CN108929191A - The technique and device of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes - Google Patents
The technique and device of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes Download PDFInfo
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- CN108929191A CN108929191A CN201810689840.1A CN201810689840A CN108929191A CN 108929191 A CN108929191 A CN 108929191A CN 201810689840 A CN201810689840 A CN 201810689840A CN 108929191 A CN108929191 A CN 108929191A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
- C01B7/0725—Purification ; Separation of hydrogen chloride by adsorption by active carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses the techniques and device of a kind of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes.Saturation hydrogen chloride of the hydrogen chloride gas with pressure that methylchlorosilane is hydrolyzed through hydrogen chloride-methanol solution washing, carbon fiber adsorption and catalytic combustion joint processing technology remove silicon-containing compound therein.Hydrogen chloride gas after purification is sent into chloromethanes synthesis reactor by graphite injector with preheated methanol liquid and synthesizes chloromethanes.Synthetic product enters cooler after demister, and gas-liquid mixture after cooling fully enters chloromethanes water wash system.Present invention reduces the adverse effects that impurity in methylchlorosilane hydrolysis hydrogen chloride synthesizes chloromethanes, take full advantage of synthesising reacting heat, have simplified technique, improve chloromethanes synthesis reactor space-time yield and chloromethanes yield, waste acid quantity is reduced, it is energy-saving, there are significant economic benefit and environmental benefit.
Description
Technical field
The invention belongs to chloromethanes synthesis technical fields, and in particular to be closed to a kind of using methylchlorosilane hydrolysis hydrogen chloride
At the technique and device of chloromethanes.
Background technique
There are three types of industrial process, i.e. by-product absorption method, methane chlorination methods, methanol hydrogen chloride method for chloromethanes.Glyphosate
Etc. a large amount of chloromethanes of production processes by-product, by-product chloromethanes entrainment impurity it is more.Methane chlorination method is that methane and chlorine exist
Chlorination is carried out under 400 DEG C of high temperature, generates chloromethanes and polychloride, single methane chloride production do not have to this method generally.Methanol
Chlorination religious services or rituals mixes hydrogen chloride and methanol in proportion, synthesizes chloromethanes under certain temperature and pressure, wherein being divided into gas phase again
The non-catalytic method of catalysis method, liquid catalytic, liquid phase.Gas-phase catalysis catalyst is activated alumina, liquid catalytic catalyst
For liquor zinci chloridi, the non-catalytic method of liquid phase does not use catalyst.It is chloromethanes that organic silicon monomer, which produces one of primary raw material, is come
There are two types of source is general, one is will utilize after glyphosate byproduct chloromethane reclaiming clean, another kind is using synthesis chloromethanes, more
More is synthesized using methanol hydrogen chloride method.There are two types of come for one of raw material using methanol hydrogen chloride method synthesis chloromethanes hydrogen chloride
Source, first is that hydrochloric acid is desorbed to obtain hydrogen chloride gas, second is that the hydrogen chloride gas with pressure hydrolyzed using dimethyldichlorosilane
Body.Organosilicon enterprise is suitble to the production technology of oneself according to the mating use of own device.Using dimethyldichlorosilane hydrolysis
Hydrogen chloride as raw material when its entrainment silane can be crosslinked under catalytic condition, the structural body of generation blocking pipeline and equipment,
Force device cannot long-term continuous operation, such as make chloromethanes synthesizer ability decline, reaction efficiency reduction is forced replacement catalysis
Agent, graphite cooler effect are deteriorated, and exchange heat blockage, the situations such as washing tower packing blocking.
Methanol hydrogen chloride method reaction principle: CH3OH+HCl=CH3Cl+H2O
Side reaction is: 2CH3OH=(CH3)2O+H2O
Reaction is step 1: 2CH3OH=(CH3)2O+H2O
Reaction is step 2: (CH3)2O+2HCl=2CH3Cl+2H2O
Dehydration esterification exothermic reaction, reaction heat 30.8kj/ occur under zinc chloride catalytic action for hydrogen chloride and methanol
Gmol chloromethanes (298.15k).The reaction is reversible reaction, increases the concentration of reactant, reacts thermal evaporation and removes reaction product
And water, carry out reaction to the right.For maintaining reaction temperature, Normal practice is led in reactor peripheral hardware collet, collet in production
Enter circulating water, or carries out extracorporal circulatory system in reactor peripheral hardware heating cooler and control reaction temperature, or by synthesis gas
Condensate liquid is back to synthesis reactor cooling by condensation, and certain heat can be lost by passing through heat exchange method in this way, and reaction heat cannot be by
The complex process equipment for making full use of, and needing.Catalysis method is synthesized because methyl ether selectivity is as reaction system methanol partial pressure is incremented by,
Therefore chlorination excess hydrogen is used to inhibit the selectivity of methyl ether, but can generate a large amount of alcohol-containing dilute hydrochloric acid.
Chinese patent CN1515528A discloses a kind of pressure synthesis process for refining of monochloro methane, using liquid catalytic
Methanol and hydrogen chloride are closed under 0.05-0.25MPa pressure 140-170 DEG C in the tank reactor equipped with catalyst in proportion
At monochloro methane, and using the dimethyl ether of concentrated sulfuric acid washing removing remaining moisture content and reaction by-product, the chlorine after purified drying
Methane gas obtains the monochloro methane product of high-purity by compression, condensation.The invention methanol and hydrogen chloride divide after overflash
It drives material into, by the extracorporal circulatory system of material, avoids reaction kettle and generate quenching, shock heating phenomenon, extend the service life of reaction kettle.
But the invention need to remove reaction solution through kettle external heat exchanger by circulating pump or additional heat, and the reactant of synthesis reactor out is passed through
Condenser condensation portion water and methanol are back to the temperature that reaction kettle adjusts reaction kettle to gas-liquid separator, by separator, therefore work
Skill stream and equipment are more, complicated for operation, and operating parameter easily fluctuates in kettle.Gas-phase methanol and hydrogen chloride are separately fed, two kinds of raw materials
It is difficult to be uniformly mixed in synthesis reactor, influences reaction efficiency.
Chinese patent CN101429093A discloses the energy-saving processing technique that a kind of liquid catalytic prepares monochloro methane, with
Liquor zinci chloridi is that catalyst, chloromethanes and methanol react in the reactor.Wherein gas phase chlorination hydrogen or gas phase chlorination hydrogen with
Gas-phase methanol of the part after the gasification of methyl alcohol vaporizing device is mixed into reactor, part or all of methanol with liquid phase state directly into
Enter reactor participation to react, starts to be passed through Liquid Phase Methanol when 150-160 DEG C of temperature in reactor, reaction product enters gas-liquid separation
After tank, liquid-phase reflux to reactor, gas phase removes pickling tower.The invention does not have to kettle outer circulation cooling and saves pump electric energy and recirculated water
Consumption, energy-saving effect are obvious.In the technical foundation that existing liquid phase method prepares chloromethanes, whole gas-phase feed modes are changed to portion
Divide liquid phase feeding, the method that reaction temperature is controlled by Liquid Phase Methanol, therefore suddenly cold and hot phenomenon can be generated to avoid reactor.
But the invention methanol liquid is fed alone all the way, is bound to cause in reactor and hydrogen chloride contact is uneven, inside reactor
Structure is complicated or agitating device is needed to can be only achieved mixed effect.Reactant leads to part reaction product by knockout drum
Condensation, liquid phase are back to reactor again, and part reaction product is caused to enter synthesis reactor, inhibit positive reaction.Reaction product 150-160
DEG C it is directly entered pickling tower, pickling tower excessive temperature differentials will certainly be made, material requires high, service life section.Liquid methanol needs to synthesize
The temperature that kettle reaches certain can be just passed through, and cause unnecessary energy consumption, or need the frequent switching factors such as cause system unstable.
Chinese patent CN102153439A discloses a kind of production technology of high-purity methane chloride, methanol and hydrogen chloride warp
Enter the reactor equipped with aluminium oxide catalyst after gasification, monochloro methane, methane, chloroethanes, dichloromethane are generated in reactor
The mixture of alkane；The mixture of generation enters chiller through dilute hydrochloric acid Quench to 50-100 DEG C, and pickling tower, alkali cleaning are entered after separation
Thick monochloro methane is made in tower, sulfuric acid drying system after compression；It is isolated that thick monochloro methane enters the progress of monochloro methane treating column
Single-minded chloromethanes.Monochloro methane content can be made greater than 99.98% in this technique.But reaction temperature and pressure are high, want to equipment
Ask high, byproduct of reaction is more, also rectifying column is needed further to refine.
Chinese patent CN106008151A discloses a kind of synthetic method of chloromethanes.Hydrochloric acid is directly mixed with methanol,
Chloromethanes is directly synthesized in the reaction solution of methanol, hydrogen chloride and water composition.Reactant enters rectifying column, the chlorine of the top of the distillation column
Methane is dried to obtain chloromethanes product through persulfuric acid.Wherein the molar ratio of methanol and chloride is 1-1.7:1, and mixture exists
0.15-1.0MPa, 100-150 DEG C under catalysts conditions without reacting.The invention, as raw material, is reduced using the hydrochloric acid of 10-40%
Hydrochloric acid desorbs the technical process of hydrogen chloride gas, but needs more heat by water evaporation containing a large amount of water inside hydrochloric acid, and
Reduce the contact probability of methanol and hydrogen chloride, reaction efficiency is low, and energy consumption is high.Methanol is excessive, and side reaction product dimethyl ether is more,
Subsequent sulphuric acid consumption is big.The additional hot systems of reactor, complex process.
Summary of the invention
The present invention develops a kind of hydrogen chloride synthesis chlorine with pressure hydrolyzed using methylchlorosilane against the above technical problems
The technique of methane, the specific steps are as follows:
The methanol of methanol tank is squeezed into absorption tower tower reactor to 40-60% liquid level by methanol feed pump, closes inlet valve.Starting
Absorption tower circulating pump squeezes into tower reactor methanol loop at the top of absorption tower.Hydrogen chloride gas with pressure is from methylchlorosilane hydrolyzing process
Enter absorb the bottom of the tower by pipeline, methanol absorption hydrogen chloride gas gradually forms methanol-hydrogen chloride saturated solution.Absorb tower top
The hydrogen chloride gas that portion comes out adsorbs remaining organo-silicon compound, activated carbon fibre absorber bottom through activated carbon fibre absorber
Liquid phase gravity flow in portion's, which enters, absorbs tower bottoms phase region.Methanol feed pump by methanol feeding methanol preheater be preheated to 40-60 DEG C with from
The hydrogen chloride gas molar ratio that activated carbon fibre absorber comes is by hydrogen chloride: methanol=0.95-1.019:1 is through graphite injector
It is mixed into synthesis reactor gas-liquid distributor and carries out reaction generation chloromethanes in catalyst solution.The mixture of synthesis is through synthesis reactor
Enter chloromethanes cooler after the demister of top, the mixture of synthesis is cooled to by 70-100 DEG C of entrance using 50-70 DEG C of hot water
Chloromethanes water scrubber washes the alcohol-containing olefin(e) acid concentration 15-20% that tower reactor obtains, wherein methanol content≤2%.Chloromethanes is from washing
Top of tower enters after-purification system.
From silicon containing low molecule in the hydrogen chloride gas pressure 0.15-0.3MPa (G) of methylchlorosilane hydrolyzing process, hydrogen chloride
Oxygen alkane, organochlorosilane, water, content of impurities 2000-3000ppm.
Absorption tower outer circulation is equipped with heat exchanger, is exchanged heat using 3-8 DEG C of chilled water, and scrubbing tower temperature is controlled at 20-35 DEG C.
Methanol loop amount is the 1%-5% of hydrogen chloride feed volume.Being saturated hydrogen chloride solubility in methanol-hydrogen chloride solution is 40-
50g/100g methanol.
Fresh methanol all the way is set at the top of absorption tower and adds pipeline, and methanol-hydrogen chloride solution all the way is set after the circulating pump of absorption tower
Pipeline, methanol intermittent injecting are produced, methanol-hydrogen chloride solution interval produces.Methanol additional amount and methanol-hydrogen chloride produced quantity matter
Amount is than being 1:1.5-2.
Hydrogen chloride gas after activated carbon fibre absorber, inhale from absorb the bottom of the tower, activated carbon fibre is flowed by bottom liquid phases
The 0.5-1m water seal that sets communicating pipe for receiving device bottom to scrubbing tower avoids gas phase from falling to go here and there, and sets whether pipeline viewing mirror observation liquid stream leads to
Freely.Organo-silicon compound content is less than 20ppm in hydrogen chloride gas after activated carbon fibre absorber.
Chloromethanes synthesis reactor temperature is 135-155 DEG C, pressure 0.13-0.25MPa (G).70- is housed in synthesis reactor
80wt%, the preferably liquor zinci chloridi of 75wt% drive initial stage as catalyst, and catalyst is added by external circulation heating system
After heat to reaction temperature, stop heating, subsequent hydrogen chloride, methanol composition gas-liquid mixture enter reactor that heat release occurs be anti-
It answers.Gas phase reaction area and blistering reaction area height ratio are 1:1-1.05, and blistering reaction area height 2-3m.Make methanol and hydrogen chloride
There are enough reaction compartments and time.
According to process described above step, technical solution of the present invention also provides a kind of methylchlorosilane hydrolysis hydrogen chloride
Synthesize the device of chloromethanes.Specially methanol tank is connect with absorption tower top and methanol preheater respectively, methylchlorosilane hydrolysis
Hydrogen chloride connect with absorption tower lower part；
Methanol preheater is connected to graphite injector through converging at the top of pipeline and absorption tower through pipeline；
Graphite injector is connect with synthesis reactor, and synthesis reactor is connected to water scrubber after connecting with top with chloromethanes cooler,
Chloromethanes purification system is connected at the top of water scrubber.
The absorb the bottom of the tower is connect through circulating pump with cooler, and cooler is connected to absorption tower top.
It is connect again with graphite injector after being connect at the top of the absorption tower with activated carbon fibre absorber；Activated carbon fibre
Absorber bottom is connect through pipeline with absorption tower lower part.
The methanol preheater is connect through pipeline with chloromethanes cooler, and chloromethanes cooler is preheated through pipeline and methanol
Device connection, forms circulation loop.
The invention has the characteristics that:
1, hydrogen chloride gas with pressure is hydrolyzed using methylchlorosilane and synthesizes chloromethanes, raw material is easy to get, without desorbing hydrochloric acid
Process and the conveying of hydrogen chloride Additional pressurizations.
2, using the silicon-containing compound and other organic impurities in methanol absorption hydrogen chloride, methanol and the siliceous chemical combination with chlorine
Object can generate silicon alcohol compound with hydrolysis.Organic compound can be absorbed and be dissolved by methanol, will not to chloromethanes synthesis
Bring new impurity.Impurity in chloromethanes can be down to 20ppm, improve chloromethanes synthesis efficiency, reduce equipment and
Line clogging probability.
3, the catalyst of synthesis reactor is heated to being passed through the gas of hydrogen chloride and methanol after reaction temperature using outer circulation hot mode
Liquid mixture.Liquid Phase Methanol is vaporized in reaction kettle, while also absorbing reaction heat release, is cooled down without phegma, to save
The consumption of reactor cooling recirculated water or the power consumption of extracorporal circulatory system electromechanical equipment have been saved, energy saving purpose is reached.According to reaction machine
Reason, product remove in time, are conducive to improve to positive anti-rate and methyl chloride conversion rate, by-product diformazan ether content is lower.Generally
Hydrogen-chloride synthesis methyl chloride conversion rate 99.5% is hydrolyzed using methylchlorosilane, this technique methyl chloride conversion rate reaches
99.8% or more.
4, according to hydrogen chloride and methanol kinetics relationship, methanol and hydrogen chloride ratio have enough close to theoretical value
Gas-liquid contact time and space eliminate back reaction factor in time, and methanol conversion is high, and obtained waste hydrochloric acid is few.Common process
Every synthesis 1t chloromethanes averagely generates dilute hydrochloric acid of the 0.75t containing methanol, contains methanol 5% or so in dilute hydrochloric acid, and the every conjunction of this technique
0.35t alcohol-containing diluted acid is averagely produced at 1t chloromethanes, wherein methanol content is less than 2%.
5, the mixture of synthesis (contain methanol, hydrogen chloride, dimethyl ether, water, chloromethanes) is tentatively cooled to 80-100 DEG C, it is cold
Gas-liquid mixture after solidifying removes water scrubber, avoids the water scrubber temperature difference big, reduces to the requirement of scrubbing tower material, improves making for water scrubber
Use the service life.
6, reactor, which controls certain gas phase reaction area and sets demister in outlet, eliminates entrainment, and catalyst is retained
To reaction kettle, catalyst attrition is reduced, reactant condensation is also avoided to be mixed into reaction kettle.
Detailed description of the invention
Fig. 1 is process flow chart of the invention, in which: 1, absorption tower；2, absorption tower circulating pump；3, absorber cooler；
4, activated carbon fibre absorber；5, methanol tank；6 methanol feed pumps；7, graphite injector；8, synthesis reactor；9, demister；10, chlorine
Methane cooler；11, water scrubber；12, methanol preheater；13, pipeline viewing mirror.
Specific embodiment:
Embodiment 1
A kind of device of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes, methanol tank respectively with absorption tower top and methanol
The hydrogen chloride of preheater connection, methylchlorosilane hydrolysis is connect with absorption tower lower part；
Methanol preheater is connected to graphite injector through converging at the top of pipeline and absorption tower through pipeline；
Graphite injector is connect with synthesis reactor, and synthesis reactor is connected to water scrubber after connecting with top with chloromethanes cooler,
Chloromethanes purification system is connected at the top of water scrubber.
The absorb the bottom of the tower is connect through circulating pump with cooler, and cooler is connected to absorption tower top.
It is connect again with graphite injector after being connect at the top of the absorption tower with activated carbon fibre absorber；Activated carbon fibre
Absorber bottom is connect through pipeline with absorption tower lower part.
The methanol preheater is connect through pipeline with chloromethanes cooler, and chloromethanes cooler is preheated through pipeline and methanol
Device connection, forms circulation loop.
Embodiment 2
In synthesis reactor 75% liquor zinci chloridi through external circulating system be heated to 135-140 DEG C it is spare.Methanol feed pump (6)
The methanol of methanol tank (5) is squeezed into absorption tower (1) to 60% liquid level of tower reactor, closes inlet valve.Start absorption tower circulating pump (2)
Tower reactor methanol is squeezed at the top of absorption tower through absorber cooler (3) circulation, from the 0.15MPa of methylchlorosilane hydrolyzing process
(G) impurity 2000ppm in hydrogen chloride gas enters absorption tower (1) bottom by pipeline, methanol absorption hydrogen chloride gas gradually shape
At hydrogen chloride-methanol saturated solution, methanol absorber tower cooler (3) is passed through chilled brine, controls 20 DEG C of temperature of absorption tower (1),
The solubility 40% of hydrogen chloride in methyl alcohol, absorption tower (1) circulation fluid volume are the 1% of hydrogen chloride feed volume.Absorption tower (1)
The hydrogen chloride gas that top comes out adsorbs remaining silicon-containing compound through activated carbon fibre absorber (4), obtains hydrogen chloride gas
Middle impurity content 10pmm, the gravity flow of activated carbon absorber bottom liquid phases enter absorption tower (1) tower reactor liquid phase region.Methanol feed pump (6)
Methanol is sent into the hydrogen chloride gas that methanol preheater (12) are preheated to 40-50 DEG C with come from activated carbon fibre absorber (4)
Molar ratio is by hydrogen chloride: methanol=0.99:1 is mixed into synthesis reactor (8) gas-liquid distributor through graphite injector (7), and catalysis is anti-
Chloromethanes should be generated.Synthesis reactor (8) gas phase reaction area and blistering reaction area height ratio are 1:1, and blistering reaction area height 2m, instead
135 DEG C of temperature are answered, pressure 0.13MPa (G).Reaction mixture removes the mists such as catalyst through synthesis reactor (8) top demister (9)
Into chloromethanes cooler (10), the mixture of synthesis is cooled to 70-75 DEG C using 50 DEG C of hot water and enters chloromethanes washing
Tower (11), 1 ton of chloromethanes of every synthesis, water scrubber (11) tower reactor obtain concentration 15wt% alcohol-containing olefin(e) acid 0.4t, wherein methanol content
1.5%, chloromethanes enters after-purification system, methyl chloride conversion rate 99.9% at the top of water scrubber.Production process interval is past to be absorbed
Tower (1) adds methanol, and hydrogen chloride-methanol solution interval of tower reactor produces.Methanol additional amount and methanol-hydrogen chloride produced quantity quality
Than for 1:1.5.
Embodiment 3
In synthesis reactor 75% liquor zinci chloridi through external circulating system be heated to 140-145 DEG C it is spare.Methanol feed pump (6)
The methanol of methanol tank (5) is squeezed into absorption tower (1) to 40% liquid level of tower reactor, closes inlet valve.Start absorption tower circulating pump (2)
Tower reactor methanol is squeezed at the top of absorption tower through absorber cooler (3) circulation, from the 0.3MPa (G) of methylchlorosilane hydrolyzing process
Impurity 3000ppm in hydrogen chloride gas enters absorption tower (1) bottom by pipeline, and methanol absorption hydrogen chloride gas gradually forms
Hydrogen chloride-methanol saturated solution, methanol absorber tower cooler (3) are passed through chilled brine, control 35 DEG C of temperature of absorption tower (1), chlorine
Change the solubility 50% of hydrogen in methyl alcohol, absorption tower (1) circulation fluid volume is the 5% of hydrogen chloride feed volume.Absorption tower (1) top
The hydrogen chloride gas that portion comes out adsorbs remaining silicon-containing compound through activated carbon fibre absorber (4), obtains in hydrogen chloride gas
Impurity content 15pmm, the gravity flow of activated carbon absorber bottom liquid phases enter absorption tower (1) tower reactor liquid phase region.Methanol feed pump (6) will
Methanol feeding methanol preheater (12) is preheated to 50-60 DEG C and rubs with the hydrogen chloride gas to come from activated carbon fibre absorber (4)
That ratio is by hydrogen chloride: methanol=1:1 is mixed into synthesis reactor (8) gas-liquid distributor through graphite injector (7), and catalysis reaction generates
Chloromethanes.Synthesis reactor (8) gas phase reaction area and blistering reaction area height ratio are 1:1.05, and blistering reaction area height 3m, reaction
155 DEG C of temperature, pressure 0.25MPa (G).Reaction mixture through synthesis reactor (8) top demister (9) remove the mists such as catalyst into
Enter chloromethanes cooler (10), the mixture of synthesis is cooled to 100 DEG C using 60-70 DEG C of hot water and enters chloromethanes water scrubber
(11), 1 ton of chloromethanes of every synthesis, the concentration 16wt% alcohol-containing olefin(e) acid 0.35t that water scrubber (11) tower reactor obtains wherein methanol content
2%, chloromethanes enters after-purification system, methyl chloride conversion rate 99.9% at the top of water scrubber.The past absorption tower of production process interval
(1) methanol is added, hydrogen chloride-methanol solution interval of tower reactor produces.Methanol additional amount and methanol-hydrogen chloride produced quantity mass ratio
For 1:2.
Embodiment 4
In synthesis reactor 75% liquor zinci chloridi through external circulating system be heated to 145-150 DEG C it is spare.Methanol feed pump (6)
The methanol of methanol tank (5) is squeezed into absorption tower (1) to 60% liquid level of tower reactor, closes inlet valve.Start absorption tower circulating pump (2)
Tower reactor methanol is squeezed at the top of absorption tower through absorber cooler (3) circulation, from the 0.18MPa of methylchlorosilane hydrolyzing process
(G) impurity 2500ppm in hydrogen chloride gas enters absorption tower (1) bottom by pipeline, methanol absorption hydrogen chloride gas gradually shape
At hydrogen chloride-methanol saturated solution, methanol absorber tower cooler (3) is passed through chilled brine, controls 35 DEG C of temperature of absorption tower (1),
The solubility 40% of hydrogen chloride in methyl alcohol, absorption tower (1) circulation fluid volume are the 3% of hydrogen chloride feed volume.Absorption tower (1)
The hydrogen chloride gas that top comes out adsorbs remaining silicon-containing compound through activated carbon fibre absorber (4), obtains hydrogen chloride gas
Middle impurity content 20pmm, the gravity flow of activated carbon absorber bottom liquid phases enter absorption tower (1) tower reactor liquid phase region.Methanol feed pump (6)
Methanol is sent into the hydrogen chloride gas that methanol preheater (12) are preheated to 55-60 DEG C with come from activated carbon fibre absorber (4)
Molar ratio is by hydrogen chloride: methanol=0.95:1 is mixed into synthesis reactor (8) gas-liquid distributor through graphite injector (7), and catalysis is anti-
Chloromethanes should be generated.Synthesis reactor (8) gas phase reaction area and blistering reaction area height ratio are 1:1.05, and blistering reaction area height
3m, 140 DEG C of reaction temperature, pressure 0.15MPa (G).Reaction mixture removes catalyst through synthesis reactor (8) top demister (9)
Equal mists enter chloromethanes cooler (10), and the mixture of synthesis is cooled to 100 DEG C using 65-70 DEG C of hot water and enters chloromethane
Alkane water scrubber (11) synthesizes one ton of chloromethanes, and water scrubber (11) tower reactor obtains concentration 17wt% alcohol-containing olefin(e) acid 0.3t, wherein methanol
Content 1.5%, chloromethanes enter after-purification system, methyl chloride conversion rate 99.8% at the top of water scrubber.Production process interval is past
Methanol is added on absorption tower (1), and hydrogen chloride-methanol solution interval of tower reactor produces.Methanol additional amount and methanol-hydrogen chloride produced quantity
Mass ratio is 1:2.
Embodiment 5
In synthesis reactor 75% liquor zinci chloridi through external circulating system be heated to 150-160 DEG C it is spare.Methanol feed pump (6)
The methanol of methanol tank (5) is squeezed into absorption tower (1) to 50% liquid level of tower reactor, closes inlet valve.Start absorption tower circulating pump (2)
Tower reactor methanol is squeezed at the top of absorption tower through absorber cooler (3) circulation, from the 0.2MPa (G) of methylchlorosilane hydrolyzing process
Impurity 2500ppm in hydrogen chloride gas enters absorption tower (1) bottom by pipeline, and methanol absorption hydrogen chloride gas gradually forms
Hydrogen chloride-methanol saturated solution, methanol absorber tower cooler (3) are passed through chilled brine, control 20 DEG C of temperature of absorption tower (1), chlorine
Change the solubility 50% of hydrogen in methyl alcohol, absorption tower (1) circulation fluid volume is the 2% of hydrogen chloride feed volume.Absorption tower (1) top
The hydrogen chloride gas that portion comes out adsorbs remaining silicon-containing compound through activated carbon fibre absorber (4), obtains in hydrogen chloride gas
Impurity content 15pmm, the gravity flow of activated carbon absorber bottom liquid phases enter absorption tower (1) tower reactor liquid phase region.Methanol feed pump (6) will
Methanol feeding methanol preheater (12) is preheated to 45-55 DEG C and rubs with the hydrogen chloride gas to come from activated carbon fibre absorber (4)
That ratio is by hydrogen chloride: methanol=1.019:1 is mixed into synthesis reactor (8) gas-liquid distributor, catalysis reaction through graphite injector (7)
Generate chloromethanes.Synthesis reactor (8) gas phase reaction area and blistering reaction area height ratio are 1:1.05, and blistering reaction area height
2.5m, 145 DEG C of reaction temperature, pressure 0.18MPa (G).Reaction mixture is removed through synthesis reactor (8) top demister (9) and is catalyzed
The mists such as agent enter chloromethanes cooler (10), and the mixture of synthesis is cooled to 95 DEG C using 70 DEG C of hot water and enters chloromethanes
Water scrubber (11), water scrubber (11) tower reactor every synthesis obtained concentration 15wt% alcohol-containing olefin(e) acid 0.3t of one ton of chloromethanes, wherein first
Alcohol content 2%, chloromethanes enter after-purification system, methyl chloride conversion rate 99.8% at the top of water scrubber.Production process interval is past
Methanol is added on absorption tower (1), and hydrogen chloride-methanol solution interval of tower reactor produces.Methanol additional amount and methanol-hydrogen chloride produced quantity
Mass ratio is 1:2.
Claims (10)
1. the technique of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes, which comprises the steps of:
(1) methanol self-absorption tower top spray enters, and when liquid level is to 40-60%, closes inlet valve, starting absorption tower circulating pump will
Tower reactor methanol loop squeezes into absorption tower top；
(2) hydrogen chloride gas that methylchlorosilane hydrolyzing process comes out enters absorption tower lower part, methanol absorption chlorination by pipeline
Hydrogen produces after obtaining methanol-hydrogen chloride saturated solution, while adding methanol；
(3) enter conjunction after graphite injector mixes with from unabsorbed hydrogen chloride gas in step (2) after methanol is preheated
At kettle, reaction generates chloromethanes under the effect of the catalyst, through demisting, be cooled to 80-100 DEG C enter chloromethanes water scrubber and after
Purification system, the i.e. technique of completion methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes.
2. the technique of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes described in claim 1, which is characterized in that step (2)
In
Hydrogen chloride gas pressure 0.15-0.3MPa(G), low molecular weight polyorganosiloxane, organochlorosilane, water are contained in hydrogen chloride gas, it is miscellaneous
Matter total content 2000-3000ppm.
3. the technique of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes described in claim 1, which is characterized in that step (2)
In, use 3-8 DEG C of chilled water to exchange heat to tower temperature in the kettle as 20-35 DEG C outside absorption tower；Methanol loop amount is hydrogen chloride body of feedstock
Long-pending 1%-5% makes to be saturated hydrogen chloride solubility control 40-50g/100g methanol in methanol-hydrogen chloride solution；The methanol
Additional amount and methanol-hydrogen chloride produced quantity mass ratio are 1:1.5-2.
4. the technique of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes as claimed in claim 2, which is characterized in that step (3)
The middle preheated device of methanol is preheated to 40-60 DEG C；Unabsorbed hydrogen chloride gas is before entering graphite injector through work in step (2)
Property Carbon fibe absorber absorb after, organo-silicon compound content be less than 20ppm.
5. the technique of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes described in claim 1, which is characterized in that step (3)
The molar ratio of middle methanol and hydrogen chloride is 1:0.95-1.019；The catalyst is zinc chloride, and the mass concentration of zinc chloride is
70-80%。
6. the technique of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes described in claim 1, which is characterized in that step (3)
Middle synthesis temperature in the kettle control is 135-155 DEG C, and pressure control is 0.13-0.25MPa in synthesis reactor；In reaction process, synthesis
Gas phase reaction area and blistering reaction area are formed in kettle, wherein gas phase reaction area and blistering reaction area height ratio are 1:1-1.05.
7. used by the technique for realizing methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes described in any one of claims 1-6
Device, which is characterized in that
Methanol tank is connect with absorption tower top and methanol preheater respectively, the hydrogen chloride of methylchlorosilane hydrolysis and absorption tower lower part
Connection；
Methanol preheater is connected to graphite injector through converging at the top of pipeline and absorption tower through pipeline；
Graphite injector is connect with synthesis reactor, and synthesis reactor is connected to water scrubber after connecting with top with chloromethanes cooler, washing
Top of tower is connected to chloromethanes purification system.
8. the device of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes as claimed in claim 7, which is characterized in that absorption tower bottom
Portion is connect through circulating pump with cooler, and cooler is connected to absorption tower top.
9. the device of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes as claimed in claim 7, which is characterized in that absorb tower top
Portion is connect with graphite injector again after connecting with activated carbon fibre absorber；Activated carbon fibre absorber bottom is through pipeline and absorbs
The connection of tower lower part.
10. the device of methylchlorosilane hydrolysis hydrogen chloride synthesis chloromethanes as claimed in claim 7, which is characterized in that methanol is pre-
Hot device is connect through pipeline with chloromethanes cooler, and chloromethanes cooler is connect through pipeline with methanol preheater, forms circulation loop.
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| CN115945144A (en) * | 2023-02-10 | 2023-04-11 | 山东东岳有机硅材料股份有限公司 | Methyl chloride synthesis and siloxane recovery device and method for organic silicon |
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