CN110467516A - A kind of system and technique using natural gas as raw material through chloromethanes alkene - Google Patents
A kind of system and technique using natural gas as raw material through chloromethanes alkene Download PDFInfo
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- CN110467516A CN110467516A CN201910794595.5A CN201910794595A CN110467516A CN 110467516 A CN110467516 A CN 110467516A CN 201910794595 A CN201910794595 A CN 201910794595A CN 110467516 A CN110467516 A CN 110467516A
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- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C07—ORGANIC CHEMISTRY
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Abstract
The invention discloses a kind of systems using natural gas as raw material through chloromethanes alkene, including sequentially connected natural gas separative unit, methane chlorination unit and chlorizate separative unit, monochloro methane outlet in chlorizate separative unit is connected with the entrance of alkene preparation unit, alkene preparation unit is successively connect with dehydrochlorination unit and separation of hydrocarbons unit, alkene in dehydrochlorination unit prepares by-product hydrogen chloride outlet and is connected with hydrogen chloride mixer, and hydrogen chloride mixer is successively connected with chloration hydro-oxidation unit, chlorine mixer and methane chlorination unit；The invention also discloses a kind of techniques using natural gas as raw material through chloromethanes alkene, and methane chlorination is obtained monochloro methane, is then converted to low-carbon alkene.System of the invention is provided with methane chlorination unit and alkene preparation unit, realizes natural gas through chloromethanes and prepares recycling for alkene and chlorine element；Process conditions of the invention are mild, avoid generation carbon dioxide, improve total carbon utilisation rate.
Description
Technical field
The invention belongs to gas chemical industry's technical fields, and in particular to one kind is raw material through chloromethanes alkene using natural gas
System and technique.
Background technique
So that coal resources account for the major part of China's non-renewable energy, this brings pole to environment for the limitation of china natural resources structure
Big pressure.The unreasonable primary energy structure of the haze and China that annual winter necessarily occurred in recent years has much relations.Ring
Border pressure necessarily promotes the primary energy structure in China to low carbon development, and though natural gas from stock number or from low-carbon,
The optimal selection of the clean coming few decades China feature Shang Kandoushi energy development.
For low-carbon alkene as the basic raw material of industry, demand is big, and improving with social and economic level is in growing trend.By day
Right gas is converted to low-carbon alkene, it will is one of the most promising route that gas chemical industry utilizes.Methane is the master of natural gas
Ingredient is wanted, accounting is generally up to 90% or more.Methane passes through sp by a carbon and four hydrogen atoms3The mode of hydridization forms,
Therefore the structure of methane molecule is positive tetrahedral structure, and the bond distance of four keys is identical, and bond angle is equal.Methane molecule high degree of symmetry
Structure determines that its chemical property is relatively stable, and activation difficulty is larger.The activation method of methane first is that keeping all c h bonds equal
It splits, typical process is exactly steam reformation acquisition synthesis gas of the natural gas via energy-intensive, and synthesis gas is again via F- T synthesis
It is converted into liquid fuel or is converted into the chemical products such as methanol.Another activation method of methane be selectively activate it is single
C h bond rather than make all c h bond homolysis；Partial oxidation of methane methanol, methane chlorination process, methane oxidation coupling etc.
Belong to this activation method.
Manufacturing Alkene from Natural Gas technique most mature at present is to convert synthesis gas for natural gas first, and synthesis gas is using F-
The intermediates such as T synthesis or methanol (dimethyl ether) generate low-carbon alkene.However the technique transformation routes are tediously long, investment and energy consumption are high.
Especially prominent problem is the auxiliary agent or medium using oxygen molecule as methane activation, inevitably will form and discharges and is big
Carbon dioxide is measured, ecological environment, and its total carbon utilisation rate usually not more than half are not only influenced.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide one kind with natural gas
System for raw material through chloromethanes alkene.It is provided with methane chlorination unit and alkene preparation unit in the system, keeps methane first
Feeding methane chlorination unit chlorination is monochloro methane, enters back into alkene preparation unit and is converted into low-carbon alkene, realizes natural gas
The technique that alkene is prepared through chloromethanes, system composition is succinct and easily controllable, chlorizate separative unit in simultaneity factor and
Dehydrochlorination unit realizes removing hydrogen chloride recycling, continues to participate in chlorine after chloration hydro-oxidation unit is converted into regeneration chlorine
Change reaction, realize recycling for chlorine element, effectively reduce energy consumption, reduce the waste of raw material, improves total carbon utilization
Rate.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: one kind is raw material through chloromethanes using natural gas
The system of alkene processed, which is characterized in that natural gas separative unit, methane purifying unit, first including passing sequentially through pipeline connection
Alkane chlorination unit and chlorizate separative unit, the natural gas separative unit have raw natural gas entrance, methane purifying list
Member has thick methane entrance, and the thick methane entrance is connected with the outlet of natural gas separative unit, the methane chlorination unit tool
There are purification methane entrance, mixing chlorine inlet and unreacted methane entrance, the purification methane entrance and methane purifying unit
Outlet is connected, and the unreacted methane entrance is connected with the outlet of chlorizate separative unit, the chlorizate separative unit
With chlorizate entrance, monochloro methane outlet and the outlet of methane chlorination by-product hydrogen chloride, the chlorizate entrance and methane
The outlet of chlorination unit is connected, and monochloro methane outlet is connected with the entrance of alkene preparation unit, and methane chlorination by-product hydrogen chloride goes out
Mouth is connected with hydrogen chloride mixer；
The alkene preparation unit passes sequentially through pipeline and connect with dehydrochlorination unit and separation of hydrocarbons unit, the dechlorination
Change hydrogen unit prepares product inlet with alkene and alkene prepares by-product hydrogen chloride outlet, and the alkene prepares product inlet and alkene
The outlet of hydrocarbon preparation unit is connected, and the alkene prepares by-product hydrogen chloride outlet and is connected with hydrogen chloride mixer, the hydro carbons point
From unit have alkene prepare hydrocarbon product entrance, ethylene outlet and propylene outlet, the alkene prepare hydrocarbon product entrance with
The outlet of dehydrochlorination unit is connected；
The hydrogen chloride mixer by pipeline successively with chloration hydro-oxidation unit, chlorine mixer and methane chlorination unit
It is connected, chloration hydro-oxidation unit has mixed chlorinated hydrogen entrance and raw material oxygen intake, the mixed chlorinated hydrogen entrance and chlorination
The outlet of hydrogen mixer is connected, and chlorine mixer has regeneration chlorine inlet and raw material chlorine inlet, the regeneration chlorine inlet
It is connected with the outlet of chloration hydro-oxidation unit, the outlet phase of the mixing chlorine inlet and chlorine mixer of the methane chlorination unit
Even.
Methane chlorination unit and alkene preparation unit are provided in system of the invention, raw natural gas is successively through natural gas
Methane is obtained after separative unit separation and methane purifying unit, methane is sent into the progress chlorination of methane chlorination unit and is converted into a chloromethane
Alkane, is then fed into alkene preparation unit and is converted into low-carbon alkene, different alkene is obtained through separation of hydrocarbons unit, to realize day
Right gas prepares the technique of alkene through chloromethanes, and system composition is succinct and easily controllable, and equipment investment is few, at low cost, due to being not necessarily to
By the producing synthesis gas from natural gas process of ultra-high temperature, and the reaction condition of each unit is relatively mild, effectively reduces energy consumption, together
When avoid using oxygen molecule as methane activation auxiliary agent or medium, cause generate great amount of carbon dioxide influence ecological environment,
Improve total carbon utilisation rate；In addition, the chlorine that the chlorizate separative unit being arranged in present system generates methane and chlorine
Change product to be separated, removes the hydrogen chloride and unreacted methane in monochloro methane, the dehydrochlorination unit of setting is to low-carbon
Hydrogen chloride in alkene is removed, and the hydrogen chloride that separation and removing obtain obtains chlorine through oxidation reaction, is then used as raw material
It is sent into methane chlorination unit and participates in chlorination reaction, realize recycling for chlorine element, and unreacted methane is back to first
Continue chlorination reaction in alkane chlorination unit, reduce the waste of raw material, further improves total carbon utilisation rate.
In addition, the present invention also provides a kind of works for preparing alkene through the system of chloromethanes alkene using natural gas as raw material
Skill, which is characterized in that the technique the following steps are included:
Step 1: raw natural gas is sent into natural gas separative unit, makes methane and other separation of hydrocarbons, obtain thick first
Alkane is simultaneously sent into methane purifying unit and carries out purification and be purified methane, and purification methane is then sent into methane chlorination unit and chlorine
Chlorination reaction is carried out, chlorizate is generated, then chlorizate feeding chlorizate separative unit is separated, obtains a chloromethane
Alkane, hydrogen chloride and unreacted methane, unreacted methane is back in methane chlorination unit and continues to participate in chlorination reaction；
Step 2: monochloro methane obtained in step 1 is sent into alkene preparation unit, convert under the action of catalyst
It for low-carbon alkene, is then fed into dehydrochlorination unit and removes hydrogen chloride, obtain hydrogen chloride and hydrocarbon product, then by hydrocarbon product
It is sent into separation of hydrocarbons unit to be separated, obtains ethylene and propylene；
Step 3: hydrogen chloride obtained in hydrogen chloride, step 2 obtained in step 1 is sent into hydrogen chloride mixer
After mixing, it is sent into chloration hydro-oxidation unit and oxygen carries out oxidation reaction and obtains regeneration chlorine, regeneration chlorine is sent into chlorine and is mixed
After clutch is mixed with raw material chlorine, it is sent into methane chlorination unit and participates in chlorination reaction.
The present invention obtains monochloro methane using the methane in chlorine active natural gas, is then catalytically conveted to monochloro methane
Low-carbon alkene realizes the low-carbon alkene conversion of natural gas, and process conditions are mild, and technique is short, low energy consumption, avoid using oxygen
Son as methane activation auxiliary agent or medium, cause generate great amount of carbon dioxide influence ecological environment, improve total carbon utilisation rate；
In addition, the hydrogen chloride, monochloro methane in the chlorination reaction product that the present invention generates methane and chlorine are converted into low-carbon alkene mistake
The hydrogen chloride generated in journey carries out recycling oxidation and generates regeneration chlorine, so that it is participated in the chlorination of methane, realizes following for chlorine element
Ring utilizes, and to chlorination reaction is continued after unreacted methane recovery, reduces the waste of raw material, further improves total carbon
Utilization rate.
Above-mentioned technique, which is characterized in that the detailed process of purification described in step 1 are as follows: be first in temperature by thick methane
Hydroconversion reactions are carried out under conditions of 220 DEG C~500 DEG C, then carry out desulfurization under conditions of temperature is 250 DEG C~400 DEG C
It reacts, the sulfur content in the methane is 0.1ppm or less；The temperature of the chlorination reaction is 180 DEG C~450 DEG C；In step 2
The temperature that the monochloro methane is converted into low-carbon alkene under the action of catalyst is 300 DEG C~500 DEG C；It is aoxidized described in step 3
The temperature of reaction is 300 DEG C~450 DEG C.The present invention carries out hydro-conversion to thick methane at 220 DEG C~500 DEG C, makes in thick methane
Organic sulfur conversion be inorganic sulfur, then in 250 DEG C~400 DEG C removing inorganic sulfurs, so that sulfur content in methane is 0.1ppm
Hereinafter, obtaining qualified methane；Compared with the producing synthesis gas from natural gas process of ultra-high temperature in the prior art, above-mentioned each technique
Reaction condition is relatively mild, effectively reduces energy consumption.
Above-mentioned technique, which is characterized in that the detailed process of the purification are as follows: be first 350 DEG C in temperature by thick methane
Under the conditions of carry out hydroconversion reactions, then temperature be 350 DEG C under conditions of carry out desulphurization reaction；The temperature of the chlorination reaction
Degree is 450 DEG C；The temperature that the monochloro methane is converted into low-carbon alkene under the action of catalyst is 450 DEG C；The oxidation reaction
Temperature be 350 DEG C.The reaction condition of above-mentioned each technique can effectively remove the sulphur in thick methane, promote methane chlorination at a chloromethane
Alkane, monochloro methane are converted into low-carbon alkene, hydrogen chloride is converted into the efficiency of chlorine, further improve total carbon utilisation rate.
Compared with the prior art, the present invention has the following advantages:
1, methane chlorination unit and alkene preparation unit are provided in system of the invention, methane is sent into methane chlorination unit
It carries out chlorination and is converted into monochloro methane, be then fed into alkene preparation unit and be converted into low-carbon alkene, obtained through separation of hydrocarbons unit
Different alkene, to realize the technique that natural gas prepares alkene through chloromethanes, system composition is succinct and easily controllable, and equipment is thrown
Money is few, at low cost, effectively reduces energy consumption, improves total carbon utilisation rate.
2, the chlorizate separative unit and dehydrochlorination unit being arranged in system of the invention are realized to monochloro methane
In hydrogen chloride and low-carbon alkene in removing hydrogen chloride recycling, obtained chloration hydro-oxidation be converted into regeneration chlorine after continue
It is sent into methane chlorination unit and participates in chlorination reaction, realize recycling for chlorine element, reduce the waste of raw material, further
Improve total carbon utilisation rate.
3, the present invention obtains monochloro methane using the methane in chlorine active natural gas, then by monochloro methane catalyzed conversion
For low-carbon alkene, realize the low-carbon alkene conversion of natural gas, process conditions are mild, and technique is short, low energy consumption, while avoid by
Natural gas be converted into use during synthesis gas oxygen molecule as methane activation auxiliary agent or medium, cause to generate a large amount of titanium dioxides
Carbon influences ecological environment, improves total carbon utilisation rate.
Technical solution of the present invention is described in further detail below by drawings and examples.
Detailed description of the invention
Fig. 1 is component units and the company of the system by raw material of natural gas through chloromethanes alkene of the embodiment of the present invention 1
Connect relation schematic diagram.
Fig. 2 is comparative example 1 of the present invention by raw material of natural gas through synthesising gas systeming carbinol, again by the system of methanol-to-olefins
Component units and connection relationship diagram.
Description of symbols:
1-natural gas separative unit；2-methane purifying units；
3-methane chlorination units；4-chlorizate separative units；
5-alkene preparation units；6-dehydrochlorination units；
7-hydrogen chloride mixers；8-chloration hydro-oxidation units；
9-chlorine mixers；10-separation of hydrocarbons units；
11-raw natural gas entrances；12-thick methane entrances；
13-purification methane entrances；14-chlorizate entrances；
The outlet of 15-monochloro methanes；16-alkene prepare product inlet；
17-alkene prepare by-product hydrogen chloride outlet；The outlet of 18-methane chlorination by-product hydrogen chlorides；
19-mixed chlorinated hydrogen entrances；20-raw material oxygen intakes；
21-regeneration chlorine inlets；22-raw material chlorine inlets；
23-mixing chlorine inlets；24-unreacted methane entrances；
25-alkene prepare hydrocarbon product entrance；The outlet of 26-ethylene；
The outlet of 27-propylene；28-natural gas purification units；
29-producing synthesis gas from natural gas units；30-methanol synthesis units；
31-methanol-to-olefins units；32-feed water inlets；
33-purified natural gas entrances；34-synthesis gas entrances；
35-methanol inlets；36-methanol-to-olefins product inlets.
Specific embodiment
System using natural gas as raw material through chloromethanes alkene of the invention is described in detail by embodiment 1.
Embodiment 1
As shown in Figure 1, the system using natural gas as raw material through chloromethanes alkene of the present embodiment includes passing sequentially through pipe
Natural gas separative unit 1, methane purifying unit 2, methane chlorination unit 3 and the chlorizate separative unit 4 of line connection, the day
Right gas separative unit 1 has raw natural gas entrance 11, and methane purifying unit 2 has thick methane entrance 12, and the thick methane enters
Mouth 12 is connected with the outlet of natural gas separative unit 1, and the methane chlorination unit 3 has purification methane entrance 13, mixing chlorine
Entrance 23 and unreacted methane entrance 24, the purification methane entrance 13 are connected with the outlet of methane purifying unit 2, described not anti-
Methane entrance 24 and the outlet of chlorizate separative unit 4 is answered to be connected, the chlorizate separative unit 4 enters with chlorizate
Mouth 14, monochloro methane outlet 15 and methane chlorination by-product hydrogen chloride outlet 18, the chlorizate entrance 14 and methane chlorination list
The outlet of member 3 is connected, and monochloro methane outlet 15 is connected with the entrance of alkene preparation unit 5, the outlet of methane chlorination by-product hydrogen chloride
18 are connected with hydrogen chloride mixer 7；
The alkene preparation unit 5 passes sequentially through pipeline and connect with dehydrochlorination unit 6 and separation of hydrocarbons unit 10, described
There is dehydrochlorination unit 6 alkene to prepare product inlet 16 and alkene prepares by-product hydrogen chloride and exports 17, the alkene preparation production
Object entrance 16 is connected with the outlet of alkene preparation unit 5, and the alkene prepares by-product hydrogen chloride outlet 17 and hydrogen chloride mixer 7
It is connected, there is the separation of hydrocarbons unit 10 alkene to prepare hydrocarbon product entrance 25, ethylene outlet 26 and propylene outlet 27, described
Alkene prepares hydrocarbon product entrance 25 and is connected with the outlet of dehydrochlorination unit 6；
The hydrogen chloride mixer 7 by pipeline successively with chloration hydro-oxidation unit 8, chlorine mixer 9 and methane chlorination
Unit 3 is connected, and chloration hydro-oxidation unit 8 has mixed chlorinated hydrogen entrance 19 and raw material oxygen intake 20, the mixed chlorinated hydrogen
Entrance 19 is connected with the outlet of hydrogen chloride mixer 7, and chlorine mixer 9 has regeneration chlorine inlet 21 and raw material chlorine inlet
22, the regeneration chlorine inlet 21 is connected with the outlet of chloration hydro-oxidation unit 8, the mixing chlorine of the methane chlorination unit 3
Entrance 23 is connected with the outlet of chlorine mixer 9.
Be provided in system of the invention pass sequentially through pipeline connection natural gas separative unit 1, methane purifying unit 2,
Methane chlorination unit 3 and chlorizate separative unit 4, raw natural gas enter natural gas separation list from raw natural gas entrance 11
Isolated thick methane is carried out after member 1, thick methane enters purified desulfurization in methane purifying unit 2 by thick methane entrance 12 and obtains
To purification methane, methane enters the progress chlorination of methane chlorination unit 3 by purification methane entrance 13 and obtains chlorizate, then leads to
Over-chlorinated products entrance 14 is separated into chlorizate separative unit 4, and obtained monochloro methane is through monochloro methane outlet 15
Catalysis reaction is carried out into alkene preparation unit 5 and is converted into low-carbon alkene, and obtained hydrogen chloride is through methane chlorination by-product hydrogen chloride
Outlet 18 is sent into hydrogen chloride mixer 7, and obtained unreacted methane is back to methane chlorination unit 3 and continues chlorination；
Dehydrochlorination unit 6 is additionally provided in system of the invention, low-carbon alkene prepares product inlet 16 into dechlorination by alkene
Hydrogen unit 6 removes hydrogen chloride, obtains olefin product, then prepare hydrocarbon product entrance 25 by alkene and enter separation of hydrocarbons unit 10
Middle through separating, separation product is discharged from ethylene outlet 26 and propylene outlet 27 respectively, ethylene and propylene is obtained, to realize day
Right gas prepares the technique of alkene through chloromethanes, and system composition is succinct and easily controllable, and equipment investment is few, at low cost, due to being not necessarily to
By the producing synthesis gas from natural gas process of ultra-high temperature, and the reaction condition of each unit is relatively mild, effectively reduces energy consumption, mentions
High total carbon utilisation rate.
Chloration hydro-oxidation unit 8, the isolated chlorination of chlorizate separative unit 4 are additionally provided in system of the invention
Hydrogen removes obtained hydrogen chloride through methane chlorination by-product hydrogen chloride outlet 18 and dehydrochlorination unit 6 and prepares by-product through alkene
Hydrogen chloride outlet 17 is sent into hydrogen chloride mixer 7 after mixing, enters chloration hydro-oxidation list through mixed chlorinated hydrogen entrance 19
Member 8 is aoxidized to obtain regeneration chlorine with the oxygen entered in chloration hydro-oxidation unit 8 through raw material oxygen intake 20, regenerates chlorine
Gas enters in chlorine mixer 9 through regeneration chlorine inlet 21, with the raw material chlorine for entering chlorine mixer 9 through raw material chlorine inlet 22
Gas after mixing, then enters in methane chlorination unit 3 through mixing chlorine inlet 23 and participates in methane chlorination reaction, to realize
Chlorine element recycles, and unreacted methane is back in methane chlorination unit and continues chlorination reaction, reduces original
The waste of material further improves total carbon utilisation rate.
Comparative example 1
As shown in Fig. 2, this comparative example using natural gas as raw material through synthesising gas systeming carbinol, again by the system of methanol-to-olefins
Producing synthesis gas from natural gas unit 29, methanol synthesis unit 30,31 and of methanol-to-olefins unit including passing sequentially through pipeline connection
Separation of hydrocarbons unit 10, the producing synthesis gas from natural gas unit 29 have feed water inlet 32 and purified natural gas entrance 33, institute
It states purified natural gas entrance 33 to be connected with the outlet of natural gas purification unit 28, the natural gas purification unit 28 has raw material day
Right gas entrance 11, the methanol synthesis unit 30 has synthesis gas entrance 34, synthesis gas entrance 34 and producing synthesis gas from natural gas list
The outlet of member 29 is connected, and the methanol-to-olefins unit 31 has methanol inlet 35, methanol inlet 35 and methanol synthesis unit 30
Outlet be connected, the separation of hydrocarbons unit 10 have methanol-to-olefins product inlet 36, ethylene outlet 26 and propylene outlet 27,
Methanol-to-olefins product inlet 36 is connected with the outlet of methanol-to-olefins unit 31.
Producing synthesis gas from natural gas unit 29, methanol synthesis unit 30 and methanol system are disposed in the system of this comparative example
Olefin unit 31, raw natural gas is entered in natural gas purification unit 28 by raw natural gas entrance 11 carries out purification sulphur removal,
Obtained purified natural gas enters producing synthesis gas from natural gas unit 29 and enters producing synthesis gas from natural gas with by feed water inlet 32
The water of unit 29, which reacts, generates synthesis gas, and synthesis gas catalyzes and synthesizes first into methanol synthesis unit 30 through synthesis gas entrance 34
Alcohol, methanol enters in methanol-to-olefins unit 31 by methanol inlet 35 is converted into olefin product, and olefin product enters hydro carbons point
From unit 10 through separating, and it is corresponding by 27 discharge of ethylene outlet 26 and propylene outlet, obtain ethylene and propylene.
Embodiment 1 and comparative example 1 are compared it is found that system of the invention is to producing synthesis gas from natural gas list in comparative example
Member 29, methanol synthesis unit 30 and methanol-to-olefins unit 31 are improved, and are prepared using methane chlorination unit 3 and alkene single
Member 5 is as replacement, thus by by raw material of natural gas through synthesising gas systeming carbinol, again by the system reform of methanol-to-olefins for day
Right gas is system of the raw material through chloromethanes alkene, reduces the equipment investment in system, shortens process flow, reduce into
Sheet and energy consumption.
Utilization of the invention passes through implementation by the technique that raw material prepares alkene through the system of chloromethanes alkene of natural gas
2~embodiment of example 5 and comparative example 2 are described in detail, wherein system of the 2~embodiment of embodiment 5 using embodiment 1, comparison
The system that example 2 uses embodiment 2.
Embodiment 2
The technique of the present embodiment the following steps are included:
Step 1: raw natural gas is sent into natural gas separative unit 1 with the flow of 100t/h, make methane and other hydro carbons
Separation, obtains thick methane and is sent into methane purifying unit 2 being purified to obtain the methane that sulfur content is 0.08ppm, then by first
Alkane is sent into methane chlorination unit 3 and chlorine and carries out chlorination reaction under conditions of temperature is 450 DEG C, generates chlorizate, then will
Chlorizate is sent into chlorizate separative unit 4 and is separated, and monochloro methane, hydrogen chloride and unreacted methane are obtained, will not
The methane of reaction is back in methane chlorination unit 3 and continues to participate in chlorination reaction；The detailed process of the purification are as follows: first by thick first
Alkane carries out hydroconversion reactions under conditions of temperature is 350 DEG C, and it is anti-that desulfurization is then carried out under conditions of temperature is 350 DEG C
It answers；
Step 2: monochloro methane obtained in step 1 is sent into alkene preparation unit 5, urged in silicoaluminophosphamolecular molecular sieves
Agent acts on, is converted into low-carbon alkene under conditions of 450 DEG C, is then fed into dehydrochlorination unit 6 and removes hydrogen chloride, obtains chlorine
Change hydrogen and hydrocarbon product, then hydrocarbon product feeding separation of hydrocarbons unit 10 is separated, obtains ethylene and propylene；
Step 3: hydrogen chloride obtained in hydrogen chloride, step 2 obtained in step 1 is sent into hydrogen chloride mixer 7
After mixing, it is sent into chloration hydro-oxidation unit 8 and oxygen and is aoxidized under conditions of ruthenium-based catalyst acts on, temperature is 350 DEG C
Reaction obtains chlorine, after chlorine feeding chlorine mixer 9 is mixed with raw material chlorine, is sent into methane chlorination unit 3 and participates in chlorine
Change reaction.
Comparative example 2
The technique of this comparative example the following steps are included:
It is 350 DEG C in temperature Step 1: raw natural gas is sent into natural gas purification unit 28 with the flow of 100t/h
Under conditions of successively carry out hydroconversion reactions and desulphurization reaction, obtain sulfur content be 0.08ppm purified natural gas, then will
Purified natural gas enters producing synthesis gas from natural gas unit 29 and water and carries out steam conversion under conditions of 850 DEG C, generates synthesis gas；
Step 2: the synthesis gas generated in step 1 is entered in methanol synthesis unit 30 through synthesis gas entrance 34, in phosphorus
Sour Si-Al molecular sieve catalyst action, pressure 5MPa, temperature catalyze and synthesize methanol under conditions of being 250 DEG C, and then methanol passes through
It crosses methanol inlet 35 to enter in methanol-to-olefins unit 31, be converted under conditions of molecular sieve catalyst effect, temperature are 450 DEG C
For olefin product, enters back into separation of hydrocarbons unit 10 and separated, obtain ethylene and propylene.
CO2 emission, energy consumption and the investment in fixed assets of unit olefin product will be prepared in embodiment 2 and comparative example 2
It is compared, as a result as shown in table 1 below.
1 embodiment 2 of table is thrown with CO2 emission, energy consumption and the fixed assets for preparing unit olefin product in comparative example 2
Money
As known from Table 1, with using natural gas as raw material through synthesising gas systeming carbinol, again by the comparative example of methanol-to-olefins 1 compared with,
Embodiment 2 reduces 58% through the CO2 emission of chloromethanes alkene using natural gas as raw material, and energy consumption reduces 37%, Gu
Determining assets investment reduces 20%, illustrates that system of the invention reduces equipment investment, effectively reduces energy consumption, and of the invention
While technique realizes the low-carbon alkene conversion of natural gas, technique requirement is reduced, avoids and converts synthesis for natural gas
Use during gas oxygen molecule as methane activation auxiliary agent or medium, cause to generate great amount of carbon dioxide influence ecological environment,
Improve total carbon utilisation rate.
Embodiment 3
The technique of the present embodiment the following steps are included:
Step 1: raw natural gas is sent into natural gas separative unit 1 with the flow of 100t/h, make methane and other hydro carbons
Separation, obtains thick methane and is sent into methane purifying unit 2 being purified to obtain the methane that sulfur content is 0.1ppm, then by methane
It is sent into methane chlorination unit 3 and chlorine and carries out chlorination reaction under conditions of temperature is 180 DEG C, generate chlorizate, then by chlorine
Change product feeding chlorizate separative unit 4 to be separated, obtains monochloro methane, hydrogen chloride and unreacted methane, it will be not anti-
The methane answered is back in methane chlorination unit 3 and continues to participate in chlorination reaction；The detailed process of the purification are as follows: first by thick methane
Hydroconversion reactions are carried out under conditions of temperature is 500 DEG C, then carry out desulphurization reaction under conditions of temperature is 400 DEG C；
Step 2: monochloro methane obtained in step 1 is sent into alkene preparation unit 5, urged in silicoaluminophosphamolecular molecular sieves
Agent acts on, is converted into low-carbon alkene under conditions of 500 DEG C, is then fed into dehydrochlorination unit 6 and removes hydrogen chloride, obtains chlorine
Change hydrogen and hydrocarbon product, then hydrocarbon product feeding separation of hydrocarbons unit 10 is separated, obtains ethylene and propylene；
Step 3: hydrogen chloride obtained in hydrogen chloride, step 2 obtained in step 1 is sent into hydrogen chloride mixer 7
After mixing, it is sent into chloration hydro-oxidation unit 8 and oxygen and is aoxidized under conditions of ruthenium-based catalyst acts on, temperature is 300 DEG C
Reaction obtains chlorine, after chlorine feeding chlorine mixer 9 is mixed with raw material chlorine, is sent into methane chlorination unit 3 and participates in chlorine
Change reaction.
Embodiment 4
The technique of the present embodiment the following steps are included:
Step 1: raw natural gas is sent into natural gas separative unit 1 with the flow of 100t/h, make methane and other hydro carbons
Separation, obtains thick methane and is sent into methane purifying unit 2 being purified to obtain the methane that sulfur content is 0.05ppm, then by first
Alkane is sent into methane chlorination unit 3 and chlorine and carries out chlorination reaction under conditions of temperature is 350 DEG C, generates chlorizate, then will
Chlorizate is sent into chlorizate separative unit 4 and is separated, and monochloro methane, hydrogen chloride and unreacted methane are obtained, will not
The methane of reaction is back in methane chlorination unit 3 and continues to participate in chlorination reaction；The detailed process of the purification are as follows: first by thick first
Alkane carries out hydroconversion reactions under conditions of temperature is 220 DEG C, and it is anti-that desulfurization is then carried out under conditions of temperature is 250 DEG C
It answers；
Step 2: monochloro methane obtained in step 1 is sent into alkene preparation unit 5, urged in silicoaluminophosphamolecular molecular sieves
Agent acts on, is converted into low-carbon alkene under conditions of 300 DEG C, is then fed into dehydrochlorination unit 6 and removes hydrogen chloride, obtains chlorine
Change hydrogen and hydrocarbon product, then hydrocarbon product feeding separation of hydrocarbons unit 10 is separated, obtains ethylene and propylene；
Step 3: hydrogen chloride obtained in hydrogen chloride, step 2 obtained in step 1 is sent into hydrogen chloride mixer 7
After mixing, it is sent into chloration hydro-oxidation unit 8 and oxygen and is aoxidized under conditions of ruthenium-based catalyst acts on, temperature is 450 DEG C
Reaction obtains chlorine, after chlorine feeding chlorine mixer 9 is mixed with raw material chlorine, is sent into methane chlorination unit 3 and participates in chlorine
Change reaction.
Embodiment 5
The technique of the present embodiment the following steps are included:
Step 1: raw natural gas is sent into natural gas separative unit 1 with the flow of 100t/h, make methane and other hydro carbons
Separation, obtains thick methane and is sent into methane purifying unit 2 being purified to obtain the methane that sulfur content is 0.03ppm, then by first
Alkane is sent into methane chlorination unit 3 and chlorine and carries out chlorination reaction under conditions of temperature is 300 DEG C, generates chlorizate, then will
Chlorizate is sent into chlorizate separative unit 4 and is separated, and monochloro methane, hydrogen chloride and unreacted methane are obtained, will not
The methane of reaction is back in methane chlorination unit 3 and continues to participate in chlorination reaction；The detailed process of the purification are as follows: first by thick first
Alkane carries out hydroconversion reactions under conditions of temperature is 300 DEG C, and it is anti-that desulfurization is then carried out under conditions of temperature is 300 DEG C
It answers；
Step 2: monochloro methane obtained in step 1 is sent into alkene preparation unit 5, urged in silicoaluminophosphamolecular molecular sieves
Agent acts on, is converted into low-carbon alkene under conditions of 350 DEG C, is then fed into dehydrochlorination unit 6 and removes hydrogen chloride, obtains chlorine
Change hydrogen and hydrocarbon product, then hydrocarbon product feeding separation of hydrocarbons unit 10 is separated, obtains ethylene and propylene；
Step 3: hydrogen chloride obtained in hydrogen chloride, step 2 obtained in step 1 is sent into hydrogen chloride mixer 7
After mixing, it is sent into chloration hydro-oxidation unit 8 and oxygen and is aoxidized under conditions of ruthenium-based catalyst acts on, temperature is 400 DEG C
Reaction obtains chlorine, after chlorine feeding chlorine mixer 9 is mixed with raw material chlorine, is sent into methane chlorination unit 3 and participates in chlorine
Change reaction.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (4)
1. a kind of system using natural gas as raw material through chloromethanes alkene, which is characterized in that including passing sequentially through pipeline connection
Natural gas separative unit (1), methane purifying unit (2), methane chlorination unit (3) and chlorizate separative unit (4), it is described
Natural gas separative unit (1) has raw natural gas entrance (11), and methane purifying unit (2) has thick methane entrance (12), institute
It states thick methane entrance (12) to be connected with the outlet of natural gas separative unit (1), the methane chlorination unit (3) has purification methane
Entrance (13), mixing chlorine inlet (23) and unreacted methane entrance (24), the purification methane entrance (13) with it is methane purifying
The outlet of unit (2) is connected, and the unreacted methane entrance (24) is connected with the outlet of chlorizate separative unit (4), described
Chlorizate separative unit (4) has chlorizate entrance (14), monochloro methane outlet (15) and methane chlorination by-product hydrogen chloride
It exports (18), the chlorizate entrance (14) is connected with the outlet of methane chlorination unit (3), and monochloro methane exports (15) and alkene
The entrance of hydrocarbon preparation unit (5) is connected, and methane chlorination by-product hydrogen chloride outlet (18) is connected with hydrogen chloride mixer (7)；
The alkene preparation unit (5) passes sequentially through pipeline and connect with dehydrochlorination unit (6) and separation of hydrocarbons unit (10), institute
It states dehydrochlorination unit (6) and prepares product inlet (16) with alkene and alkene prepares by-product hydrogen chloride and exports (17), the alkene
Hydrocarbon prepares product inlet (16) and is connected with the outlet of alkene preparation unit (5), and the alkene prepares by-product hydrogen chloride outlet (17)
It is connected with hydrogen chloride mixer (7), the separation of hydrocarbons unit (10) is with alkene prepares hydrocarbon product entrance (25), ethylene goes out
Mouth (26) and propylene outlet (27), the alkene prepare hydrocarbon product entrance (25) and are connected with the outlet of dehydrochlorination unit (6)；
The hydrogen chloride mixer (7) by pipeline successively with chloration hydro-oxidation unit (8), chlorine mixer (9) and methane chlorine
Change unit (3) to be connected, chloration hydro-oxidation unit (8) has mixed chlorinated hydrogen entrance (19) and raw material oxygen intake (20), described
Mixed chlorinated hydrogen entrance (19) is connected with the outlet of hydrogen chloride mixer (7), and chlorine mixer (9) has regeneration chlorine inlet
(21) and raw material chlorine inlet (22), regeneration chlorine inlet (21) is connected with the outlet of chloration hydro-oxidation unit (8), described
The mixing chlorine inlet (23) of methane chlorination unit (3) is connected with the outlet of chlorine mixer (9).
2. a kind of utilize the work described in claim 1 for preparing alkene through the system of chloromethanes alkene using natural gas as raw material
Skill, which is characterized in that the technique the following steps are included:
Step 1: raw natural gas is sent into natural gas separative unit (1), makes methane and other separation of hydrocarbons, obtain thick first
Alkane and be sent into methane purifying unit (2) carry out purification be purified methane, then will purification methane be sent into methane chlorination unit (3)
Chlorination reaction is carried out with chlorine, generates chlorizate, then chlorizate feeding chlorizate separative unit (4) is separated,
Monochloro methane, hydrogen chloride and unreacted methane are obtained, unreacted methane is back in methane chlorination unit (3) and continues to join
With chlorination reaction；
Step 2: monochloro methane obtained in step 1 is sent into alkene preparation unit (5), it is converted under the action of catalyst
Low-carbon alkene is then fed into dehydrochlorination unit (6) and removes hydrogen chloride, obtains hydrogen chloride and hydrocarbon product, then hydro carbons is produced
Object is sent into separation of hydrocarbons unit (10) and is separated, and ethylene and propylene are obtained；
It is mixed Step 3: hydrogen chloride obtained in hydrogen chloride, step 2 obtained in step 1 is sent into hydrogen chloride mixer (7)
After conjunction, it is sent into chloration hydro-oxidation unit (8) and oxygen carries out oxidation reaction and obtains regeneration chlorine, regeneration chlorine is sent into chlorine and is mixed
After clutch (9) is mixed with raw material chlorine, it is sent into methane chlorination unit (3) and participates in chlorination reaction.
3. technique according to claim 2, which is characterized in that the detailed process of purification described in step 1 are as follows: first will be thick
Methane carries out hydroconversion reactions under conditions of temperature is 220 DEG C~500 DEG C, the item for being then 250 DEG C~400 DEG C in temperature
Desulphurization reaction is carried out under part, the sulfur content in the methane is 0.1ppm or less；The temperature of chlorination reaction described in step 1 is
180 DEG C~450 DEG C；Monochloro methane described in step 2 be converted under the action of catalyst low-carbon alkene temperature be 300 DEG C~
500℃；The temperature of oxidation reaction described in step 3 is 300 DEG C~450 DEG C.
4. technique according to claim 3, which is characterized in that the detailed process of the purification are as follows: first by thick methane in temperature
Degree carries out hydroconversion reactions under conditions of being 350 DEG C, then carries out desulphurization reaction under conditions of temperature is 350 DEG C；It is described
The temperature of chlorination reaction is 450 DEG C；The temperature that the monochloro methane is converted into low-carbon alkene under the action of catalyst is 450 DEG C；
The temperature of the oxidation reaction is 350 DEG C.
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| WO2024082393A1 (en) * | 2022-10-21 | 2024-04-25 | 上海科技大学 | Method for efficient conversion of hydrocarbon raw materials and device thereof |
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