CN103380100A

CN103380100A - Manufacture of at least one ethylene derivative compound

Info

Publication number: CN103380100A
Application number: CN2012800090524A
Authority: CN
Inventors: 多米尼克·巴尔萨尔特; 米歇尔·朗珀勒
Original assignee: Solvay SA
Current assignee: Solvay SA
Priority date: 2011-02-15
Filing date: 2012-02-08
Publication date: 2013-10-30
Also published as: AR085233A1; WO2012110371A1

Abstract

Ethylene-containing composition comprises a hydrocarbon compounds containing 2 carbon atoms (a) between 75 and 99.9 % by volume; and (b) a quantity of ethylene such that the ratio of this quantity to the total quantity of hydrocarbon compounds containing 2 carbon atoms is comprised between 97 and 99.5 %. The invention discloses a process for the manufacture of such ethylene-containing composition, a process for the manufacture of at least one ethylene derivative compound starting from such ethylene-containing composition, and a process for the manufacture of ethylene dichloride according to which the ethylene-containing composition is subjected to a chlorination and/or an oxychlorination in order to produce ethylene dichloride, further pyrolyzed in order to produce vinyl chloride, further polymerized in order to produce polyvinyl chloride.

Description

The manufacturing of at least a ethylene derivative compounds

The application requires the right of priority of the European application submitted on February 15th, 2011 numbers 11154555.4, is combined in by reference this for the full content of all purpose this application.

The present invention relates to a kind of composition that contains ethene.Particularly, the present invention relates to a kind of at least a ethene derivatives that is suitable for making, more especially make a kind of composition that contains ethene of ethylene dichloride (EDC).It also relates to a kind of method of the composition that contains ethene for the manufacture of this kind and relates to for the manufacture of at least a ethylene derivative compounds, a kind of method of preferred EDC/ vinylchlorid (VC) and polyvinyl chloride (PVC).

Alkene is produced by catalysis or steam cracking process from petroleum traditionally.These cracking process, especially steam cracking have produced basic alkene from the hydrocarbons raw material, for example ethene and/or propylene.Ethene and propylene be many for the manufacture of the process of plastics and other compounds in useful staple commodities petroleum chemicals.Ethene is used to make multiple vinyon, and for the manufacture of other chemical, for example EDC/VC/PVC, ethylene oxide, ethylbenzene and alcohols.Propylene is used to make multiple acrylic plastering, and for the manufacture of other chemical, for example vinyl cyanide and propylene oxide.

Known for some time in petrochemical industry: oxygenate, especially alcohol can change into basic alkene, for example ethene and propylene.This process is called as oxygenate to process or the OTO process of alkene.The preferred oxygenate that is used for the production of basic alkene is methyl alcohol.The conversion process of this methanol to olefins is called as process or the MTO process of methanol to olefins.

This from the preferred MTO reactor of OTO() outflow stream comprise the alkene that makes us wishing, for example ethene and propylene, together with the by product of undesirable high density, the value of these by products can make ethene and propylene defective and it should be removed to make afterwards and have highly purified olefin product stream for their preferred disposal (for example polyreaction).

Therefore the removal of by product means the processing that some carry out the outflow stream that flows out from the OTO/MTO reactor, to produce very highly purified alkene (alkene that is called the polyreaction grade), particularly be characterized as greater than by volume 99.8%, often be the ethene of the polyreaction grade of 99.9% purity at least by volume.

Provide the example that is used for from this process of the efficient separation method of the ethene of isolating the polyreaction grade from an initial outflow stream of the reactive system of methanol to olefins and propylene and system among US7094971, to find.

For the alkene that the polyreaction grade is provided and particularly calculate for the necessary equipment of the ethene that the polyreaction grade is provided and resource (material and energy) can substantially increase running cost.

Therefore, for provide a kind of composition that contains ethene to have a kind of needs with low cost, this composition can contain dissimilar impurity and be in can forbidden level to its application in the future.

So purpose of the present invention partly provides a kind of composition that contains ethene, this composition preferably is suitable for making at least a the ethylene derivative compounds, particularly EDC of the purity with the ethene that is lower than the polyreaction grade.This composition that contains ethene is preferably from a kind of oxygenate raw material, obtain by the process of a kind of new oxygenate to alkene.

For this purpose, the present invention relates to a kind of composition that contains ethene, comprise

(a) hydrocarbon compound that contains 2 carbon atoms between 75% and 99.9% by volume; And

(b) ethene of a value, thus so that this value and the ratio of total amount value that contains the hydrocarbon compound of 2 carbon atoms are between 97% and 99.5%.

To be used to refer to comprise that ethene is as a kind of composition of main ingredient in this manual by " composition that contains ethene ".

The composition that contains ethene according to the present invention is included in by volume between 75% and 99.9%, preferably between 77% and 99.9%, more preferably at the hydrocarbon compound that contains 2 carbon atoms between 96.5% and 99.9% between 96% and 99.9% and most preferably.Particularly preferably be most following a kind of composition that contains ethene, it is included in the by volume hydrocarbon compound that contains 2 carbon atoms between 97% and 99.9%.

Statement " hydrocarbon that contains 2 carbon atoms " is interpreted as for the purposes of the present invention referring to containing at least carbon and hydrogen atom and contains any organic compound of 2 carbon atoms.

Preferably, be ethene, ethane and acetylene at the hydrocarbon compound that contains 2 carbon atoms that comprises in the composition of ethene that contains according to the present invention.

The composition that contains ethene according to the present invention comprises the ethene of a value, thereby so that the hydrocarbon compound that this value and this contain 2 carbon atoms (preferably, ethene, ethane and acetylene) the ratio of total amount value be between 97% and 99.5%, preferably between 97.5% and 99.5%, more preferably between 98% and 99.2%, and most preferably between 98.5% and 99.2%.The composition that contains ethene that comprises the ethene of following value is the most particularly preferred, and this value is so that the ratio of total amount value of this value and the hydrocarbon compound (preferably, ethene, ethane and acetylene) that contains 2 carbon atoms is between 98.8% and 99.2%.

Therefore, the composition that contains ethene according to the present invention comprises advantageously by volume between 72.8% and 99.4%, preferably between 75.1% and 99.4%, more preferably at the ethene of a value between 95.1% and 99.1% between 94.1% and 99.1% and most preferably.Particularly, following a kind of composition that contains ethene most preferably, it is included in the by volume ethene between 95.8% and 99.1%.

Therefore this composition that contains ethene advantageously is not a kind of ethene of polymerization grade, that is, it is characterized by greater than by volume 99.8%, often is 99.9% purity at most by volume.

The composition that contains ethene according to the present invention advantageously comprises less than the hydrocarbon compound that contains 3 carbon atoms of 100ppm by volume and less than by volume oxygenate and the water of 100ppm at least.

Statement " hydrocarbon that contains at least 3 carbon atoms " is interpreted as for the purposes of the present invention referring to containing at least carbon and hydrogen atom and comprises any organic compound of at least 3 carbon atoms ".The example that this kind comprises the hydrocarbon compound of at least 3 carbon atoms be propane, propylene, butane and their unsaturated derivative together with all saturated or undersaturated heavier compound.

Statement " oxygenate " is interpreted as referring at least a following organic compound for the purposes of the present invention, this compound comprises at least carbon and hydrogen atom and at least one Sauerstoffatom, for example fatty alcohol, ether, carbonyl compound (aldehyde, ketone, carboxylic acid, carbonic ether, ester and analogue).The example of oxygenate includes but not limited to methyl alcohol, ethanol, n-propyl alcohol, Virahol, C ₄-C ₂₀Alcohol, dme, diethyl ether, methyl ethyl ether, Di Iso Propyl Ether, dipropyl ether, propyl group methyl ether, isopropyl methyl ether, propyl group ethyl ether, sec.-propyl ethyl ether, formaldehyde, acetaldehyde, propionic aldehyde, dimethyl carbonate, dimethyl ketone, formic acid and ester, acetic acid and ester thereof, propionic acid and propionate and their mixture.Preferably, these oxygenate be selected from following one or more: methyl alcohol, ethanol, dme, diethyl ether, formaldehyde, acetaldehyde, acetic acid and ester thereof or their a kind of mixture.More preferably, these oxygenate are to be selected from: methyl alcohol, dme, acetaldehyde, acetic acid and ester thereof or their a kind of mixture.

The composition that contains ethene according to the present invention advantageously comprises by volume less than 100, preferably less than 50, more preferably less than 25, most preferably less than 10 and special most preferably less than the hydrocarbon compound that contains at least 3 carbon atoms of 5ppm.

The composition that contains ethene according to the present invention advantageously comprises by volume oxygenate and the water less than 100ppm.

The composition that contains ethene according to the present invention advantageously comprises by volume less than 100, preferably less than 50, more preferably less than 20 and most preferably less than oxygenate and the water of 10ppm.

The composition that contains ethene according to the present invention advantageously comprises by volume less than 100, preferably less than 50, more preferably less than 20, special more preferably less than 10, most preferably less than 5ppm and special most preferably less than the oxygenate of 2ppm.

The composition that contains ethene according to the present invention advantageously comprises by volume less than 100, preferably less than 50, more preferably less than 20 and most preferably less than the water of 10ppm.

The composition that contains ethene according to the present invention further comprise by volume less than 2500ppm, preferably less than 1800, more preferably less than 100 and most preferably less than the acetylene of 50ppm.Particularly, particularly preferably be following a kind of composition that contains ethene most, it comprises by volume the acetylene less than 20ppm.

The composition that contains ethene according to the present invention advantageously comprises by volume greater than 0.1, be preferably more than 0.3 and more preferably greater than the acetylene of 0.5ppm.

The invention still further relates to a kind of method of the composition for the manufacture of containing ethene, according to the method:

A) make a kind of from an oxygenate to the process of alkene and stood a kind of processed conventionally, the outflow that contains ethene and other compositions stream E and stood the outflow stream E ' that a preconditioning processes to obtain a compression; And

The outflow stream E ' that b) will compress separates to obtain a kind of according to the composition that contains ethene of the present invention in one to three distillation tower.

The method according to this invention is for from begin to make a kind of method of the composition that contains ethene to the outflow stream E that contains ethene and other compositions of the process of alkene from a kind of oxygenate.

Statement " oxygenate is to the process (OTO process) of alkene " is interpreted as referring to for the purposes of the present invention beginning and producing a kind of a kind of method that contains the outflow stream E of ethene and other compositions from a kind of oxygenate raw material.

It is a kind of raw material that statement " oxygenate raw material " is interpreted as for the purposes of the present invention, and this raw material is one or more fatty alcohols or ether.

The example of oxygenate raw material includes but not limited to methyl alcohol, ethanol, n-propyl alcohol, Virahol, C ₄-C ₂₀Alcohol, dme, diethyl ether, methyl ethyl ether, Di Iso Propyl Ether, dipropyl ether, propyl group methyl ether, isopropyl methyl ether, propyl group ethyl ether, sec.-propyl ethyl ether or their mixture.Preferably, these oxygenate raw materials are to be selected from: methyl alcohol, ethanol, dme, methyl ethyl ether, diethyl ether or their a kind of mixture.More preferably, these oxygenate raw materials are to be selected from: methyl alcohol, dme or their a kind of mixture.

Method for the manufacture of a kind of composition that contains ethene according to the present invention is preferably so that this outflow stream E that contains ethene and other compositions is the process from a kind of methanol to olefins.In the process of this kind methanol to olefins, these oxygenate raw materials preferably: methyl alcohol, dme or their a kind of mixture.

This oxygenate raw material can be by any process production known in the art, comprises synthesis gas (synthetic gas) fermentation or reaction derived from plastics, municipal waste or any other organic materials of Sweet natural gas, petroleum liquid, carbonaceous material (for example coal), recirculation.Preferably, this oxygenate raw material is by the reaction production of synthetic gas.

The synthetic gas production process be know and comprise conventional steam reforming, from thermal transition or their a kind of combination.

Preferably, synthetic gas is produced by the steam reforming of Sweet natural gas.Generally, production of syngas comprises: Sweet natural gas (great majority are methane) is originated with a kind of oxygen and is generated the combustion reactions of hydrogen, carbon monoxide and/or carbonic acid gas.

Generally, then a kind of heterogeneous catalyst (typically a kind of catalyzer based on copper) is contacted to produce a kind of stream that contains oxygenate with a kind of stream (typically carbonic acid gas and carbon monoxide and hydrogen) of synthesis gas.

Can be with one or more thinners, picture helium, argon gas, nitrogen, carbon monoxide, carbonic acid gas, water, basically nonreactive alkane (the especially for example alkane of methane, ethane and propane), basically nonreactive alkene, basically nonreactive aromatics and their mixture add in this oxygenate raw material, typically are used for reducing the concentration of the activeconstituents in this incoming flow.Most preferred thinner is water.

Can also comprise hydrocarbon as the part of this oxygenate raw material, namely as co-fed.Comprise propylene, butylene, amylene, C as co-fed preferred hydrocarbon ₄₊Hydrocarbon mixture, C ₅₊Hydrocarbon mixture and their mixture.C more preferably ₄₊Hydrocarbon mixture wherein most preferably obtains and is recycled to the C in the reactor from separate ₄₊Hydrocarbon mixture.

From separation (step b) subsequently) other oxygenate of obtaining can be recycled in this reactor.

According to according to the present invention for the manufacture of a kind of method that contains the composition of ethene, preferably this outflow stream E that contains ethene and other compositions is to alkene, the preferably process of methanol to olefins from a kind of oxygenate.

This kind production is advantageously carried out in the presence of a kind of catalyzer, preferred a kind of molecular sieve catalyst or a kind of molecular sieve catalyst composition.This molecular sieve catalyst composition advantageously comprises molecular sieve and tackiness agent and/or substrate material.

Preferred molecular sieve catalyst is molecular sieve zeolite or zeolite type.Alternately, this preferred molecular sieve is a kind of aluminate or phosphate (ALPO) molecular sieve and/or a kind of aluminosilicophosphate (SAPO) molecular sieve and replacement, the ALPO and/or the SAPO molecular sieve that replace of metal preferably, is included in the molecular sieve that has the coexisting material of two or more different phases or crystalline structure in the combination of molecular sieve.Adhesive material can comprise aluminum oxide, silica and/or other inorganic oxide sols of dissimilar hydrations.Substrate material can comprise one or more rare earth metals, metal oxide and natural clay.

Employed reactor can be a kind of fixed-bed reactor, a kind of fluidized-bed reactor (continuous fluidized-bed reactor or continuous high velocity stream fluidized bed reactor), a kind ofly have a plurality of fine and close bed or fixed bed zone and/or the mixing reactor of fast fluidized bed conversion zone, a kind of fluidized-bed reactor of circulation, a kind of riser reactor and an analogue that links together.

The outflow stream E that comprises ethene and other compositions that produces advantageously comprises desirable olefin product, picture ethene and propylene are together with by product, picture, hydrogen, methane, carbon monoxide, carbonic acid gas, water, ethane, propane, propylene are together with than propane and the heavier component of propylene, for example C ₄ ⁺Component (olefinic with aliphatic), multiple undersaturated component, for example oxygenate of acetylene, methylacetylene and propadiene and above definition.

Before standing to separate, make a kind of from oxygenate to the process (optimization methane is to the process of alkene) of alkene and stood a kind of outflow stream E processed conventionally, that contain ethene and other compositions and stood a preconditioning and process to obtain the outflow of a compression and flow E.

Advantageously, conventional processing comprises this E cooling of outflow stream and/or chilling, and preferably includes the condensation product of removing generation.Preferably, conventional processing comprises this E cooling of outflow stream and chilling, and preferably includes the condensation product of removing generation.

Advantageously, this preconditioning is processed and is comprised: i) will flow out the E compression and remove simultaneously the condensation product of generation; Ii) remove sour gas (wherein being carbonic acid gas and analogue) and iii) carry out adsorption treatment to remove undesirable oxygenate (be interpreted as, refer to for the purposes of the present invention comprise at least carbon, oxygen and hydrogen atom and have the organic compound of the normal boiling point that is higher than 0 ℃) and water.

Removing sour gas (wherein being carbonic acid gas and analogue) can be undertaken by any known method (appropriate means is included in the aqueous solution of alkaline aqueous solution, amine or the methanol steam and absorbs).

Adsorption treatment can use any known sorbent material to carry out that (suitable sorbent material comprises aluminum oxide, aluminosilicate, the molecular sieve of aluminum oxide, activation, for example

With

Molecular sieve, lime, magnesium hydroxide and analogue).

Preferably, this preconditioning is processed and is comprised i) use the interstage cooler between each grade that this outflow stream E is carried out stage compression, remove the condensation product of generation; Ii) remove sour gas (wherein being carbonic acid gas and class thing) and iii) carry out adsorption treatment to remove undesirable oxygenate and water.

More preferably, this preconditioning is processed and comprised: the interstage cooler between each grade carries out stage compression to this outflow stream E, removes the condensation product of generation; And remove the sour gas between the level second from the bottom and last of this compressor with a kind of neutralizing treatment and carry out adsorption treatment with except anhydrating and undesirable oxygenate at a kind of suitable sorbent material.

The outflow stream E ' of this compression advantageously comprises by volume the at most oxygenate of 1000ppm and the by volume water of maximum 100ppm.

The outflow of this compression stream E ' advantageously comprises by volume at most 1000ppm, maximum 800ppm preferably, and more preferably maximum 600 and the oxygenate of 400ppm at least most preferably.

The outflow of this compression stream E ' advantageously comprises by volume at most 100ppm, maximum 50ppm preferably, and more preferably maximum 20 and the water of 10ppm at least most preferably.

Along with this flows out the variation of the composition of stream E, the maximum magnitude of the maximum magnitude of oxygenate and water can be independent of above-mentioned preference degree and the above value of independently mentioning taken into consideration in flowing out stream E '.

In step a) afterwards, the outflow of this compression stream E ' is separated obtain the composition that a kind of (namely as defined above) according to the present invention contains ethene in one to three distillation tower.

Before being introduced into distillation tower, can be so that stand a thermal conditioning step from the outflow stream E ' of a) compression.Statement thermal conditioning step is interpreted as referring to a series of heat exchanges of optimization energy use, for example in a cover interchanger, this outflow stream E ' is cooled off step by step, at first use untreated water cooling, and then use icy water, and then add that with gradually cold fluid the cross exchange device reclaims the sensible heat of the stream that produces.

Described outflow stream E ' can be used as a single cut or is introduced in this distillation tower as several sub-cuts.It is introduced preferably as a single cut.

Each distillation tower advantageously comprises the tower of a stripping section and/or a rectifying section.If two kinds of sections all exist, this rectifying section preferably is positioned on this stripping section.

Each distillation tower advantageously is selected from the distillation tower that comprises above-mentioned these two kinds of sections and the tower that only comprises one of these two kinds of sections.Preferably, each distillation tower comprises two kinds of above-mentioned sections.

Each distillation tower advantageously is furnished with relevant utility appliance, for example as at least one reboiler and at least one condenser.The device of withdrawing from the middle of allowing and an intermediate heat exchange can add in this distillation tower.

When this distillation tower be equipped with a condenser and as below mention, when a kind of composition or cut are separated at the top of this distillation tower, be understood that for the purposes of the present invention this composition or cut are separated in the exit of this condenser.

First embodiment of the method according to this invention, in step a) afterwards, the outflow of this compression stream E ' is separated in a distillation tower T1 this distillation tower T1 top a kind of and contains the composition C1 of ethene and be separated in the enrichment of this distillation tower T1 bottom a cut H1 who contains the compound of at least 3 carbon atoms.

This of the method according to this invention the first embodiment, above-mentioned steps b) advantageously at least 8 bar, preferred at least 12 bar and in a particularly preferred mode, carrying out under the pressure of at least 15 bar.Step b) advantageously at maximum 45 bar, preferred maximum 40 bar and in a particularly preferred mode, carrying out under the pressure of maximum 35 bar.

According to this first embodiment, step b) temperature when carrying out at this distillation tower T1 top advantageously at least-60 ℃, preferably at least-55 ℃ and in a particularly preferred mode at least-50 ℃.Advantageously be maximum 10 ℃ at distillation tower T1 top, preferred maximum 5 ℃ and be maximum 0 ℃ in a particularly preferred mode.

According to this first embodiment, step b) temperature when carrying out advantageously is at least 0 in this distillation tower T1 bottom, preferably at least 10 ℃ and in a particularly preferred mode at least 20 ℃.Advantageously be maximum 120 ℃ in distillation tower T1 bottom, preferably maximum 110 ℃ and be maximum 100 ℃ in a particularly preferred mode.

Second embodiment of the method according to this invention, in step a) afterwards, flow E ' with the outflow of this compression and separate by following steps in two distillation towers:

B1) first separating step, this step are the outflow of this compression stream E is separated into one at the cut F2 at this distillation tower T2 top and has been separated in the enrichment of this distillation tower T2 bottom the cut H2 that contains the compound of at least 4 carbon atoms in first a distillation tower T2; And

B2) second separating step, this step are this cut F2 is separated in a second column T2 ' this distillation tower T2 ' top a kind of and contain the composition C2 of ethene and be separated in the enrichment of this distillation tower T2 ' bottom a cut H2 ' who contains the compound of at least 3 carbon atoms.

This of the method according to this invention the second embodiment, above-mentioned steps b1) (the first separating step) and step b2) (the second separating step) advantageously at least 8 bar, preferred at least 12 bar and carrying out under the pressure of at least 15 bar in a particularly preferred mode.Step b1) advantageously at maximum 45 bar, preferred maximum 40 bar and in a particularly preferred mode, carrying out under the pressure of maximum 35 bar.A compression can apply between these two separating steps.

According to this second embodiment, step b1) temperature when carrying out at this distillation tower T2 top advantageously at least-20 ℃, preferably at least-15 ℃ and in a particularly preferred mode at least-10 ℃.Advantageously be maximum 50 ℃ preferred maximum 45 ℃ and in a particularly preferred mode, be maximum 40 ℃ at distillation tower T2 top.

According to this second embodiment, step b1) temperature when carrying out advantageously is at least 50 ℃ in this distillation tower T2 bottom, preferably at least 60 ℃ and in a particularly preferred mode at least 70 ℃.Advantageously be maximum 160 ℃ in distillation tower T2 bottom, preferably maximum 150 ℃ and be maximum 140 ℃ in a particularly preferred mode.

According to this second embodiment, step b2) temperature when carrying out at this distillation tower T2 ' top advantageously at least-70 ℃, preferably at least-60 ℃ and in a particularly preferred mode at least-50 ℃.Advantageously be maximum 0 at distillation tower T2 ' top, preferably at most-5 ℃ and be maximum 10 ℃ in a particularly preferred mode.

According to this second embodiment, step b2) temperature when carrying out advantageously is at least 0 and in a particularly preferred mode at least 20 ℃ at this distillation tower T2 ' top.Advantageously be maximum 120 ℃ in distillation tower T2 ' bottom, preferably maximum 110 ℃ and be maximum 100 ℃ in a particularly preferred mode.

The 3rd embodiment of the method according to this invention, in step a) afterwards, flow E ' with the outflow of this compression and separate by following steps in three distillation towers:

B1) first separating step, this step be the cut F3 that the outflow of this compression stream E ' is separated at this distillation tower T3 top and be separated into a cut F3 ' in this distillation tower T3 bottom in first a distillation tower T3,

B2) second separating step, this step are the cut F3 ' ' that this cut F3 ' is separated at this distillation tower T3 ' top and have been separated in the enrichment of this distillation tower T3 ' bottom a cut H3 who contains the compound of at least 4 carbon atoms in a second column T3 '; And

B3) the 3rd separating step, this step is this cut F3 and F3 " at the 3rd a distillation tower T3 " in be separated at this distillation tower T3 " top a kind of contain the composition C3 of ethene and be separated at this distillation tower T3 " and the enrichment of bottom contain a cut H3 ' of the compound of at least 3 carbon atoms.

This of the method according to this invention the 3rd embodiment, above-mentioned steps b1) (the first separating step), step b2) (the second separating step) and step b3) (the 3rd separating step) advantageously at least 8 bar, preferred at least 12 bar and carrying out under the pressure of at least 15 bar in a particularly preferred mode.Step b1) advantageously at maximum 45 bar, preferred maximum 40 bar and in a particularly preferred mode, carrying out under the pressure of maximum 35 bar.Compression can be in these three separating steps applies between each and each.

According to this 3rd embodiment, step b1) temperature when carrying out at this distillation tower T3 top advantageously at least-70 ℃, preferably at least-60 ℃ and in a particularly preferred mode at least-50 ℃.Advantageously be maximum 0 at distillation tower T3 top, preferably at most-5 ℃ and be maximum-10 ℃ in a particularly preferred mode.

According to this 3rd embodiment, temperature when step b1) carrying out advantageously is at least 0 in this distillation tower T3 bottom, preferably at least 10 ℃ and in a particularly preferred mode at least 20 ℃ advantageously be maximum 120 ℃ in distillation tower T3 bottom, preferably maximum 110 ℃ and be maximum 100 ℃ in a particularly preferred mode.

According to this 3rd embodiment, step b2) temperature when carrying out advantageously is at least 0 at this distillation tower T3 ' top, preferably at least 10 ℃ and in a particularly preferred mode at least 20 ℃.Advantageously be maximum 100 ℃ at distillation tower T3 ' top, preferably maximum 90 ℃ and be maximum 80 ℃ in a particularly preferred mode.

According to this 3rd embodiment, step b2) temperature when carrying out advantageously is at least 20 ℃ in this distillation tower T3 ' bottom, preferably at least 30 ℃ and in a particularly preferred mode at least 40 ℃.Advantageously be maximum 160 ℃ in distillation tower T3 ' bottom, preferably maximum 150 ℃ and be maximum 140 ℃ in a particularly preferred mode.

According to this 3rd embodiment, step b3) temperature when carrying out at this distillation tower T3 ' ' top advantageously at least-70 ℃ preferably at least-60 ℃ and in a particularly preferred mode at least-50 ℃.Advantageously be maximum 0 at distillation tower T3 ' ' top, preferably at most-5 ℃ and be maximum 10 ℃ in a particularly preferred mode.

According to this 3rd embodiment, step b3) temperature when carrying out advantageously is at least 0 in this distillation tower T3 ' ' bottom, preferably at least 10 ℃ and in a particularly preferred mode at least 20 ℃.Advantageously be maximum 120 ℃ in distillation tower T3 ' ' bottom, preferably maximum 110 ℃ and be maximum 100 ℃ in a particularly preferred mode.

Enrichment contain the compound of at least 3 carbon atoms cut H1, H2 ' can be used as it is or can be further purified into very highly purified propylene (propylene that is called the polyreaction grade) with H3 ' with for the manufacture of the propylene derived compounds.

Statement " compound that contains at least 3 carbon atoms " is interpreted as referring to such as hydrocarbon compound above definition, that contain at least 3 carbon atoms for the purposes of the present invention.

As the example of propylene derived compounds, can mention except other things vinyl cyanide and derivative thereof together with the polymkeric substance by its manufacturing, the homopolymer of propylene oxide and derivative thereof and propylene and multipolymer (hereinafter referred to as polypropylene).Polypropylene is preferred propylene derived compound.

Enrichment contain the compound of at least 4 carbon atoms cut H2 can be used as it is or can be further purified into very highly purified grade with H3 so that as valuable hydro carbons grade or as fuel.

Statement " compound that contains at least 4 carbon atoms " is interpreted as for the purposes of the present invention referring to containing at least carbon and hydrogen atom and comprises any organic compound of at least 4 carbon atoms.This type of example that comprises the compound of at least 4 carbon atoms be butane, butylene together with all saturated or undersaturated heavier compound.

The method according to this invention is further characterized in that: at step b) afterwards, it is saturated to make this composition that contains ethene stand a kind of acetylene.

For the purposes of the present invention, saturated being interpreted as of acetylene is to allow the partly saturated any operation of the triple bond of acetylene.These the operation in, can mention a kind of be hydrogenization (it is preferred).

Above-mentioned acetylene step of hydrogenation can be undertaken by any known hydrogenation catalyst, for example based on the catalyzer of palladium, platinum, rhodium, ruthenium or iridium, this catalyzer places on the carrier, for example aluminum oxide, silica, silica/alumina, carbon, calcium carbonate or barium sulfate, however also have catalyzer and those catalyzer based on the cobalt-molybdenum complex compound based on nickel.Preferably, this hydrogenization step is undertaken by a kind of catalyzer based on palladium or platinum.In a particularly preferred mode, it is undertaken by a kind of catalyzer based on palladium.

About this carrier, this hydrogenization step is undertaken by a catalyzer based on above-claimed cpd (preferred palladium or platinum are palladiums in particularly preferred mode), preferably deposits on aluminum oxide, carbon, calcium carbonate or the barium sulfate.

The amount of palladium in this catalyzer advantageously is in by weight 1% grade.

Advantageously at least 5 ℃ of temperature when so this acetylene hydrogenization step is carried out, preferably at least 20 ℃ is at least 25 ℃ in a kind of particularly preferred mode, is at least 40 ℃ in the most particularly preferred a kind of mode and is at least 50 ℃ in a kind of truly the most particularly preferred mode.It advantageously maximum 150 ℃, preferred maximum 120 ℃, and in a particularly preferred mode maximum 100 ℃.

About this pressure, it is advantageously more than or equal to 1, is preferably more than or equals 5, is more than or equal to 10 in a particularly preferred mode and is more than or equal to 15 bar in a mode the most particularly preferred.It advantageously is less than or equal to 50, preferably is less than or equal to 45, in a particularly preferred mode is to be less than or equal to 40 and be to be less than or equal to 30 bar in a mode the most particularly preferred.

Advantageously, thereby the step of hydrogenation of this acetylene uses a large amount of hydrogen to carry out making its hydrogenation to carry out fully, that is to say preferably at least 99%.The value of this hydrogen is advantageously so that hydrogen: the mol ratio of acetylene is to be equal to or greater than 1, preferably be equal to or greater than 1.5, in a particularly preferred mode, be to be equal to or greater than 2, and be to be equal to or greater than 3 and be to be equal to or greater than 4 in the most particularly preferred mode truly at one in a mode the most particularly preferred.

After this acetylene is saturated, can randomly carry out drying.

The method according to this invention is further characterized in that: at step b) afterwards, make this composition that contains ethene more preferably stand an additional separating step (being called demethanation) with the cut of the compound lighter than ethene of having isolated enrichment thus.

Than the light compound of ethene advantageously methane, hydrogen, carbon monoxide, nitrogen and other rare gas elementes.

This additional separating step is advantageously at least 8 bar, preferred at least 12 bar and carrying out under the pressure of at least 15 bar in a particularly preferred mode.It is advantageously at maximum 45 bar, preferred maximum 40 bar and carrying out under the pressure of maximum 35 bar in a particularly preferred mode.Can before this additional separating step, apply a compression.

Temperature when this additional separating step carries out at this demethanation distillation tower DM top advantageously at least-130 ℃, preferably at least-125 ℃ and in a particularly preferred mode at least-120 ℃.Advantageously be-50 ℃ at most at the distillation tower DM top of this demethanation, preferred-60 ℃ and be maximum-70 ℃ in a particularly preferred mode at most.

Temperature when this additional separating step carries out in this demethanation distillation tower DM bottom advantageously at least-50 ℃, preferably at least-47 ℃ and in a particularly preferred mode at least-45 ℃.Advantageously be maximum 10 ℃ at the distillation tower DM top of this demethanation, preferred maximum 5 ℃ and be maximum 0 ℃ in a particularly preferred mode.

More preferably, the method according to this invention, first, second and the 3rd embodiment together with this method is characterized in that: at step b) afterwards, make this composition that contains ethene at first stand an acetylene saturation and then stand an additional separating step (being called demethanation) with the cut of the compound lighter than ethene of having isolated enrichment thus.

Most preferred first embodiment of the method according to this invention describes with reference now to the appended Fig. 1 of this explanation.

Will be from an oxygenate to the process of alkene (preferred MTO) and stood outflow stream E a kind of conventional processing (cooling, chilling and remove the condensation product that produces), that contain ethene and other compositions and stood a preconditioning by compression in a compressor and process PCT, remove simultaneously the condensation product of generation, and carry out neutralizing treatment to remove wherein as CO ₂Sour gas with analogue.Before the outflow stream E ' that will compress joins among the distillation tower T1 that is equipped with a reboiler and a condenser, residual water and undesirable oxygenate are removed at a kind of sorbent material at last.Composition C1 who contains ethene isolate at the top of this distillation tower T1 and an enrichment contain the compound of at least 3 carbon atoms cut H1 isolate in the bottom of this distillation tower T1.Then the composition C1 that this is contained ethene stood a saturated AS1 of acetylene before the distillation tower DM1 that joins the demethanation that is equipped with a reboiler and a condenser.An enrichment composition C1 ' ' that cut L1 isolates at the top of the distillation tower DM1 of this demethanation and this contains ethene of the compound lighter than ethene isolate in the base product section of this demethanation.

Most preferred second embodiment of the method according to this invention describes with reference now to the appended Fig. 2 of this explanation.

Will be from an oxygenate to the process of alkene (preferably MTO) and stood outflow stream E a kind of conventional processing (cooling, chilling and remove the condensation product of generation), that contain ethene and other compositions and stood a preconditioning by compression in a compressor and process PCT, remove simultaneously the condensation product of generation, and carry out neutralizing treatment to remove wherein as CO ₂Sour gas with analogue.Before the outflow stream E ' that will compress joins the distillation tower T2 that is equipped with a reboiler and a condenser, residual water and undesirable oxygenate are removed at a kind of sorbent material at last.Cut F2 isolate at the top of this distillation tower T2 and an enrichment contain the compound of at least 4 carbon atoms cut H2 isolate in the bottom of this distillation tower T2.Cut F2 is sent to a distillation tower T2 ' who is equipped with a reboiler and a condenser.Composition C2 who contains ethene isolate at the top of this distillation tower T2 ' and an enrichment contain the compound of at least 3 carbon atoms cut H2 ' isolate in the bottom of this distillation tower T2 '.Then the composition C2 that this is contained ethene stood a saturated AS2 of acetylene before the distillation tower DM2 that joins the demethanation that is equipped with a reboiler and a condenser.An enrichment composition C2 ' ' that cut L2 isolates at the top of the distillation tower DM2 of this demethanation and this contains ethene of the compound lighter than ethene isolate in the base product section of this demethanation.

Most preferred the 3rd embodiment of the method according to this invention describes with reference now to the appended Fig. 3 of this explanation.

Will be from an oxygenate to the process of alkene (preferably MTO) and stood outflow stream E a kind of conventional processing (cooling, chilling and remove the condensation product of generation), that contain ethene and other compositions and stood a preconditioning by compression in a compressor and process PCT, remove simultaneously the condensation product of generation, and carry out neutralizing treatment to remove wherein as CO ₂Sour gas with analogue.Before the outflow stream E ' that will compress joins the distillation tower T3 that is equipped with a reboiler and a condenser, residual water and undesirable oxygenate are removed at a kind of sorbent material at last.Cut F3 isolates at the top of this distillation tower T3 and a cut F3 ' isolates in the bottom of this distillation tower T3.Cut F3 ' is sent to a distillation tower T3 ' who is equipped with a reboiler and a condenser.Cut F3 ' ' isolate at the top of this distillation tower T3 ' and an enrichment contain the compound of at least 4 carbon atoms cut H3 isolate in the bottom of this distillation tower T3 '.Cut F3 and F3 ' ' are sent to a distillation tower T3 ' ' who is equipped with a reboiler and a condenser.Composition C3 who contains ethene isolate at the top of this distillation tower T3 ' ' and an enrichment contain the compound of at least 3 carbon atoms cut H3 ' isolate in the bottom of this distillation tower T3 '.Then the composition C3 that this is contained ethene stood a saturated AS3 of acetylene before the distillation tower DM3 that joins the demethanation that is equipped with a reboiler and a condenser.An enrichment composition C3 ' ' that cut L3 isolates at the top of the distillation tower DM3 of this demethanation and this contains ethene of the compound lighter than ethene isolate in the base product section of this demethanation.

The invention still further relates to a kind of method for begin to make at least a ethylene derivative compounds from a kind of composition that contains ethene according to the present invention.

For the purposes of the present invention, statement " at least a ethylene derivative compounds " is interpreted as making a kind of or more than a kind of ethylene derivative compounds; Preferably make a kind of ethylene derivative compounds.

Statement " ethylene derivative compounds " is used in this article with odd number or plural form, be interpreted as referring to for the purposes of the present invention, any ethylene derivative compounds that directly begins to make from ethene together with any by its compound of deriving.

Statement " the ethylene derivative compounds that directly begins to make from ethene " is used in this article with odd number or plural form, is interpreted as referring to for the purposes of the present invention any compound of directly being made by ethene.

Statement " by its compound of deriving " is used in this article with odd number or plural form, be interpreted as referring to for the purposes of the present invention, from a kind of itself by any compound of the compound manufacturing of ethene manufacturing together with any compound of being derived by it.

As the example of this type of ethylene derivative compounds that directly begins to make from ethene, can mention except other things: the homopolymer of oxyethane, linear alpha-alkene, linear primary alcohol, ethene and multipolymer, ethylbenzene, vinyl-acetic ester, acetaldehyde, ethanol, propionic aldehyde and EDC.

As the example of this kind by its compound of deriving, can mention except other things,

-glycols and the ethers made by oxyethane,

-by the vinylbenzene of ethylbenzene manufacturing and derived from cinnamic styrene polymer,

-the VC that made by EDC,

-derived from vinylidene chloride, fluorinated hydrocarbons and the PVC of VC, and derived from the fluorinated polymer of fluoridizing hydro carbons, and

-derived from the polyvinylidene dichloride of vinylidene chloride and the hydro carbons of fluoridizing (and polymkeric substance of fluoridizing).

The method that begins to make at least a ethylene derivative compounds from the composition that contains ethene according to the present invention preferably a kind of for the manufacture of oxyethylene, ethylbenzene and/or EDC(as the ethylene derivative compounds that directly begins to make from ethene) together with the method for any compound of deriving thus.Statement " and/or " meaning is that the method can be for the manufacture of a kind of method or for the manufacture of the method for a kind of combination of two or three above-mentioned ethylene derivative compounds only in the above-mentioned derivative compound.

More preferably, the method that begins to make at least a ethylene derivative compounds from the composition that contains ethene according to the present invention preferably a kind of for the manufacture of ethylbenzene and/or EDC(as the ethylene derivative compounds that directly begins to make from ethene) together with the method for any compound of deriving thus.

Most preferably, the method that begins to make at least a ethylene derivative compounds from the composition that contains ethene according to the present invention preferably a kind of for the manufacture of EDC(as the ethylene derivative compounds that directly begins to make from ethene) together with the method for any compound of deriving thus, preferred VC and then be PVC.

Therefore, an object of the present invention is a kind of method for the manufacture of ethylene dichloride, make the composition (as defined above) that contains ethene according to the present invention stand a kind of chlorization and/or a kind of oxychlorination to produce ethylene dichloride according to the method.

This chlorination reaction (being commonly referred to direct chlorination) is advantageously containing a kind of catalyzer of dissolving (FeCl for example ₃Perhaps other Lewis acids) carry out in the liquid phase (preferably being mainly EDC).Might advantageously this catalyzer and promotor (for example alkali metal chloride) be made up.A pairing that has provided good result is FeCl ₃With the complex compound of LiCl (tetrachloro ferrate-lithium-as described in the patent application NL6901398).

Employed FeCl ₃The FeCl of the about 0.03g to 30g of amount advantageously every kg liquid masterbatch ₃FeCl ₃With the mol ratio of LiCl advantageously be 0.5 to 2 rank.

In addition, this chlorination reaction is preferably carried out in a kind of organic liquid medium of chlorination.More preferably, the organic liquid medium of this chlorination is also referred to as the liquid masterbatch, mainly is made of EDC.

Advantageously under the temperature between 30 ℃ and 150 ℃, carry out according to chlorination reaction of the present invention.Pipe pressure is not how, is being lower than boiling point (at the chlorination process under the subcooling condition) and has all obtained good result under the temperature of the boiling point process of chlorination (at the boiling point time) itself.

When chlorination process according to the present invention is chlorination process under a kind of overcooling condition, obtained good result by operating in following temperature with under a pressure under the gas phase, this temperature advantageously is higher than or equals 50 ℃ and preferably be higher than or equal 60 ℃, but advantageously be lower than or equal 80 ℃ and preferably be lower than or equal 70 ℃, and this pressure advantageously is higher than or equals 1 and preferably be higher than or equal 1.1 bar absolute pressures, but advantageously be lower than or equal 20, preferably be lower than or equal 10 and particularly preferably be lower than or equal 6 bar absolute pressures.

The method of chlorination can preferably reclaim this reaction heat effectively under boiling point.In this case, this reaction advantageously occurs under 60 ℃ the temperature being higher than or equaling, preferably be higher than or equal 70 ℃ and particularly preferably be higher than or equal 85 ℃, but advantageously be lower than or equal 150 ℃ and preferably be lower than or equal 135 ℃, and the pressure in this gas phase advantageously is higher than or equals 0.2, preferably be higher than or equal 0.5, particularly preferably be higher than or equal 1.1 and more particularly preferably be higher than or equal 1.3 bar absolute pressures, but advantageously be lower than or equal 10 and preferably be lower than or equal 6 bar absolute pressures.

This chlorination process also can be mixed circuit cooling (hybrid loop-cooled) process of a kind of chlorination under boiling point.Statement " the mixed circuit process of cooling of chlorination under boiling point " is interpreted as referring to a process, wherein for example by being immersed in interchanger in this reaction medium or by a loop at an interchanger internal recycle this reaction medium being cooled off, in gas phase, produce simultaneously the EDC that is at least formed amount.Advantageously, regulating this temperature of reaction and pressure leaves the EDC that produces and removes surplus heat from this reaction medium by the swap table area in gas phase.

Can will carry out the composition that contains ethene of chlorination and also have mol-chloric (itself is pure or dilution) to introduce together or individually this reaction medium with any known equipment.It may be favourable being introduced separately into the composition that contains ethene that has stood chlorization, and to increase its dividing potential drop and to promote its dissolving, this consists of a conditioning step of the method usually.

Ethene adds to transform most of chlorine with enough amounts, and does not require and add excessive chlorine.The ratio of used ethene/chlorine is preferably between 1.2mol/mol and 0.8mol/mol, and particularly preferably between 1.05mol/mol and 0.95mol/mol.

The product of the chlorination that obtains mainly contains EDC and also has a small amount of by product, for example vinyl trichloride or a small amount of ethane or the chlorizate of methane.

Separating the EDC that obtains from the product flow that derives from this chlorination reactor is to carry out according to known mode, and makes it generally to utilize the heat of this chlorination reaction.Then, it preferably separates with gas/liquid to carry out by condensation.

Then advantageously making unconverted product (methane, ethane, carbon monoxide, nitrogen, oxygen and hydrogen) stand score separates from necessary easier one of the pure ethylene that originates in this initial mixture.

This oxi-chlorination advantageously carries out in the presence of a kind of catalyzer that comprises active element, and this active element comprises the copper that is deposited on a kind of inert support.This inert support advantageously is selected from the carrier of aluminum oxide, silica gel, mixed oxide, clay and other natural origins.Aluminum oxide consists of a kind of preferred inert support.

The catalyzer that preferably comprises active element, the number of this active element advantageously is at least two, one of them is copper.In these active elements except copper, can mention basic metal, alkaline-earth metal, rare earth metal and the metal that is selected from lower group, the consisting of of this group: ruthenium, rhodium, palladium, osmium, iridium, platinum and gold.The catalyzer that comprises following active element is particularly advantageous: copper/magnesium/potassium, copper/magnesium/sodium; Copper/magnesium/lithium, copper/magnesium/caesium, copper/magnesium/sodium/lithium, copper/magnesium/potassium/lithium and copper/magnesium/caesium/lithium, copper/magnesium/sodium/potassium, copper/magnesium/sodium/caesium and copper/magnesium/potassium/caesium.Particularly preferably be most the catalyzer described in patent application EP-A255156, EP-A494474, EP-A657212 and EP-A657213, these patent applications are combined in this by reference.

The content of copper calculates with metallic forms, advantageously between 30g/kg and 90g/kg, preferably between 40g/kg and the 80g/kg and particularly preferably between 50g/kg and 70g/kg catalyzer.

The content of magnesium calculates with metallic forms, advantageously between 10g/kg and 30g/kg, preferably between 12g/kg and the 25g/kg and particularly preferably between 15g/kg and 20g/kg catalyzer.

Alkali-metal content calculates with metallic forms, advantageously between 0.1g/kg and 30g/kg, preferably between 0.5g/kg and the 20g/kg and particularly preferably between 1g/kg and 15g/kg catalyzer.

Copper: magnesium: one or more alkali-metal atomic ratios are 1:0.1-2:0.05-2 advantageously, preferably 1:0.2-1.5:0.1-1.5 and particularly preferably 1:0.5-1:0.15-1.

The specific surface area that catalyzer has is advantageously at 25m ²/ g and 300m ²Between/the g, preferably at 50m ²/ g and 200m ²Between/the g and particularly preferably at 75m ²/ g and 175m ²It is particularly advantageous (recording with nitrogen according to the BET method) between/g.

This catalyzer can use in a fixed bed or a fluidized-bed.It is preferred that the second is selected.This oxychlorination process this reaction usually operate in the condition and range of suggestion.Temperature is advantageously between 150 ℃ and 300 ℃, preferably between 200 ℃ and 275 ℃ and most preferably from 215 ℃ to 255 ℃.Pressure is advantageously more than normal atmosphere.Value between 2 bar absolute values and 10 bar absolute values has provided good result.Scope between 4 bar absolute values to 7 bar absolute value is preferred.This pressure can be regulated effectively, to obtain at a most optimal retention time in this reactor and to keep percent of pass constant for different operating speed.Common residence time scope is from 1 second to 60 seconds, and preferably from 10 seconds to 40 seconds.

The oxygen source of this oxychlorination can be air, pure oxygen or their a kind of mixture, preferred pure oxygen.

These reactants can be introduced this bed by any known device.For safety factors, it is favourable generally that oxygen and other reactants are separated introducing.These safety factorss also require remaining outside flammable limit under the pressure and temperature that the gaseous mixture that leaves or be recycled to this reactor is being discussed.Preferably keep a kind of so-called enrichment mixture, that is to say and with respect to the fuel that will ignite, contain very few oxygen.In this respect, have at this compound under the condition of wide flammability range, hydrogen (〉 2vol%, preferred〉5vol%) abundance exist and will consist of a shortcoming.

The ratio of employed hydrogenchloride/oxygen is advantageously between 3mol/mol and 6mol/mol.The ratio of this ethylene/hydrogen chloride is advantageously between 0.4mol/mol and 0.6mol/mol.

Resulting chlorizate mainly comprises EDC and also has a small amount of by product, for example vinyl trichloride.

Isolated EDC can mix or not mix with isolated EDC from the product flow of oxychlorination reactor before the EDC cleavage step from the product flow that derives from chlorination reactor.When two kinds of EDC mix, they completely or partially can be mixed.

Therefore, be further characterized in that for the manufacture of the method for ethylene dichloride (making the composition (as defined above) that contains ethene according to the present invention stand a kind of chlorization and/or a kind of oxychlorination to produce ethylene dichloride according to the method): it preferably includes the ethylene dichloride pyrolysis to produce vinylchlorid.

Then EDC can stand an EDC pyrolysis (being also referred to as cracking) and produce thus vinylchlorid (VC) and hydrogenchloride.

The condition that the EDC cleavage step can be carried out is well known by persons skilled in the art.The EDC cracking can not carried out when the 3rd compound exists or do not exist, and that can mention in these the 3rd compounds has a catalyzer; The EDC cracking is a kind of catalytic EDC cracking in this case.Yet the EDC cracking is preferably being carried out under the effect in heat in the presence of the 3rd compound and only; The EDC cracking often is called pyrolysis in this case.

This pyrolysis advantageously obtains by a reaction in gas phase in a tube furnace.Common pyrolysis temperature is between 400 ℃ and 600 ℃, preferably the scope between 480 ℃ and 540 ℃.The residence time is advantageously between 1 second and 60 seconds, preferably from 5 seconds to 25 seconds scope.For the formation that limits by product and the contamination in boiler tube road, the transformation efficiency of this EDC advantageously is limited in 45% to 75%.

The VC that separation obtains from the product flow that derives from pyrolysis and hydrogenchloride are to use any known device to carry out according to known mode, to collect VC and the hydrogenchloride of purifying.After the purifying, advantageously unconverted EDC is delivered to this pyrolysis oven.

Therefore, be further characterized in that for the manufacture of the method for ethylene dichloride (making the composition (as defined above) that contains ethene according to the present invention stand a kind of chlorization and/or a kind of oxychlorination to produce ethylene dichloride according to the method): it preferably includes the ethylene dichloride pyrolysis to produce vinylchlorid, and more preferably it is characterized in that: it comprises that further the polyreaction of vinylchlorid is to produce polyvinyl chloride.

The manufacturing of PVC can be a kind of body, solution or aqueous dispersion polymerization method, and it is a kind of aqueous dispersion polymerization method preferably.

The expression aqueous dispersion polymerization is interpreted as referring to radical polymerization in waterborne suspension and the radical polymerization in water-based emulsion, and the polymerization in aqueous microsuspension.

Radical polymerization in the expression aqueous dispersion liquid is interpreted as referring to any radical polymerization process in aqueous medium, in the presence of dispersion agent and oil soluble radical initiator.

Radical polymerization in the expression aqueous emulsion is interpreted as referring to any radical polymerization process in aqueous medium, in the presence of emulsifying agent and water-soluble radical initiator.

Expression aqueous microsuspension (being also referred to as the polymerization in the aqueous dispersion of homogenizing) is interpreted as referring to having used oil-soluble initiator and because strong mechanical stirring and any radical polymerization process under the condition of the emulsion of preparation monomer droplet in the presence of emulsifying agent.

An advantage of the invention is that the cost that it allows to lower obtains a kind of composition that contains ethene.

Another advantage of the present invention is the composition that contains ethene that has obtained to have the purity of the ethene that is lower than the polymerization grade.

Meaningfully, obtained following a kind of composition that contains ethene, this composition can comprise dissimilar impurity and be to be in its not forbidden level of application in the future.

In addition, compare significantly with the ethene that obtains the polyreaction grade and reduced for obtaining the desired thermal power of composition that contains ethene according to the present invention.

At last, for the composition that contains ethene according to the present invention obtain total Recovery rate of ethylene significantly higher with comparing of obtaining for the polyreaction grade.

If the disclosure content in any patent, patent application and publication that is combined in by reference this and the application's the afoul degree of explanation are to making it may make a term unclear, then this explanation should be preferential.

Following example is intended to illustrate the present invention, but is not intended to limit its scope.

These examples are from the Ai Si present technique company (ASPEN TECHNOLOGY INC) on the Wheeler road, Burlinton city (Wheeler Road) 200 of Massachusetts, United States

Under the help of V7.2 software based on for pure component and mixture

The V7.2 database calculates.

Example 1(is according to the present invention)

A kind of from a methyl alcohol to the process of alkene and stood outflow stream E a kind of conventional processing (cooling, chilling and remove the condensation product of generation), that contain ethene and other compositions and have the detailed composition that in following table 1a, provides.

Make this outflow stream E stand described below

The V7.2 software simulation and in Fig. 1 patterned process.The mole flow velocity is 29.156kmol/h, wherein 13.476kmol ethene/h.The temperature of this outflow stream E is that 40 ℃ and its absolute pressure are 2.5 bar in the ingress of this process.

Then will flow out the absolute pressure of E by at first in 3 stage compressors that are equipped with interstage cooler between at different levels, being compressed to 20 bar and be cooled in the exit 40 ℃ temperature will flow out stream, remove simultaneously the condensation product of generation.Then will wherein be CO be used to removing ₂And a neutralizing treatment liquid of the sour gas of analogue is incorporated between second and the third stage of this compressor.The outflow of the compression that will produce stream E add be equipped with a reboiler and a condenser and comprise 20 theoretical stages distillation tower T1 of (comprising this reboiler and condenser) before, residual water and undesirable oxygenate are removed at a kind of sorbent material at last.To flow out E ' and be incorporated on the 14th grade, the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio of this tower is fixed on 3.Isolated at the top of distillation tower T1 (outlet of condenser) that of 444.68kg/h contains the composition C1 of ethene and isolated an enrichment in the bottom of distillation tower T1 the cut H1 that contains the compound of at least 3 carbon atoms.Be fixed on 20 bar at the top of distillation tower T1 and the absolute pressure of bottom.Estimate it is that the temperature computation of bottom of-37.6 ℃ and distillation tower T1 is 57.3 ℃ in the temperature at the top of distillation tower T1 (outlet of condenser).

Then the composition C1 that this is contained ethene is heated to 50 ℃, the H pure with 0.0474kmol/h ₂Under the absolute pressure of 50 ℃ and 20 bar, mix and join in the deacetylation device, so that its acetylene saturation AS1 who stands to carry out adiabaticly.It is 99% that the transformation efficiency of acetylene is estimated, the selectivity estimation of ethene be 60.1% and the selectivity estimation of ethane be 39.9%.After the deacetylated effect, the composition C1 ' that contains ethene that produces is cooled to-30.7 ℃ and join and be equipped with a reboiler and a condenser and comprise among the demethanation distillation tower DM1 of 20 theoretical stages (comprising this reboiler and condenser).This composition C1 ' that contains ethene is incorporated on the 15th grade, and the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio stuck-at-１ 0 of the distillation tower of this demethanation.An enrichment composition C1 ' ' that cut L1 isolates at the top of the distillation tower DM1 of this demethanation (outlet of condenser) and this contains ethene of the 63kg/h compound lighter than ethene isolate in the base product section of this demethanation.Be fixed on 20 bar at the top of this demethanation distillation tower and the absolute pressure of bottom.Estimate it is that the temperature computation of-107.6 ℃ and this demethanation distillation tower bottom is-29.2 ℃ in the temperature at the top of this demethanation distillation tower (outlet of condenser).

Containing composition C1, C1 ' and C1 ' ' provides in table 1a together with the outflow stream E of the composition that contains ethene of cut H1 and L1 and the feature of E '.Rare gas element, hydrogen, methane, CO ₂, acetylene, ethene, ethane, propylene, other C3, C4, C5, H ₂The value of O, oxygenate and total amount are expressed as % by volume, and except in the bracket those, they are ppm by volume.

This mole flow velocity that contains the composition C1 ' ' of ethene reaches 13.617kmol/h, wherein 13.437kmol ethene/h.Total ethene (C1 ' ' in ethene/outflow stream E in ethene) rate of recovery reaches 99.71%.This contain ethylene content among the composition C1 ' ' of ethene reached by volume 98.68% and the ratio of ethene and total ethene, ethane, acetylene be 98.99%.This contains the propylene content that acetylene content among the composition C1 ' ' of ethene reached among the composition C1 ' ' that 19.4ppm by volume and this contain ethene and has reached by volume 0.3ppm.The thermal power in the reboiler of distillation tower T1 that calculates, and the power in the reboiler of this demethaniser (demethaniser) DM1 provides in table 2.This heat consumption rate that contains among the composition C1 ' ' of ethene has reached 0.264kWh/kg.

Example 2(comparison example)

Outflow stream E that will be identical with example 1 processes in the mode identical with example 1.After this, this composition C1 ' ' that contains ethene is sent to an ethene splitter S1 who is equipped with 40 theoretical stages (comprising reboiler and condenser).This composition C1 ' ' that contains ethene is incorporated on the 10th grade, and the 1st grade is that condenser and the 40th grade are reboilers.The quality reflux ratio of this tower is fixed on 5.Contain ethene and enrichment the cut of 360.00kg/h of the compound lighter than ethene isolate at the top of this ethene splitter S1 (outlet of condenser) and the cut H1 ' that still contains the rich ethane of ethene isolates in this ethene splitter S1 bottom.Be fixed on 20 bar at the top of this ethene splitter S1 and the absolute pressure of bottom.Estimate it is that the temperature computation of-28.9 ℃ and this ethene splitter S1 bottom is-25.4 ℃ in the temperature at the top of this ethene splitter S1 (outlet of condenser).Then will contain ethene and enrichment the cut of the compound lighter than ethene be sent to 20 theoretical stages are equipped with a tower DL1(further from ethene, to separate the compound lighter than ethene) to produce a kind of ethene of polyreaction grade.This charging is incorporated into the bottom of this tower.Quality reflux ratio stuck-at-１ 00.The cut L1 ' of 4kg/h isolates at the top of this tower (outlet of condenser) and the ethene C1 ' ' ' of a polyreaction grade isolates at this tower bottom.Be fixed on 20 bar at the top of this tower and the absolute pressure of bottom.Estimate it is that the temperature computation of-37.5 ℃ and this distillation tower DL1 bottom is-28.9 ℃ in the temperature at the top of this distillation tower DL1 (outlet of condenser).

The ethene C1 ' ' ' of this polymerization grade provides in table 1b together with the feature of cut H1 ' and L1 '.Rare gas element, hydrogen, methane, CO ₂, acetylene, ethene, ethane, propylene, other C3, C4, C5, H ₂The value of O, oxygenate and total amount are expressed as % by volume, and except in the bracket those, they are ppm by volume.

Table 1b

The mole flow velocity of the ethene C1 ' ' ' of this polyreaction grade reaches 12.693kmol/h, wherein 12.684kmol ethene/h.Total ethene (ethene among the ethene among the C1 ' ' '/outflow stream E) rate of recovery reaches 94.12%.The ethylene content of the ethene C1 ' ' ' of this polyreaction grade reached by volume 99.93% and the ratio of ethene and total ethene, ethane, acetylene be 99.98%.The propylene content that acetylene content among the ethene C1 ' ' ' of this polyreaction grade has reached among 0.3ppm by volume and the C1 ' ' ' is by volume less than 0.1ppm.The thermal power in the reboiler of distillation tower T1 that calculates, and the power in the reboiler of this demethaniser DM1 provide in table 2 in reboiler and the thermal power in the reboiler of this tower DL1 of ethene splitter S1.The heat consumption rate of the ethene C1 ' ' ' of this polyreaction grade has reached 0.855kWh/kg.

Table 2

From the data of example 1 and 2, the desired thermal power of ethene C1 ' ' ' that obtains the polymerization grade seemingly obtain to contain ethene the desired thermal power of composition C1 ' ' greater than 3.2 times.In addition, from above-mentioned total Recovery rate of ethylene seemingly, compare with the composition C1 ' ' that contains ethene is separated, when the ethene C1 ' ' ' to the polymerization grade carries out the separation of ethene from flow out stream E, lost about 5.59% ethene.The ethene of this loss can be recovered behind the more investment of cost and energy.

Example 3(is according to the present invention)

Make to form with the identical outflow stream E(of example 1 and in following table 3a, provide) stand described below

The V7.2 software simulation and in Fig. 2 patterned process.The mole flow velocity is 29.156kmol/h, wherein 13.476kmol ethene/h.The temperature of this outflow stream E is that 40 ℃ and its absolute pressure are 2.5 bar in the ingress of this process.

A preconditioning of describing in detail in example 1 is processed after the PCT, the outflow stream E ' of the compression that produces is joined be equipped with a reboiler and a condenser and comprise among 20 theoretical grades distillation tower T2 of (comprising this reboiler and condenser).To flow out E ' and be incorporated on the 10th grade, the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio of this tower is fixed on 2.794.76kg/h a cut F2 isolate at the top of distillation tower T2 (outlet of condenser) and an enrichment contain the compound of at least 4 carbon atoms cut H2 isolate in the bottom of distillation tower T2.Be fixed on 20 bar at the top of distillation tower T2 and the absolute pressure of bottom.Estimate it is that the temperature computation of-8.5 ℃ and distillation tower T2 bottom is 107.5 ℃ in the temperature at the top of distillation tower T2 (outlet of condenser).

Cut F2 is sent to a distillation tower T2 ' who is equipped with a reboiler and a condenser and comprises 20 theoretical stages (comprising this reboiler and condenser).Cut F2 is incorporated on the 10th grade, and the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio of this tower is fixed on 3.445.00kg/h one contain that the composition C2 of ethene isolates at the top of distillation tower T2 ' (outlet of condenser) and an enrichment contain the compound of at least 3 carbon atoms cut H2 ' isolate in the bottom of distillation tower T2 '.Be fixed on 20 bar at the top of distillation tower T2 and the absolute pressure of bottom.Estimate it is that the temperature computation of-37.6 ℃ and distillation tower T2 ' bottom is 48.6 ℃ in the temperature at the top of distillation tower T2 ' (outlet of condenser).

Then the composition C2 that this is contained ethene is heated to 50 ℃, the H pure with 0.0528kmol/h ₂Under the absolute pressure of 50 ℃ and 20 bar, mix and join in the deacetylation device, so that its acetylene saturation AS2 who stands to carry out adiabaticly.It is 99% that the transformation efficiency of acetylene is estimated, the selectivity estimation of ethene be 60.1% and the selectivity estimation of ethane be 39.9%.After the deacetylated effect, the composition C2 that contains ethene that produces is cooled to-30.7 ℃ and join and be equipped with a reboiler and a condenser and comprise among the demethanation distillation tower DM2 of 20 theoretical stages (comprising this reboiler and condenser).This composition C2 ' that contains ethene is incorporated on the 15th grade, and the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio stuck-at-１ 0 of the distillation tower of this demethanation.An enrichment composition C2 ' ' that cut L2 isolates at the top of the distillation tower DM2 of this demethanation (outlet of condenser) and this contains ethene of the 63kg/h compound lighter than ethene isolate in the base product section of this demethanation.Be fixed on 20 bar at the top of this demethanation distillation tower and the absolute pressure of bottom.Estimate it is that the temperature computation of-107.6 ℃ and this demethanation distillation tower bottom is-29.2 ℃ in the temperature at the top of this demethanation distillation tower (outlet of condenser).

Composition C2, the C2 ' and the C2 ' ' that contain ethene provide in table 3a together with the outflow stream E of cut F2, H2, H2 ' and L2 and the feature of E '.Rare gas element, hydrogen, methane, CO ₂, acetylene, ethene, ethane, propylene, other C3, C4, C5, H ₂The value of O, oxygenate and total amount are expressed as % by volume, and except in the bracket those, they are ppm by volume.

This mole flow velocity that contains the composition C2 ' ' of ethene reaches 13.628kmol/h, wherein 13.449kmol ethene/h.Total ethene (C2 ' ' in ethene/outflow stream E in ethene) rate of recovery reaches 99.80%.This ethylene content that contains the composition C2 ' ' of ethene reached by volume 98.69% and the ratio of ethene and total ethene, ethane, acetylene be 99.00%.This contains acetylene content among the composition C2 ' ' of ethene, and to have reached propylene content among the composition C2 ' ' that 19.4ppm by volume and this contain ethene be less than 0.1ppm by volume.The thermal power in the reboiler of distillation tower T2 and T2 ' that calculates, and the power in the reboiler of this demethaniser DM2 provides in table 4.This heat consumption rate that contains the composition C2 ' ' of ethene has reached 0.674kWh/kg.

Example 4(comparison example)

Outflow stream E that will be identical with example 3 processes in the mode identical with example 3.After this, this composition C2 ' ' that contains ethene is sent to an ethene splitter S2(who is equipped with 40 theoretical stages comprises reboiler and condenser).This composition C2 ' ' that contains ethene is incorporated on the 10th grade, and the 1st grade is that condenser and the 40th grade are reboilers.The quality reflux ratio of this tower is fixed on 5.Contain ethene and enrichment the cut of 360.00kg/h of the compound lighter than ethene isolate at the top of ethene splitter S2 (outlet of condenser) and the cut H2 ' ' that still contains the rich ethane of ethene isolates in ethene splitter S2 bottom.Be fixed on 20 bar at the top of ethene splitter S2 and the absolute pressure of bottom.Estimate it is that the temperature computation of-28.9 ℃ and ethene splitter S2 bottom is-25.5 ℃ in the temperature at the top of ethene splitter S2 (outlet of condenser).Then will contain ethene and enrichment the cut of the compound lighter than ethene be sent to 20 theoretical stages are equipped with a tower DL2(further from ethene, to separate the compound lighter than ethene) to produce a kind of ethene of polyreaction grade.This charging is incorporated into the bottom of this tower.Quality reflux ratio stuck-at-１ 00.The cut L2 ' of 4kg/h isolates at the top of this tower (outlet of condenser) and the ethene C2 ' ' ' of a polyreaction grade isolates at this tower bottom.Be fixed on 20 bar at the top of this tower and the absolute pressure of bottom.Estimate it is that the temperature computation of-37.5 ℃ and distillation tower DL2 bottom is-28.9 ℃ in the temperature at the top of distillation tower DL2 (outlet of condenser).

The ethene C2 ' ' of this polymerization grade is together with cut H2 " and the feature of L2 ' in following table 3b, provide.Rare gas element, hydrogen, methane, CO ₂, acetylene, ethene, ethane, propylene, other C3, C4, C5, H ₂The value of O, oxygenate and total amount are expressed as % by volume, and except in the bracket those, they are ppm by volume.

Table 3b

The mole flow velocity of the ethene C2 ' ' ' of this polyreaction grade reaches 12.693kmol/h, wherein 12.684kmol ethene/h.Total ethene (ethene among the ethene among the C2 ' ' '/outflow stream E) rate of recovery reaches 94.12%.The ethylene content of the ethene C2 ' ' ' of polyreaction grade reached by volume 99.93% and the ratio of ethene and total ethene, ethane, acetylene be 99.98%.The propylene content that the acetylene content of the ethene C2 ' ' ' of this polyreaction grade has reached among 0.3ppm by volume and the cut C2 ' ' ' is by volume less than 0.1ppm.The thermal power in the reboiler of distillation tower T2 and T2 ' that calculates, the power in the reboiler of this demethaniser DM2 provides in table 4 in reboiler and the thermal power in the reboiler of this tower DL2 of splitter S2.The heat consumption rate of the ethene C2 ' ' ' of this polyreaction grade has reached 1.296kWh/kg.

Table 4

Find out from the data of example 3 and 4, the desired thermal power of ethene C2 ' ' ' that obtains this polymerization grade seemingly obtain to contain ethene the desired thermal power of composition C2 ' ' greater than 1.9 times.In addition, from above-mentioned total Recovery rate of ethylene seemingly, compare with the composition C2 ' ' that contains ethene is separated, when the ethene C2 ' ' ' to the polymerization grade carries out the separation of ethene from flow out stream E, lost about 5.68% ethene.The ethene of this loss can be recovered behind the more investment of cost and energy.

Example 5(according to the present invention)

Make to form with the identical outflow stream E(of example 1 and in following table 5a, provide) stand described below

The V7.2 software simulation and in Fig. 3 patterned process.The mole flow velocity is 29.156kmol/h, wherein 13.476kmol ethene/h.The temperature of this outflow stream E is that 40 ℃ and its absolute pressure are 2.5 bar in the ingress of this process.

A preconditioning of describing in detail in example 1 is processed after the PCT, the outflow stream E ' of the compression that produces is joined be equipped with a reboiler and a condenser and comprise among 20 theoretical grades distillation tower T3 of (comprising this reboiler and condenser).To flow out E ' and be incorporated on the 10th grade, the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio of this tower is fixed on 2.The cut F3 of a 419.76kg/h isolates at the top of distillation tower T3 (condensator outlet) and a cut F3 ' isolates in the bottom of distillation tower T3.Be fixed on 20 bar at the top of distillation tower T3 and the absolute pressure of bottom.Estimate it is that the temperature computation of-38.2 ℃ and distillation tower T3 bottom is 45.7 ℃ in the temperature at the top of distillation tower T3 (outlet of condenser).

Cut F3 is sent to a distillation tower T3 ' who is equipped with a reboiler and a condenser and comprises 20 theoretical stages (comprising this reboiler and condenser).Cut F3 ' is incorporated on the 10th grade, and the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio of this tower is fixed on 2.375.00kg/h a cut F3 ' ' isolate at the top of distillation tower T3 ' (outlet of condenser) and an enrichment contain the compound of at least 4 carbon atoms cut H3 isolate in the bottom of distillation tower T3 '.Be fixed on 20 bar at the top of distillation tower T3 ' and the absolute pressure of bottom.Estimate it is that the temperature computation of 44.3 ℃ and distillation tower T3 ' bottom is 107.3 ℃ in the temperature at the top of distillation tower T3 ' (outlet of condenser).

Cut F3 and F3 ' ' are sent to a distillation tower T3 ' ' who is equipped with a reboiler and a condenser and comprises 20 theoretical stages (comprising this reboiler and condenser).Cut F3 and F3 ' ' are incorporated on the 10th grade, and the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio of this tower is fixed on 3.445.00kg/h a composition C3 who contains ethene isolate (outlet of condenser) and an enrichment at the top of distillation tower T3 ' ' contain the compound of at least 3 carbon atoms cut H3 ' isolate in the bottom of distillation tower T3 ' '.Be fixed on 20 bar at the top of distillation tower T3 ' ' and the absolute pressure of bottom.Estimate it is that the temperature computation of-37.6 ℃ and distillation tower T3 ' ' bottom is 48.6 ℃ in the temperature at the top of distillation tower T3 ' ' (outlet of condenser).

Then the composition C3 that this is contained ethene is heated to 50 ℃, the H pure with 0.0528kmol/h ₂Under the absolute pressure of 50 ℃ and 20 bar, mix and join in the deacetylation device, so that its acetylene saturation AS3 who stands to carry out adiabaticly.It is 99% that the transformation efficiency of acetylene is estimated, the selectivity estimation of ethene be 60.1% and the selectivity estimation of ethane be 39.9%.After the deacetylated effect, the composition C3 that contains ethene that produces is cooled to-30.7 ℃ and join and be equipped with a reboiler and a condenser and comprise among the demethanation distillation tower DM3 of 20 theoretical stages (comprising this reboiler and condenser).This composition C3 ' that contains ethene is incorporated on the 15th grade, and the 1st grade is that condenser and the 20th grade are reboilers.The quality reflux ratio stuck-at-１ 0 of the distillation tower of this demethanation.An enrichment composition C3 ' ' that cut L3 isolates at the top of the distillation tower DM3 of this demethanation (outlet of condenser) and this contains ethene of 63kg/h of the compound lighter than ethene isolate in the base product section of this demethanation.Be fixed on 20 bar at the top of this demethanation distillation tower and the absolute pressure of bottom.Estimate it is that the temperature computation of-107.6 ℃ and this demethanation distillation tower bottom is-29.2 ℃ in the temperature at the top of this demethanation distillation tower (outlet of condenser).

Composition C3, the C3 ' and the C3 ' ' that contain ethene provide in table 5a together with the outflow stream E of cut F3, F3 ', F3 ' ', H3, H3 ' and L3 and the feature of E '.Rare gas element, hydrogen, methane, CO ₂, acetylene, ethene, ethane, propylene, other C3, C4, C5, H ₂The value of O, oxygenate and total amount are expressed as % by volume, and except in the bracket those, they are ppm by volume.

This mole flow velocity that contains the composition C3 ' ' of ethene reaches 13.628kmol/h, wherein 13.449kmol ethene/h.Total ethene (C3 ' ' in ethene/outflow stream E in ethene) rate of recovery reaches 99.80%.This ethylene content that contains the composition C3 ' ' of ethene reached by volume 98.69% and the ratio of ethene and total ethene, ethane, acetylene be 99%.It is less than 0.1ppm by volume that this acetylene content that contains the composition C3 ' ' of ethene has reached by volume 19.4ppm and this propylene content that contains the composition C3 ' ' of ethene.The thermal power in the reboiler of distillation tower T3, T3 ' and T3 ' ' that calculates, and the power in the reboiler of this demethaniser DM3 provides in table 6.This heat consumption rate that contains the composition C3 ' ' of ethene has reached 0.642kWh/kg.

Example 6(comparison example)

Outflow stream E that will be identical with example 3 processes in the mode identical with example 5.After this, this composition C3 ' ' that contains ethene is sent to an ethene splitter S3(who is equipped with 40 theoretical stages comprises reboiler and condenser).This composition C3 ' ' that contains ethene is incorporated on the 10th grade, and the 1st grade is that condenser and the 40th grade are reboilers.The quality reflux ratio of this tower is fixed on 5.Contain ethene and enrichment the cut of 360.00kg/h of the compound lighter than ethene isolate at the top of ethene splitter S3 (outlet of condenser) and the cut H3 ' ' that still contains the rich ethane of ethene isolates in ethene splitter S3 bottom.Be fixed on 20 bar at the top of ethene splitter S3 and the absolute pressure of bottom.Estimate it is that the temperature computation of-28.9 ℃ and ethene splitter S3 bottom is-25.5 ℃ in the temperature at the top of ethene splitter S3 (outlet of condenser).Then will contain ethene and enrichment the cut of the compound lighter than ethene be sent to 20 theoretical stages are equipped with a tower DL3(further from ethene, to separate the compound lighter than ethene) to produce a kind of ethene of polyreaction grade.This charging is incorporated into the bottom of this tower.Quality reflux ratio stuck-at-１ 00.The cut L3 ' of 4kg/h isolates at the top of this tower (outlet of condenser) and the ethene C3 ' ' ' of a polyreaction grade isolates at this tower bottom.Be fixed on 20 bar at the top of this tower and the absolute pressure of bottom.Estimate it is that the temperature computation of-37.5 ℃ and this distillation tower DL3 bottom is-28.9 ℃ in the temperature at the top of this distillation tower DL3 (outlet of condenser).

The ethene C3 of this polymerization grade " ' together with cut H3 " and the feature of L3 ' in following table 5b, provide.Rare gas element, hydrogen, methane, CO ₂, acetylene, ethene, ethane, propylene, other C3, C4, C5, H ₂The value of O, oxygenate and total amount are expressed as % by volume, and except in the bracket those, they are ppm by volume.

Table 5b

The mole flow velocity of the ethene C3 ' ' ' of this polyreaction grade reaches 12.693kmol/h, wherein 12.684kmol ethene/h.Total ethene (ethene among the ethene among the C3 ' ' '/outflow stream E) rate of recovery reaches 94.12%.The ethylene content of the ethene C3 ' ' ' of this polyreaction grade reached by volume 99.93% and the ratio of ethene and total ethene, ethane, acetylene be 99.98%.It is less than 0.1ppm by volume that the acetylene content of the ethene C3 ' ' ' of this polyreaction grade has reached propylene content among 0.3ppm by volume and this cut C3 ' ' '.The thermal power in the reboiler of distillation tower T3, T3 ' and T3 ' ' that calculates, the power in the reboiler of this demethaniser DM3 provides in table 6 in reboiler and the thermal power in the reboiler of this tower DL3 of splitter S3.The heat consumption rate of the ethene C3 ' ' ' of this polyreaction grade has reached 1.260kWh/kg.

Table 6

From the data of example 5 and 6, the desired thermal power of ethene C3 ' ' ' that obtains this polymerization grade be obtain to contain ethene the desired thermal power of composition C3 ' ' greater than 1.9 times.In addition, from above-mentioned total Recovery rate of ethylene seemingly, compare with the composition C3 ' ' that contains ethene is separated, when the ethene C3 ' ' ' to the polymerization grade carries out the separation of ethene from flow out stream E, lost about 5.68% ethene.The ethene of this loss can be recovered behind the more investment of cost and energy.

Claims

1. contain the composition of ethene, it comprises:

(b) ethene of certain value, thus so that this value and the ratio of total amount value that contains the hydrocarbon compound of 2 carbon atoms are between 97% and 99.5%.

2. the composition that contains ethene according to claim 1 is characterized in that the described hydrocarbon compound that contains 2 carbon atoms is ethene, ethane and acetylene.

According to claim 1 and 2 in each described composition that contains ethene, it is characterized in that it comprises less than the hydrocarbon compound that contains 3 carbon atoms of 100ppm by volume and less than by volume oxygenate and the water of 100ppm at least.

4. for the manufacture of the method for the composition that contains ethene, according to the method:

A) make from oxygenate to the process of alkene and stood processed conventionally, as to contain ethene and other composition outflow stream E and stood preconditioning and process the outflow stream E ' that obtains to compress; And

B) each described composition that contains ethene in one to three distillation tower, separating to obtain according to claim 1 to 3 outflow of described compression stream E '.

5. method according to claim 4 is characterized in that the described outflow stream E of ethene and other composition that contains is from the process of methyl alcohol to alkene.

6. the outflow stream E ' that according to claim 4 or one of 5 described methods, it is characterized in that described compression contains by volume at most the oxygenate of 1000ppm and the maximum water of 100ppm by volume.

7. each described method in 6 according to claim 4, wherein in step a) afterwards, the composition C1 that contains ethene that the outflow of described compression stream E ' is separated in a distillation tower T1 at this distillation tower T1 top and be separated in the enrichment of this distillation tower T1 bottom the cut H1 that contains the compound of at least 3 carbon atoms.

8. each described method in 6 according to claim 4, wherein in step a) afterwards, the outflow stream E ' of described compression is separated by following steps in two distillation towers:

B1) the first separating step, this step are the cut F2 that the outflow of described compression stream E ' is separated at this distillation tower T2 top and have been separated in the enrichment of this distillation tower T2 bottom the cut H2 that contains the compound of at least 4 carbon atoms in the first distillation tower T2; And

B2) the second separating step, this step are the composition C2 that contains ethene that described cut F2 is separated at this distillation tower T2 ' top and have been separated in the enrichment of this distillation tower T2 ' bottom the cut H2 ' that contains the compound of at least 3 carbon atoms in second column T2 '.

9. each described method in 6 according to claim 4, wherein in step a) afterwards, the outflow stream E ' of described compression is separated by following steps in three distillation towers:

B1) the first separating step, this step be the cut F3 that the outflow of described compression stream E ' is separated at this distillation tower T3 top and be separated into cut F3 ' in this distillation tower T3 bottom in the first distillation tower T3,

B2) the second separating step, this step are the cut F3 ' ' that described cut F3 ' is separated at this distillation tower T3 ' top and have been separated in the enrichment of this distillation tower T3 ' bottom the cut H3 that contains the compound of at least 4 carbon atoms in second column T3 '; And

B3) the 3rd separating step, this step are described cut F3 and F3 " at the 3rd distillation tower T3 " in be separated at this distillation tower T3 " the composition C3 that contains ethene at top and be separated at this distillation tower T3 " enrichment of bottom contain the cut H3 ' of the compound of at least 3 carbon atoms.

10. each described method in 9 according to claim 4 is characterized in that, at step b) afterwards, make the described composition that contains ethene stand the acetylene saturation.

11. each described method in 10 according to claim 4, it is characterized in that, at step b) afterwards, make separating step (being called demethanation) that the described composition that contains ethene stands to replenish with the cut of the compound lighter than ethene of having isolated enrichment thus.

12. from according to claim 1 to 3 each described composition that contains ethene begin to make the method for at least a ethylene derivative compounds.

13. for the manufacture of the method for ethylene dichloride, make according to claim 1 in 3 each described composition that contains ethene stand chlorization and/or oxychlorination to produce ethylene dichloride according to the method.

14. method according to claim 13, the method further comprise the ethylene dichloride pyrolysis to produce vinylchlorid.

15. further comprising, method according to claim 14, the method make chloroethylene polymerization to produce polyvinyl chloride.