CN101538205B - Process system and method for continuously preparing long chain alkyl dimethyl tertiary amine - Google Patents
Process system and method for continuously preparing long chain alkyl dimethyl tertiary amine Download PDFInfo
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- CN101538205B CN101538205B CN200810085073A CN200810085073A CN101538205B CN 101538205 B CN101538205 B CN 101538205B CN 200810085073 A CN200810085073 A CN 200810085073A CN 200810085073 A CN200810085073 A CN 200810085073A CN 101538205 B CN101538205 B CN 101538205B
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to the technical field of preparing a compound, namely long chain alkyl dimethyl tertiary amine, and in particular relates to a process system and a method for continuously preparing long chain alkyl dimethyl tertiary amine. The invention provides the process system for continuously preparing the long chain alkyl dimethyl tertiary amine by taking a fixed bed reactor as basic characteristic, and uses the system, fatty alcohol and dimethylamine as raw materials to continuously prepare the long chain alkyl dimethyl tertiary amine via a catalytic dehydrogenation amination reaction in reductive hydrogen atmosphere. The process for producing the long chain alkyl dimethyl tertiary amine by the system and the method is continuous and stable, and the process condition is easily controlled; the system and the method avoid frequent stoppage of an intermittent production device, and have high utilization rate of heat recovery and low energy consumption; and the production process is long-term closed operation, and effectively avoids environmental pollution caused by dimethylamine escape.
Description
Technical field
The invention belongs to the technical field of preparation compound long chain alkyl dimethyl tertiary amine, the process system and the method for particularly continuous preparation long chain alkyl dimethyl tertiary amine.
Background technology
Use Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline to carry out the research that the catalytic dehydrogenation amination reaction prepares tertiary amine and start from the thirties in last century (E.J.Schwoegler, et al.Preparation of certain amines [J] .JAOCS, 1939,61:3499～3502.) as raw material.Document by delivering at that time sees that the tertiary amine selectivity is very low, and industrialized value is far from.Up to the sixties in last century, the technology of fatty alcohol catalyzing amination system tertiary amine does not also reach the level of practical application.The seventies in the last century later stage and the beginning of the eighties in last century; Use Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline to make progress as the catalyst research that raw material carries out catalytic dehydrogenation amination reaction generation long chain alkyl dimethyl tertiary amine; Many documents and materials have been delivered about Preparation of Catalyst; The catalyst activity component has Cu-Co (Bowman R C1Method ofproducing amines [P] .US:4806690; 1989～02～21.), Cu-Ni, Cu-Cr-Ba (Baiker A.Catalytic amination of aliphatic alcohols.The role of hydrogen as inhibitor for catalyst deactivation [J] .Ind Eng Chem ProdRes Dev, 1981; 20:615～618.), Cu-Mo, Cu-W (Slaugh I H.Verfahahren zurhestellung eines amines [P] .Ger offen; 2749064; 1978～05～18.), Cu-Sn-Na (Hubert H J, Klaus D Tillmetz; Olfen-Vinnum.Method for making amines [P] .US:4621158; 1986～11～04.), Cu-Zn-Ba (Pak Y Fong, Kim R Smith; Joe Dsacer.Amination for alcohols [P] .EP:4994620; 1991～02～19.) and Cu-Ni-Ba (ZdzislawWDuzinski.Amine compositions produced by catalytic alkylaion ofmethylamine by long chain alcohols [P] .US:4594455,1986～06～10.) etc., the kind of carrier has 13X molecular sieve, CaCO
3, (Baiker A.Catalytic amination of aliphaticalcohols.The role of hydrogen as inhibitor for catalyst deactivation [J] .Ind EngChem Prod Res Dev such as ZnO; 1981; 20:615～618.), catalyst performance has the Cu of German Hoecht company preferably
2-Cr, the Cu of Japanese Kao company
2Ni
2Cu, the Ni of Ba and Chinese daily use chemicals institute is the compound G20 catalyzer of quaternary on basis.
The process system of preparation long chain alkyl dimethyl tertiary amine and method thereof are with the German (H.Hoffmann of BASF AG; Et al.Basisches; Zur herstellung eines kupfer ethal2 tenden katalysators geeignetes carbonat [P] .Ger Offen:2445303; 1974～09～21.), German Hoechst (J.Strauss, et al.Process for the preparation of tertiary aliphatic amines [P] .US:4138437,1979～12～06.), Japanese Kao (the Kimura ocean. third stage ア シ ソ method for making [P] 1JP: clear 56-43; 248; 1981～04～21.) be representative, up to the present, the Fatty Alcohol(C12-C14 and C12-C18) of practical application and n n dimetylaniline generation catalytic dehydrogenation amination reaction; The process system and the method thereof of producing the long chain alkyl dimethyl tertiary amine are traditional stirred-tank reactor; Switzerland Biazzi company has from top to bottom axially suction, can the reaction kettle upper gas be sucked liquid phase, reach gas-solid liquid three-phase blended " self-priming " stirred-tank reactor through stirring action again; Three types of the loop spray reactor drums of Switzerland Buss company and the exploitation of Switzerland EC Chem company all belong to slurry intermittent type catalytic reaction system.The optimization processing condition of corresponding slurry batch reaction system receive the influence of catalyst performance and reactor types; The approximate range of main technologic parameters is: temperature of reaction is 180～250 ℃; Generally below 0.13MPa, the hydrogen dividing potential drop is 40%～80% of a stagnation pressure to reaction pressure.
The seventies in the last century later stage and the beginning of the eighties in last century are the peak periods of fatty alcohol catalyzing amination technical development.From the later stage eighties in last century so far, both at home and abroad fatty alcohol catalyzing amination technology is in ripe plateau.The emphasis of technological development turns to the exploitation of through engineering approaches.
Summary of the invention
The purpose of this invention is to provide a kind of is the process system of the continuous preparation long chain alkyl dimethyl tertiary amine of essential characteristic with fixed-bed reactor.
It is essential characteristic with fixed-bed reactor that a purpose more of the present invention provides a kind of, is raw material with Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline, under reductive hydrogen atmosphere, prepares the method for long chain alkyl dimethyl tertiary amine continuously through the catalytic dehydrogenation amination reaction.
The process system of continuous preparation long-chain alkyl tertiary amine of the present invention comprises fixed-bed reactor, heat exchanger, well heater, gas-liquid separator, liquid liquid/gas separator, n n dimetylaniline gasification condensing surface, underpressure distillation separator, water condenser, mist trap, recycle compressor, watercooler, Fatty Alcohol(C12-C14 and C12-C18) pump, diformazan amine pump and hydrogen supply source gas line referring to Fig. 1, Fig. 2;
The discharge port of fixed-bed reactor bottom links to each other with the top hot-fluid opening for feed of heat exchanger through pipeline; The hot-fluid discharge port of heat exchanger bottom links to each other with the opening for feed of gas-liquid separator downside through pipeline; The liquid outlet opening of gas-liquid separator bottom links to each other with the opening for feed on liquid liquid/gas separator top through pipeline; The discharge port of liquid liquid/gas separator upper side links to each other or links to each other with the opening for feed of product storage tank with opening for feed with the underpressure distillation separator of heat-conducting oil heating through pipeline, and the discharge port of liquid liquid/gas separator downside passes through pipeline and links to each other with the opening for feed of water storage tank; The pneumatic outlet at underpressure distillation separator top links to each other with the opening for feed at external condensation device top through pipeline, and the discharge port of underpressure distillation separator bottom links to each other with the opening for feed of by product storage tank through pipeline; The liquid outlet opening of external condensation device bottom links to each other with smart product storage tank, and the non-condensable gas outlet on external condensation device top links to each other with vacuum pipe;
The pneumatic outlet at gas-liquid separator top links to each other with the gas feed at water condenser top through pipeline; The pneumatic outlet on water condenser top links to each other through the gas feed of pipeline with n n dimetylaniline gasification condenser overhead, and the pneumatic outlet on n n dimetylaniline gasification condensing surface top links to each other with the gas feed of mist trap upper side through pipeline; The liquid exit of water condenser, n n dimetylaniline gasification condensing surface and mist trap bottom all links to each other with the withdrawing fluid import of gas-liquid separator top-side through pipeline;
The pneumatic outlet at mist trap top links to each other with the import of recycle compressor through pipeline; The pneumatic outlet of recycle compressor links to each other with the gas feed at watercooler top through pipeline; The pneumatic outlet of watercooler bottom links to each other through the gas feed of pipeline with n n dimetylaniline gasification condensing surface lower side; The pneumatic outlet of n n dimetylaniline gasification condensing surface upper lateral part links to each other with the gas feed of heat exchanger lower side through pipeline, and the pneumatic outlet of heat exchanger upper lateral part links to each other with the gas feed at the well heater top of heat-conducting oil heating through pipeline;
The pneumatic outlet of heater base links to each other with the gas feed at fixed-bed reactor top through pipeline;
The liquid fat raw polyol is linked to each other with the gas feed pipeline of heat exchanger lower side through pipeline by the Fatty Alcohol(C12-C14 and C12-C18) pump discharge; The n n dimetylaniline raw material is linked to each other through the gas feed pipeline of pipeline with n n dimetylaniline gasification condensing surface lower side by the n n dimetylaniline pump discharge; Hydrogen source gas is supplied with source gas line through the hydrogen that decompression venting valve is installed and is linked to each other with the cycle gas pipe of recycle compressor pneumatic outlet.
The number of described fixed-bed reactor is 1～3, when the number of fixed-bed reactor during greater than 1, is to be connected in series through pipeline.
The material of described pipeline is a stainless steel.
Major equipment of the present invention is existing installation, and its principle performance is:
The fixed-bed reactor profile is a right cylinder, and the bottom in fixed-bed reactor is equipped with the porous catalyst bracing member, and reactor drum shaft sidewall is equipped with six temperature measuring gauges from top to bottom, is used for observation control, reaction process is stablized carried out effectively.
Heat exchanger, well heater, n n dimetylaniline gasification condensing surface, water condenser and watercooler are for the metal partition being the equipment of heat exchange between cold and hot two kinds of fluids of media.
Gas-liquid separator and underpressure distillation separator are to utilize the mixture different components, and relative volatility is different under differing temps, is impellent with heat energy; Directly carry out thermal exchange between material composition; Carry out the isolating equipment of material composition, can heat outward, the energy that supply needs.
The liquid liquid/gas separator is to utilize between the different liqs material immiscible and difference of specific gravity to carry out isolating equipment.
The continuous method for preparing long-chain alkyl tertiary amine of the present invention may further comprise the steps:
1) in fixed-bed reactor, fill porosu solid catalyzer with identical shaped size after, make each equipment of system be in health state;
2) hydrogen that is connected through the cycle gas pipe with the recycle compressor pneumatic outlet is supplied with source gas line and is given continuously the initial hydrogen of introducing 0.4～0.6MPa in the process system of preparation long chain alkyl dimethyl tertiary amine;
3) start recycle compressor, hydrogen is flowed along circulation loop in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously;
4) well heater feeds heat-conducting oil heating circulating hydrogen air-flow, makes the fixed-bed reactor temperature of reaction reach 210～250 ℃, and preferable reaction temperature is 225～250 ℃;
5) the Fatty Alcohol(C12-C14 and C12-C18) pipeline through linking to each other with the gas feed pipeline of heat exchanger lower side quantitatively injects C by the pump that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine
8-18Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed are 0.2～1.3h
-1(inlet amount (the m of the long chain alkyl dimethyl tertiary amine that in fixed-bed reactor, adds
3/ h)/catalytic amount (m
3)), be preferably 0.25～0.5h
-1The n n dimetylaniline pipeline that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface lower side simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the fresh feed pump that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine;
6) hydrogen that is connected through the cycle gas pipe with the recycle compressor pneumatic outlet is supplied with the decompression venting valve on the source gas line, and the reaction pressure of adjustment fixed-bed reactor is 0.6～1.6MPa, is preferably 0.6～1.3MPa; Control reaction end gas hydrogen content is preferably 80～95% 60～98%; Recycled offgas flow and C
8-18The volume ratio of Fatty Alcohol(C12-C14 and C12-C18) inlet amount (vapour-liquid ratio) is 2000～6000, is preferably 2600～5500;
7) C in the process system of the continuous preparation of entering long chain alkyl dimethyl tertiary amine
8-18After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor; Behind the heat exchanger cooling condensing heat-exchange; Get into the gas-liquid separator bottom, tell liquid-phase reaction product long chain alkyl dimethyl tertiary amine and water, go out gas hydrogen and unreacted reactant methylamine from the gas-liquid separator top portion from the gas-liquid separator bottom; As recycled offgas, recycle through recycle compressor;
8) liquid-phase reaction product long chain alkyl dimethyl tertiary amine and the water told from the gas-liquid separator bottom get into the liquid liquid/gas separator; The long chain alkyl dimethyl tertiary amine is told from the outlet of liquid liquid/gas separator upper lateral part continuously; Obtain the long chain alkyl dimethyl tertiary amine product of tertiary amine content >=95%, water exports from liquid liquid/gas separator lower side and tells continuously.
The described long chain alkyl dimethyl tertiary amine product that exports tertiary amine content >=95% of telling continuously from liquid liquid/gas separator upper lateral part; Can further get into and to carry out proceeding in the isolating underpressure distillation separator of continuous still battery the continuous still battery separation; Obtain the smart product of long chain alkyl dimethyl tertiary amine of tertiary amine content >=97% from underpressure distillation separator top, by product, high boiling material are discharged from underpressure distillation separator bottom.
Described vapour-liquid ratio v/v is the internal circulating load of tail gas under standard state and the volume ratio of Fatty Alcohol(C12-C14 and C12-C18) inlet amount; The liquid phase air speed is a unit time liquid feeding amount and the ratio of catalyst volume.
The effect that the present invention has:
1. production process continous-stable, control easily.
2. avoided the frequent start-stop car of intermittent production equipment, it is high to have the heat recovery and utilization rate, and energy expenditure is low.
3. the long-term closed-loop operation of production process, the environmental pollution of effectively having avoided n n dimetylaniline to escape and cause.
4. raw material consumption is few, and long chain alkyl dimethyl tertiary amine yield is high, steady quality.
Description of drawings
Fig. 1. the process system synoptic diagram of continuous preparation long-chain alkyl tertiary amine of the present invention.
Fig. 2. the process system synoptic diagram of two placed in-line continuous preparation long-chain alkyl tertiary amines of fixed-bed reactor of the present invention.
Reference numeral
1. fixed-bed reactor 2. heat exchangers 3. well heaters
4. gas-liquid separator 5. liquid liquid/gas separators 6. n n dimetylaniline gasifications condensing surface
7. underpressure distillation separator 8. water condensers 9. mist traps
10. recycle compressor 11. watercoolers
A. Fatty Alcohol(C12-C14 and C12-C18) pump b. diformazan amine pump c. hydrogen is supplied with source gas line
Embodiment
Embodiment 1
See also Fig. 1.A reactor volume is 0.4m
3The discharge port of fixed-bed reactor 1 bottom link to each other with the top hot-fluid opening for feed of heat exchanger 2 through pipeline; The hot-fluid discharge port of heat exchanger 2 bottoms links to each other with the opening for feed of gas-liquid separator 4 downsides through pipeline; The liquid outlet opening of gas-liquid separator 4 bottoms links to each other with the opening for feed on liquid liquid/gas separator 5 tops through pipeline; The discharge port of liquid liquid/gas separator 5 upper sides links to each other or links to each other with the opening for feed of product storage tank with opening for feed with the underpressure distillation separator 7 of heat-conducting oil heating through pipeline, and the discharge port of liquid liquid/gas separator 5 downsides passes through pipeline and links to each other with the opening for feed of water storage tank; The pneumatic outlet at underpressure distillation separator 7 tops links to each other with the top hot-fluid opening for feed of external condensation device through pipeline; The discharge port of underpressure distillation separator 7 bottoms links to each other with the opening for feed of by product storage tank through pipeline; The liquid outlet opening of external condensation device bottom links to each other with the smart product storage tank that loads the smart product of long chain alkyl dimethyl tertiary amine, and the non-condensable gas outlet on external condensation device top links to each other with vacuum pipe.
The pneumatic outlet at gas-liquid separator 4 tops links to each other with the gas feed at water condenser 8 tops through pipeline; The pneumatic outlet on water condenser 8 tops links to each other through the gas feed of pipeline with n n dimetylaniline gasification condensing surface 6 tops, and the pneumatic outlet on n n dimetylaniline gasification condensing surface 6 tops links to each other with the gas feed of mist trap 9 upper sides through pipeline; The liquid exit of water condenser 8, n n dimetylaniline gasification condensing surface 6 and mist trap 9 bottoms all links to each other with the withdrawing fluid import of gas-liquid separator 4 top-side through pipeline.
The pneumatic outlet at mist trap 9 tops links to each other with the import of recycle compressor 10 through pipeline; The pneumatic outlet of recycle compressor 10 links to each other with the gas feed at watercooler 11 tops through pipeline; The pneumatic outlet of watercooler 11 bottoms links to each other through the gas feed of pipeline with n n dimetylaniline gasification condensing surface 6 lower sides; The pneumatic outlet of n n dimetylaniline gasification condensing surface 6 upper lateral parts links to each other with the gas feed of heat exchanger 2 lower sides through pipeline, and the pneumatic outlet of heat exchanger 2 upper lateral parts links to each other with the gas feed at well heater 3 tops of heat-conducting oil heating through pipeline.
The pneumatic outlet of well heater 3 bottoms links to each other with the gas feed at fixed-bed reactor 1 top through pipeline.
The liquid fat raw polyol is linked to each other with the gas feed pipeline of heat exchanger 2 lower sides through pipeline by the discharge port of Fatty Alcohol(C12-C14 and C12-C18) pump a; The n n dimetylaniline raw material is linked to each other through the gas feed pipeline of pipeline with n n dimetylaniline gasification condensing surface 6 lower sides by the discharge port of diformazan amine pump b; Hydrogen source gas is supplied with source gas line c through the steel hydrogen that decompression venting valve is installed and is linked to each other with the cycle gas pipe of recycle compressor 10 pneumatic outlets.
0.4m packs in fixed-bed reactor 1
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
12-14Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Supply with source gas line c through the steel hydrogen that is connected with the outlet cycle gas pipe of recycle compressor 10 and give the initial hydrogen of introducing 0.4MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds the heat-conducting oil heating circulating hydrogen and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 225 ℃.Fatty Alcohol(C12-C14 and C12-C18) pipeline through the gas feed pipeline with heat exchanger 2 lower sides links to each other quantitatively injects C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine
12-14Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed are 0.25/h.The n n dimetylaniline pipeline that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by n n dimetylaniline feedstock pump b in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Control reaction end gas hydrogen content after reaction process is basicly stable, is adjusted reaction pressure to 0.6MPa, recycled offgas flow and C through the controlling valve of voltage regulation of Hydrogen Line c 95%
12-14The volume ratio of Fatty Alcohol(C12-C14 and C12-C18) inlet amount (vapour-liquid ratio) is 2600.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
12-14After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from the outlet of liquid liquid/gas separator 5 upper lateral parts continuously; Obtain long chain alkyl dimethyl tertiary amine product (tertiary amine content >=95%) or be called thick product, water exports from liquid liquid/gas separator 5 lower sides and tells continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 98.0%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Embodiment 2
Adopt the process system of the continuous preparation long-chain alkyl tertiary amine of embodiment 1.0.4m packs in fixed-bed reactor 1
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
8-10Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.8MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds the heat-conducting oil heating circulating hydrogen and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 240 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipes, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
8-10Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.5/h.The n n dimetylaniline pipeline that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through hydrogen steel pipe c arrives 1.3MPa, controls the reaction end gas hydrogen content 90%, after reaction process is basicly stable, and recycled offgas flow and C
8-10Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 3800.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
8-10After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 96.0%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 98.2%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Embodiment 3
Adopt the process system of the continuous preparation long-chain alkyl tertiary amine of embodiment 1.0.4m packs in fixed-bed reactor 1
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
12-14Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.6MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 235 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
12-14Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.3/h.The n n dimetylaniline pipeline that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through hydrogen steel pipe c arrives 1.0MPa, controls the reaction end gas hydrogen content 85%, after reaction process is basicly stable, and recycled offgas flow and C
12-14Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 5500.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
12-14After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 96.4%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 99.0%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Embodiment 4
Adopt the process system of the continuous preparation long-chain alkyl tertiary amine of embodiment 1.0.4m packs in fixed-bed reactor 1
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
16-18Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.5MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 250 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
16-18Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.5/h.The n n dimetylaniline pipeline that links to each other through the inlet gas pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through external steel pipe c arrives 0.8MPa, controls the reaction end gas hydrogen content 80%, after reaction process is basicly stable, and recycled offgas flow and C
16-18Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 4500.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
16-18After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 95.0%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 97.6%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Adopt the process system of the continuous preparation long-chain alkyl tertiary amine of embodiment 1.0.4m packs in fixed-bed reactor 1
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
16-18Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Be connected steel hydrogen through cycle gas pipe and supply with source gas line c to the initial hydrogen of introducing 0.6MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously with recycle compressor 10 outlets; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 240 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
16-18Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.5/h.The n n dimetylaniline pipeline that links to each other through the inlet gas pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through external steel pipe c arrives 0.9MPa, controls the reaction end gas hydrogen content 90%, after reaction process is basicly stable, and recycled offgas flow and C
16-18Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 4500.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
16-18After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 95.2%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 99.2%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Embodiment 6
The process system of preparation long-chain alkyl tertiary amine is basically with embodiment 1 continuously, and just adopting two placed in-line reactor volumes is 0.4m
3Fixed-bed reactor, as shown in Figure 2.
In two fixed-bed reactor 1, be respectively charged into 0.4m
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
12-14Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.4MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 225 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
12-14, liquid phase air speed 0.25/h.The n n dimetylaniline pipeline that links to each other through the inlet gas pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through hydrogen steel pipe c arrives 0.6MPa, controls the reaction end gas hydrogen content 95%, after reaction process is basicly stable, and recycled offgas flow and C
12-14Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 2600.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
12-14After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 95.0%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 98.8%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Embodiment 7
Adopt embodiment 6 process system of preparation long-chain alkyl tertiary amine continuously, in two fixed-bed reactor 1, be respectively charged into 0.4m
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
8-10Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.8MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 240 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
8-10Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.5/h.The n n dimetylaniline pipeline that links to each other through the inlet gas pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through hydrogen steel pipe c arrives 1.3MPa, controls the reaction end gas hydrogen content 90%, after reaction process is basicly stable, and recycled offgas flow and C
8-10Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 3800.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
8-10After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 95.3%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 98.9%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Adopt embodiment 6 process system of preparation long-chain alkyl tertiary amine continuously, in two fixed-bed reactor 1, be respectively charged into 0.4m
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
12-14Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.6MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 235 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
12-14Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.3/h.The n n dimetylaniline pipeline that links to each other through the inlet gas pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through hydrogen steel pipe c arrives 1.0MPa, controls the reaction end gas hydrogen content 85%, after reaction process is basicly stable, and recycled offgas flow and C
12-14Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 5500.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
12-14After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 95.8%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 99.1%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Embodiment 9
Adopt embodiment 6 process system of preparation long-chain alkyl tertiary amine continuously, in two fixed-bed reactor 1, be respectively charged into 0.4m
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
16-18Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.5MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 250 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
16-18Fatty Alcohol(C12-C14 and C12-C18) liquid phase air speed is at the C of 0.4/h
16-18Fatty Alcohol(C12-C14 and C12-C18).The stainless steel pipes that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through external steel pipe c arrives 0.8MPa, controls the reaction end gas hydrogen content 80%, after reaction process is basicly stable, and recycled offgas flow and C
16-18Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 4500.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
16-18After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 96.0%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 99.1%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Adopt embodiment 6 process system of preparation long-chain alkyl tertiary amine continuously, in two fixed-bed reactor 1, be respectively charged into 0.4m
3Copper be tubular porosu solid catalyzer, make each equipment of system be in health state, raw material C
16-18Fatty Alcohol(C12-C14 and C12-C18), n n dimetylaniline and hydrogen are prepared to put in place, and water, electricity, steam and thermal oil supply are normal.Steel hydrogen through the cycle gas pipe with recycle compressor 10 outlets is connected is supplied with source gas line c to the initial hydrogen of introducing 0.6MPa in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously; Start recycle compressor 10, and hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously.Well heater 3 feeds heat-conducting oil heating and heats up, and makes fixed-bed reactor 1 temperature of reaction slowly be warmed up to 240 ℃.Through the Fatty Alcohol(C12-C14 and C12-C18) pipeline that links to each other with heat exchanger 2 lower side inlet gas pipelines, in the process system of continuous preparation long chain alkyl dimethyl tertiary amine, quantitatively inject C by the pump a that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided
16-18Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed 0.35/h.The n n dimetylaniline pipeline that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface 6 lower sides simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the pump b that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine.Controlling valve of voltage regulation adjustment reaction pressure through external steel pipe c arrives 0.9MPa, controls the reaction end gas hydrogen content 90%, after reaction process is basicly stable, and recycled offgas flow and C
16-18Fatty Alcohol(C12-C14 and C12-C18) inlet amount volume ratio (vapour-liquid ratio) is 4500.Get into the C in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously
16-18After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor 1; After over-heat-exchanger 2 cooling condensation heat exchange; Get into gas-liquid separator 4 bottoms; Tell liquid-phase reaction product long-chain alkyl tertiary amine and water from gas-liquid separator 4 bottoms, go out gas hydrogen and unreacted reactant methylamine, recycle through recycle compressor 10 from gas-liquid separator 4 top portion.Liquid-phase reaction product long-chain alkyl tertiary amine of telling from gas-liquid separator 4 bottoms and water get into liquid liquid/gas separator 5; Long-chain alkyl tertiary amine is told from liquid liquid/gas separator 5 upper lateral parts continuously; Obtaining the thick product tertiary amine content of long chain alkyl dimethyl tertiary amine is 96.2%, and water is told from liquid liquid/gas separator 5 lower sides continuously.
The thick product of telling continuously from liquid liquid/gas separator 5 upper lateral parts of long chain alkyl dimethyl tertiary amine can get into underpressure distillation separator 7 continuously and carry out fractionation by distillation; The long chain alkyl dimethyl tertiary amine content that obtains smart product from underpressure distillation separator 7 tops is 99.1%, and the by product high boiling material is discharged from underpressure distillation separator 7 bottoms.
Claims (9)
1. a process system for preparing long-chain alkyl tertiary amine continuously comprises fixed-bed reactor, heat exchanger, well heater, gas-liquid separator, liquid liquid/gas separator, n n dimetylaniline gasification condensing surface, underpressure distillation separator, water condenser, mist trap, recycle compressor, watercooler, Fatty Alcohol(C12-C14 and C12-C18) pump, diformazan amine pump and hydrogen supply source gas line; It is characterized in that:
The discharge port of fixed-bed reactor bottom links to each other with the top hot-fluid opening for feed of heat exchanger through pipeline; The hot-fluid discharge port of heat exchanger bottom links to each other with the opening for feed of gas-liquid separator downside through pipeline; The liquid outlet opening of gas-liquid separator bottom links to each other with the opening for feed on liquid liquid/gas separator top through pipeline; The discharge port of liquid liquid/gas separator upper side links to each other or links to each other with the opening for feed of product storage tank with opening for feed with the underpressure distillation separator of heat-conducting oil heating through pipeline, and the discharge port of liquid liquid/gas separator downside passes through pipeline and links to each other with the opening for feed of water storage tank; The pneumatic outlet at underpressure distillation separator top links to each other with the top fed mouth of external condensation device through pipeline, and the discharge port of underpressure distillation separator bottom links to each other with the opening for feed of by product storage tank through pipeline; The liquid outlet opening of external condensation device bottom links to each other with smart product storage tank, and the non-condensable gas outlet on external condensation device top links to each other with vacuum pipe;
The pneumatic outlet at gas-liquid separator top links to each other with the gas feed at water condenser top through pipeline; The pneumatic outlet on water condenser top links to each other through the gas feed of pipeline with n n dimetylaniline gasification condenser overhead, and the pneumatic outlet on n n dimetylaniline gasification condensing surface top links to each other with the gas feed of mist trap upper side through pipeline; The liquid exit of water condenser, n n dimetylaniline gasification condensing surface and mist trap bottom all links to each other with the withdrawing fluid import of gas-liquid separator top-side through pipeline;
The pneumatic outlet at mist trap top links to each other with the import of recycle compressor through pipeline; The pneumatic outlet of recycle compressor links to each other with the gas feed at watercooler top through pipeline; The pneumatic outlet of watercooler bottom links to each other through the gas feed of pipeline with n n dimetylaniline gasification condensing surface lower side; The pneumatic outlet of n n dimetylaniline gasification condensing surface upper lateral part links to each other with the gas feed of heat exchanger lower side through pipeline, and the pneumatic outlet of heat exchanger upper lateral part links to each other with the gas feed at the well heater top of heat-conducting oil heating through pipeline;
The pneumatic outlet of heater base links to each other with the fixed-bed reactor top inlet through pipeline;
The liquid fat raw polyol is linked to each other with the gas feed pipeline of heat exchanger lower side through pipeline by the Fatty Alcohol(C12-C14 and C12-C18) pump discharge; The n n dimetylaniline raw material is linked to each other through the gas feed pipeline of pipeline with n n dimetylaniline gasification condensing surface lower side by the n n dimetylaniline pump discharge; Hydrogen source gas is supplied with source gas line through the hydrogen that decompression venting valve is installed and is linked to each other with the cycle gas pipe of recycle compressor pneumatic outlet.
2. the process system of continuous preparation long-chain alkyl tertiary amine according to claim 1 is characterized in that: the number of described fixed-bed reactor is 1～3, when the number of fixed-bed reactor during greater than 1, is to be connected in series through pipeline.
3. a process system that utilizes claim 1 or 2 described continuous preparation long-chain alkyl tertiary amines prepares the method for long-chain alkyl tertiary amine continuously, it is characterized in that this method may further comprise the steps:
1) in fixed-bed reactor, fill the porosu solid catalyzer after, make each equipment of system be in health state;
2) hydrogen that is connected through the cycle gas pipe with the recycle compressor pneumatic outlet is supplied with source gas line and is given continuously the initial hydrogen of introducing 0.4～0.6MPa in the process system of preparation long chain alkyl dimethyl tertiary amine;
3) start recycle compressor, hydrogen is circulated in the process system for preparing the long chain alkyl dimethyl tertiary amine continuously;
4) well heater feeds heat-conducting oil heating circulating hydrogen air-flow, makes the fixed-bed reactor temperature of reaction reach 210～250 ℃:
5) the Fatty Alcohol(C12-C14 and C12-C18) pipeline through linking to each other with the gas feed pipeline of heat exchanger lower side quantitatively injects C by the pump that Fatty Alcohol(C12-C14 and C12-C18) liquid is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine
8-18Fatty Alcohol(C12-C14 and C12-C18), liquid phase air speed are 0.2～1.3h
-1The n n dimetylaniline pipeline that links to each other through the gas feed pipeline with n n dimetylaniline gasification condensing surface lower side simultaneously quantitatively injects the n n dimetylaniline that satisfied reaction requires by the fresh feed pump that n n dimetylaniline is provided in the process system of continuous preparation long chain alkyl dimethyl tertiary amine;
6) hydrogen that is connected through the cycle gas pipe with the recycle compressor pneumatic outlet is supplied with the decompression venting valve on the source gas line, and the reaction pressure of adjustment fixed-bed reactor is 0.6～1.6MPa; Control reaction end gas hydrogen content is 60～98%; Recycled offgas flow and C
8-18The volume ratio of Fatty Alcohol(C12-C14 and C12-C18) inlet amount is 2000～6000;
7) C in the process system of the continuous preparation of entering long chain alkyl dimethyl tertiary amine
8-18After Fatty Alcohol(C12-C14 and C12-C18) and n n dimetylaniline react in fixed-bed reactor; Behind the heat exchanger cooling condensing heat-exchange; Get into the gas-liquid separator bottom, tell liquid-phase reaction product long chain alkyl dimethyl tertiary amine and water, go out gas hydrogen and unreacted reactant methylamine from the gas-liquid separator top portion from the gas-liquid separator bottom; As recycled offgas, recycle through recycle compressor;
8) liquid-phase reaction product long chain alkyl dimethyl tertiary amine and the water told from the gas-liquid separator bottom get into the liquid liquid/gas separator; The long chain alkyl dimethyl tertiary amine is told from the outlet of liquid liquid/gas separator upper lateral part continuously; Obtain the long chain alkyl dimethyl tertiary amine product of tertiary amine content >=95%, water exports from liquid liquid/gas separator lower side and tells continuously.
4. method according to claim 3; It is characterized in that: the described long chain alkyl dimethyl tertiary amine product that exports tertiary amine content >=95% of telling continuously from liquid liquid/gas separator upper lateral part; Can further get into and to carry out proceeding in the isolating underpressure distillation separator of continuous still battery the continuous still battery separation; Obtain the smart product of long chain alkyl dimethyl tertiary amine of tertiary amine content >=97% from underpressure distillation separator top, by product, high boiling material are discharged from underpressure distillation separator bottom.
5. method according to claim 3 is characterized in that: the described temperature of reaction of step 4) is 225～250 ℃.
6. method according to claim 3 is characterized in that: the described injection of step 5) C
8-18Fatty Alcohol(C12-C14 and C12-C18) liquid phase air speed is at 0.25～0.5h
-1
7. method according to claim 3 is characterized in that: the reaction pressure of the described adjustment fixed-bed reactor of step 6) is 0.6～1.3Mpa.
8. method according to claim 3 is characterized in that: the described control reaction end gas of step 6) hydrogen content is 80～95%.
9. method according to claim 3 is characterized in that: described recycled offgas flow of step 6) and C
8-18The volume ratio of Fatty Alcohol(C12-C14 and C12-C18) inlet amount is 2600～5500.
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|---|---|---|---|---|
| CN1211565A (en) * | 1998-09-10 | 1999-03-24 | 中国日用化学工业研究所 | Production method for preparing mono-alkyl dimethyl tertiary amine by use of aliphatic nitrile |
| CN1304913A (en) * | 2000-07-17 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Process for synthesizing hydrocarbon from syntehtic gas |
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