid (M) contact with hydrogenation catalyst, become fluid that paraffin concentration is improved and be supplied in steam cracking process flow process.Now, in preferably fluid (M), the total concn of aromatics is less than 5.0 volume %.

In addition, in fluid liquid (M) carbonatoms be 4 hydrocarbon concentration low time, also can directly fluid (M) be mixed with the cracked naphtha of steam cracking process flow process etc.In this case, contained in preferably fluid (M) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

In addition, fluid (R) and fluid (S) is separated into through the common separating steps such as distillation i.e. the 2nd separation and purification system 60 at least partially preferably by fluid liquid (M), in described fluid (R), aromatic concentrations is than low in fluid (M), and in described fluid (S), carbonatoms is low in the hydrocarbon concentration ratio fluid (M) of 4.Wherein, fluid (R) after separation is removed via pipe arrangement 111, but 1 place in the pipe arrangement 305,307,314,315,302 that preferably fluid (R) turns back to fluid (K), fluid (L), fluid (N), fluid (P), fluid (Q) circulate or many places.

On the other hand, fluid (S) is taken out by pipe arrangement 312, and this fluid (S) can mix with the cracked naphtha of steam cracking process flow process etc.In this case, contained in preferably fluid (S) carbonatoms is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

Above-mentioned operation of being taken out outside technical process by fluid (P) is optional, but in order to prevent the accumulation of paraffinic, preferably a part at least any one fluid is taken out from technical process.

Embodiment

Below, enumerate embodiment and more specific description is carried out to the present invention, but the present invention is not by any restriction of following embodiment.

[preparation of catalyzer]

The catalyzer used in following embodiment, comparative example is prepared by the following method.

The preparation example > of < catalyzer

26.6g bromination four n-propyl ammonium (TPABr) and 4.8g sodium hydroxide are dissolved in 280g water successively, more slowly add 75g colloid silica (SiO ₂=40 % by weight, Al < 0.1 % by weight) and the mixed solution of 35g water, fully stir, obtain aqueous gel.Then, this gel is joined in 1000ml autoclave, from pressure, while carry out stirring with 300rpm, the Hydrothermal Synthesis of 72 hours is carried out on limit at 170 DEG C.From resultant, isolate solids component by pressure filtration, after fully washing, at 100 DEG C, carry out drying in 24 hours.Dried catalyzer carries out firing for 6 hours in 550 DEG C under air circulation, obtains Na type silico-aluminate.

2.0g above-mentioned Na type silico-aluminate is suspended in the 1M aqueous ammonium nitrate solution of 40ml, and carries out stirring for 2 hours at 80 DEG C.From the solution after process, isolate solids component by suction filtration, after fully washing, again make it be suspended in the 1M aqueous ammonium nitrate solution of 40ml, and carry out stirring for 2 hours at 80 DEG C.From the solution after process, solids component is isolated by suction filtration, after fully washing, drying 24 hours at 100 DEG C.Dried catalyzer carries out firing for 4 hours in 500 DEG C under air circulation, obtains H type silico-aluminate.

By carrying out XRD (X-ray diffraction) to above-mentioned catalyzer, confirming it zeolite structured is MFI type.Carry out quantitatively by chemical analysis to the composition of catalyzer, its SiO ₂/ Al ₂o ₃=1100 (mol ratios).

[preparation of propylene]

Below for using embodiment and the comparative example of above-mentioned catalyst preparing propylene.

< embodiment 1>

Above-mentioned catalyzer is used to carry out the preparation of propylene.

Using atmospheric fixed bed circulation reaction unit in reaction, is the mixture of filling the above-mentioned catalyzer of 0.10g, 1.0g quartz sand in the quartz reaction tubes of 6mm at internal diameter.In this reactor, the gas prepared by iso-butylene (40 volume %), methyl alcohol (20 volume %), benzene (0.8 volume %), divinyl (0.1 volume %) and Trimethylmethane (39.1 volume %) is supplied as the analog gas being equivalent to reactor inlet gas of the present invention (pipe arrangement 104 of Fig. 1 or Fig. 2) and forming by vaporizer.Temperature of reaction (reactor inlet gas temperature) is 550 DEG C.Reaction beginning, after 70 minutes, carries out the analysis of product by gas-chromatography.Reaction conditions now and reaction result as shown in table 1.

The selection rate of propylene is 54.8%, is very high level.

Proceed reaction, using until the low conversion rate of the methyl alcohol time in 99% time as catalyst life, evaluate.Result catalyst life is 312 hours.

< embodiment 2>

Except making, the benzene concentration be supplied in reactor is 1.6 volume %, concentration of isobutane is except 38.3 volume %, all reacts according to the method identical with embodiment 1.Reaction beginning, after 70 minutes, carries out the analysis of product by gas-chromatography.Reaction conditions now and reaction result as shown in table 1.

The selection rate of propylene is 54.4%, is very high level.

Proceed reaction, using until the low conversion rate of the methyl alcohol time in 99% time as catalyst life, evaluate.Result catalyst life is 305 hours.

< comparative example 1>

Except making, the benzene concentration be supplied in reactor is 3.2 volume %, concentration of isobutane is except 36.7 volume %, all reacts according to the method identical with embodiment 1.Reaction beginning, after 70 minutes, carries out the analysis of product by gas-chromatography.Reaction conditions now and reaction result as shown in table 1.

The selection rate of propylene is 51.4%, is in a ratio of low-down level with embodiment 1 and 2.

This is because raw material butylene and/or methyl alcohol and benzene react, and generates alkylated benzenes, and the butylene that should be used for generating propylene and/or methyl alcohol are consumed meaninglessly.

Proceed reaction, using until the low conversion rate of the methyl alcohol time in 99% time as catalyst life, evaluate.Result catalyst life is 221 hours, is in a ratio of very short result with embodiment 1 and 2.Infer that this is because catalyzer pore blocks by abovementioned alkyl benzene, and promote coking.

Like this, according to method of the present invention, by by the taking-up at least partially of aromatics instead of be recycled in reactor, reduce the aromatic concentrations of reactor inlet, this is for realizing high propylene yield and suppressing catalyst coking deterioration to be very effective.

[table 1]

^*1: the selection rate of the alkene of carbonatoms more than 5

^*2: total selection rate of aromatics and paraffinic hydrocarbons

Although with reference to specific embodiment to invention has been detailed description, only it will be understood by those skilled in the art that otherwise exceeding present inventive concept and scope, various changes and modifications can be carried out to it.

The Japanese patent application (Japanese Patent Application 2006-255504) that the Japanese patent application (Japanese Patent Application 2006-255503) that the application filed an application based on September 21st, 2006, on September 21st, 2006 file an application completes, and the content of above-mentioned application is introduced in the present invention as a reference.

Industrial applicibility

The invention provides a kind of for the preparation of the novel of propylene and the technical process of cheapness and this technical process combined with steam cracking process flow process novel and the technical process of cheapness, the described technical process for the preparation of propylene makes the olefine reaction of at least one in methyl alcohol and dme and carbonatoms more than 4 to prepare the technical process of propylene.

Claims

1. the preparation method of a propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and raw material containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1), the technical process of (2) and (3A) forms

Step (1): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (D) from step (3A) recirculation are supplied to reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 70%, under the reaction conditions, make above-mentionedly to be supplied to material in reactor and above-mentioned catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the reactor outlet gas of aromatics and water, and, in this step, the mol ratio of the alkene total amount of carbonatoms more than 4 contained in the total amount and this whole raw material of the aromatics contained by described being supplied in whole raw materials of reactor is less than 0.05,

Step (3A) a: part (B) for fluid (A) in above-mentioned steps (2) is taken out from this technical process, remaining fluid (C) is made to be separated into fluid (D) and fluid (E), and above-mentioned fluid (D) is recycled in reactor, above-mentioned fluid (E) takes out from this technical process, in wherein said fluid (D), aromatic concentrations is than low in fluid (C), in described fluid (E), carbonatoms is low in the hydrocarbon concentration ratio fluid (C) of 4, in this step, described fluid (B) is supplied in steam cracking process flow process, use as cracking stock.

2. the preparation method of propylene according to claim 1, wherein, above-mentioned reactor comprises the plural reacting part be connected in series, by above-mentioned be supplied to the methyl alcohol in reactor and at least one in dme, the olefin feedstock of carbonatoms more than 4 and recirculation be supplied to the 1st section of reacting part and the 2nd section or later reacting part containing at least one segmentation in the fluid (D) of hydrocarbon.

3. the preparation method of the propylene described in claim 1 or 2, wherein, makes contacting with hydrogenation catalyst at least partially of above-mentioned fluid (B), is then supplied in steam cracking process flow process.

4. the preparation method of the propylene described in claim 1 or 2, wherein, the total concn of aromatics contained in above-mentioned fluid (B) is less than 5.0 volume %.

5. the preparation method of the propylene described in claim 1 or 2, wherein, mixes above-mentioned fluid (E) with the cracked naphtha of steam cracking process flow process.

6. the preparation method of the propylene described in claim 1 or 2, wherein, carbonatoms contained in above-mentioned fluid (E) is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

7. the preparation method of the propylene described in claim 1 or 2, wherein, by controlling the flow of above-mentioned fluid (B) and above-mentioned fluid (E), the total concn of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

8. the preparation method of a propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and mixture containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, its by comprising the following steps (1), the technical process of (2) and (3B) forms

Step (1): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (I) from step (3B) recirculation are supplied to reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 70%, under the reaction conditions, make itself and catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the reactor outlet gas of aromatics and water, and, in this step, the mol ratio of the alkene total amount of carbonatoms more than 4 contained in the total amount and this whole raw material of the aromatics contained by described being supplied in whole raw materials of reactor is less than 0.05,

Step (3B): the fluid (A) in above-mentioned steps (2) is separated into fluid (G) and fluid (F), above-mentioned fluid (F) takes out from this technical process, and a part (I) of above-mentioned fluid (G) is recycled in reactor, remaining fluid (H) takes out from this technical process, in wherein said fluid (G), aromatic concentrations is than low in fluid (A), in described fluid (F), carbonatoms is low in the hydrocarbon concentration ratio fluid (A) of 4, in this step, described fluid (H) is supplied in steam cracking process flow process, use as cracking stock.

9. the preparation method of propylene according to claim 8, wherein, described reactor comprises the plural reacting part be connected in series, and is that hydrocarbon-containifluids fluids (I) segmentation of at least one in the olefin feedstock of more than 4, methyl alcohol and dme and recirculation is supplied to the 1st section of reacting part and the 2nd section or later reacting part by the above-mentioned carbonatoms be supplied in reactor.

10. the preparation method of the propylene described in claim 8 or 9, wherein, makes contacting with hydrogenation catalyst at least partially of described fluid (H), is then supplied in steam cracking process flow process.

The preparation method of the propylene described in 11. claims 8 or 9, wherein, the total concn of aromatics contained in described fluid (H) is less than 5.0 volume %.

The preparation method of the propylene described in 12. claims 8 or 9, wherein, mixes described fluid (F) with the cracked naphtha of steam cracking process flow process.

The preparation method of the propylene described in 13. claims 8 or 9, wherein, carbonatoms contained in described fluid (F) is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

The preparation method of the propylene described in 14. claims 8 or 9, wherein, by controlling the flow of described fluid (F) and described fluid (H), the total concn of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

The preparation method of the propylene according to any one of 15. claims 1,2,8 and 9, wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, the fluid of the fluid being then separated by distillation into the hydrocarbon being rich in carbonatoms less than 2 and the hydrocarbon being rich in carbonatoms more than 3, then the fluid by distillation the described fluid being rich in the hydrocarbon of carbonatoms more than 3 being separated into the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4.

The preparation method of the propylene according to any one of 16. claims 1,2,8 and 9, wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, the fluid of the fluid being then separated by distillation into the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon being rich in carbonatoms more than 4, the more described fluid being rich in the hydrocarbon of carbonatoms less than 3 be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and be rich in the fluid that carbonatoms is the hydrocarbon of 3.

The preparation method of the propylene according to any one of 17. claims 1,2,8 and 9, wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, then be separated by distillation into fluid that hydrocarbon containing carbonatoms less than 2 and carbonatoms are the hydrocarbon of 3 and be rich in the fluid of hydrocarbon of carbonatoms more than 3, the more described fluid being rich in the hydrocarbon of carbonatoms more than 3 is separated into the fluid of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

The preparation method of the propylene according to any one of 18. claims 1,2,8 and 9, wherein, described step (2) comprises the following steps: the condensation removing moisture from described reactor outlet gas by cooling and compression step, the fluid of the fluid being then separated by distillation into the hydrocarbon being rich in carbonatoms less than 3 and the hydrocarbon being rich in carbonatoms more than 4, the more described fluid being rich in the hydrocarbon of carbonatoms less than 3 be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and be rich in the fluid that carbonatoms is the hydrocarbon of 3.

The preparation method of the propylene according to any one of 19. claims 1,2,8 and 9, wherein, the olefin feedstock of described carbonatoms more than 4 contains the paraffinic of carbonatoms more than 4.

The preparation method of 20. propylene according to claim 19, wherein, described paraffinic contains at least one in normal butane and Trimethylmethane.

The preparation method of the propylene according to any one of 21. claims 1,2,8 and 9, wherein, is supplied in the raw material of reactor containing divinyl described.

The preparation method of the propylene according to any one of 22. claims 1,2,8 and 9, wherein, the amount being supplied to the alkene of the carbonatoms more than 4 in reactor described in is less than more than 0.2 10 with the mol ratio of 2 times of dme mole number that are supplied in this reactor and the total amount of moles of methanol.

The preparation method of the propylene according to any one of 23. claims 1,2,8 and 9, wherein, described in the olefin feedstock of carbonatoms more than 4 that is supplied in the reactor carbonatoms that contains steam cracking process flow process gained be the hydrocarbon fluid of 4.

The preparation method of 24. 1 kinds of propylene, the method is in the presence of a catalyst, make the alkene containing carbonatoms more than 4 and mixture containing at least one in methyl alcohol and dme in the reactor with catalyst exposure to prepare the method for propylene, its by comprise the following steps (1C), (2C), (3C), (4C) and (5C) technical process form

Step (1C): by least one in methyl alcohol and dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon fluid (Q) from step (4C) recirculation are supplied to reactor, relative to the molar flow of the alkene of the carbonatoms more than 4 of reactor inlet, the molar flow of the alkene of the carbonatoms more than 4 of reactor outlet is more than 20% and is less than 70%, under the reaction conditions, make above-mentionedly to be supplied to material in reactor and catalyst exposure, obtain containing propylene by reactor outlet, other alkene, paraffinic hydrocarbons, the reactor outlet gas of aromatics and water, and, in this step, the mol ratio of the alkene total amount of carbonatoms more than 4 contained in the total amount and this whole raw material of the aromatics contained by described being supplied in whole raw materials of reactor is less than 0.05,

Step (2C): cooling from the reactor outlet gas of above-mentioned steps (1C), and being separated into gaseous fluid (L) by compressing cooled gaseous fluid (K), and be rich in the hydrocarbon of carbonatoms more than 4 and contain the fluid liquid (M) of aromatics and be rich in the fluid of water;

Step (4C): (P) at least partially of above-mentioned fluid (N) is taken out from this technical process, and the fluid (Q) of remnants is recycled in reactor;

Step (5C): at least one in described fluid (M) and described fluid (P) is supplied in steam cracking process flow process, uses as cracking stock.

The preparation method of 25. propylene according to claim 24, wherein, by distillation, above-mentioned fluid liquid (M) is separated into fluid (R) and fluid (S), aromatic concentrations in wherein said fluid (R) is than low in fluid liquid (M), carbonatoms in described fluid (S) is low in the hydrocarbon concentration ratio fluid liquid (M) of 4, described fluid (R) is supplied in steam cracking process flow process, uses as cracking stock.

The preparation method of 26. propylene according to claim 25, wherein, described fluid (R) is turned back to the circulation position of any one kind or two or more fluid be selected from above-mentioned fluid (K), (L), (M), (P) and (Q).

The preparation method of the propylene according to any one of 27. claims 24 ~ 26, wherein, above-mentioned steps (3C) comprises the steps: described gaseous fluid (L) to be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and to be rich in the fluid of hydrocarbon of carbonatoms more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (N) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

The preparation method of the propylene according to any one of 28. claims 24 ~ 26, wherein, above-mentioned steps (3C) comprises the steps: described gaseous fluid (L) to be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and to be rich in the fluid (N) of hydrocarbon of carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

The preparation method of the propylene according to any one of 29. claims 24 ~ 26, wherein, above-mentioned steps (3C) comprises the steps: the fluid of the hydrocarbon described gaseous fluid (L) being separated into by distillation fluid that the hydrocarbon that comprises carbonatoms less than 2 and carbonatoms are the hydrocarbon of 3 and being rich in carbonatoms more than 3, then the fluid of the hydrocarbon being rich in carbonatoms more than 3 is separated into the fluid (N) of the hydrocarbon being rich in fluid that carbonatoms is the hydrocarbon of 3 and being rich in carbonatoms more than 4 by distillation.

The preparation method of the propylene according to any one of 30. claims 24 ~ 26, wherein, above-mentioned steps (3C) comprises the steps: described gaseous fluid (L) to be separated into the fluid of the hydrocarbon being rich in carbonatoms less than 3 by distillation and to be rich in the fluid (N) of hydrocarbon of carbonatoms more than 4, then the fluid of the hydrocarbon being rich in carbonatoms less than 3 is separated into the fluid of the hydrocarbon being rich in carbonatoms less than 2 by distillation and is rich in the fluid that carbonatoms is the hydrocarbon of 3.

The preparation method of the propylene according to any one of 31. claims 24 ~ 26, wherein, described reactor comprises the plural reacting part be connected in series, and the described at least one segmentation be supplied in the methyl alcohol in reactor and at least one in dme, the olefin feedstock of carbonatoms more than 4 and the hydrocarbon-containifluids fluids of recirculation is supplied to the 1st section of reacting part and the 2nd section or later reacting part.

The preparation method of the propylene according to any one of 32. claims 24 ~ 26, wherein, the olefin feedstock of described carbonatoms more than 4 contains the paraffinic of carbonatoms more than 4.

The preparation method of 33. propylene according to claim 32, wherein, described paraffinic contains at least one in normal butane and Trimethylmethane.

The preparation method of the propylene according to any one of 34. claims 24 ~ 26, wherein, described in be supplied in the raw material of reactor containing divinyl.

The preparation method of the propylene according to any one of 35. claims 24 ~ 26, wherein, make contacting with hydrogenation catalyst at least partially of at least one in described fluid (M) and described fluid (P), be then supplied in steam cracking process flow process.

The preparation method of the propylene according to any one of 36. claims 24 ~ 26, wherein, the total concn of aromatics contained at least one of described fluid (M) and described fluid (P) is less than 5.0 volume %.

The preparation method of the propylene according to any one of 37. claims 24 ~ 26, wherein, mixes described fluid (M) with the cracked naphtha of steam cracking process flow process.

The preparation method of the propylene according to any one of 38. claims 24 ~ 26, wherein, carbonatoms contained in described fluid (M) is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

The preparation method of the propylene according to any one of 39. claims 24 ~ 26, wherein, by controlling the flow of described fluid (M) and described fluid (P), the total concn of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

The preparation method of 40. propylene according to claim 25, wherein, makes contacting with hydrogenation catalyst at least partially of described fluid (R), is then supplied in steam cracking process flow process.

The preparation method of the propylene described in 41. claims 25 or 40, wherein, the total concn of aromatics contained in described fluid (R) is less than 5.0 volume %.

The preparation method of the propylene according to any one of 42. claims 25,26 and 40, wherein, mixes described fluid (S) with the cracked naphtha of steam cracking process flow process.

The preparation method of the propylene according to any one of 43. claims 25,26 and 40, wherein, carbonatoms contained in described fluid (S) is that the total concn of the hydrocarbon of 4 is less than 5 % by weight.

The preparation method of the propylene according to any one of 44. claims 25,26 and 40, wherein, by controlling the flow of described fluid (P), fluid (R) and fluid (S), the total concn of the alkene of the carbonatoms more than 4 contained by above-mentioned being supplied in whole raw materials of reactor, methyl alcohol and dme is controlled at 20 more than volume % 80 volume below %.

The preparation method of the propylene according to any one of 45. claims 25,26 and 40, wherein, when described fluid (R) being turned back to the position at any one or two or more the fluid place be selected from described fluid (K), (L), (N), (P) and (Q), by controlling position that described fluid (R) returns and flow thereof, the total concn of the above-mentioned alkene, methyl alcohol and the dme that are supplied to carbonatoms more than 4 contained in whole raw materials of reactor is controlled at 20 more than volume % 80 volume below %.

The preparation method of the propylene according to any one of 46. claims 24,25,26 and 40, wherein, the amount of the alkene of the above-mentioned carbonatoms more than 4 be supplied in reactor is less than more than 0.2 10 with being supplied to 2 times of mole number of the dme in this reactor with the mol ratio of the total amount of moles of methanol.

The preparation method of the propylene according to any one of 47. claims 24,25,26 and 40, wherein, the olefin feedstock of the above-mentioned carbonatoms more than 4 be supplied in reactor contains the hydrocarbon fluid of the carbonatoms more than 4 of steam cracking process flow process gained.