CN107337579A - A kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol - Google Patents
A kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol Download PDFInfo
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- CN107337579A CN107337579A CN201710756314.8A CN201710756314A CN107337579A CN 107337579 A CN107337579 A CN 107337579A CN 201710756314 A CN201710756314 A CN 201710756314A CN 107337579 A CN107337579 A CN 107337579A
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- hexylene glycol
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- phase extraction
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- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229940051250 hexylene glycol Drugs 0.000 title claims abstract description 64
- 239000007791 liquid phase Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000012071 phase Substances 0.000 claims abstract description 69
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000605 extraction Methods 0.000 claims abstract description 54
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000066 reactive distillation Methods 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 32
- 239000001361 adipic acid Substances 0.000 claims abstract description 29
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 21
- 238000004821 distillation Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 230000008878 coupling Effects 0.000 claims abstract description 5
- 238000010168 coupling process Methods 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000006200 vaporizer Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- MKFYVIXOVIEAEY-UHFFFAOYSA-N C=CC=C.[O] Chemical compound C=CC=C.[O] MKFYVIXOVIEAEY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- -1 adipic acid diformazan Ester Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol,Including reactive distillation column,Dimethyl adipate recovery tower,Around heat exchange of heat pipe,Feed heater,Hydrogenation reactor,Recycle gas compressor,Three phase extraction separator,Pressure-reducing valve,Methanol distillation column,Integrating device including pump and hexylene glycol product tower,Three phase extraction separator therein includes three-phase extractor,Dividing plate,Condenser,Return tank,Reflux pump and part vaporizer,The production technology of continuous feed reaction and the coupling of product transport disengaging height can be realized simultaneously,It can effectively ensure that the conversion ratio of reaction raw materials adipic acid and the selectivity to product hexylene glycol,It is simple to operate,It is stable,Good product quality,Environmental protection and safety coefficient are high,And production scale is easily amplified,Energy consumption and the investment of device can be significantly reduced,With good economic benefit.
Description
Technical field
The invention belongs to a kind of technology of continuous production hexylene glycol, and in particular to one kind obtains via adipic acid and methanol esterification
To dimethyl adipate, then the continuous production device and method for producing hexylene glycol via being hydrogenated with.
Background technology
Hexylene glycol is a kind of important fine chemical material increasingly attracted people's attention recently, in polyurethane, polyester, painting
The fields such as material, light curing agent, plasticizer, agricultural chemicals, dyestuff, medicine intermediate are in an increasingly wide range of applications.Hexylene glycol can be with
Improve the mechanical strength of product, improve the performances such as product resistant to hydrolysis, heat-resisting, chemical-resistant reagent.Along with polyurethane, coiled material, painting
The development of material industry, the hexylene glycol market demand of Present Global are increasing rapidly.
At present, the production technology of hexylene glycol is mainly grasped by a few countries such as Germany, Japan.German BASF uses ring
Oxygen butadiene prepares hexylene glycol, but epoxy butadiene selling at exorbitant prices；Mitsubishi Chemical, Yu Buxingchan companies and the Asahi Chemical Industry of Japan
Using adipic acid without over-churning, direct hydrogenation prepares hexylene glycol, but never realizes industrialized production for company.
Commonly used is the technology for hexylene glycol using dimethyl adipate Hydrogenation, but its esterification generally uses
Be batch tank esterifier, produce that a large amount of acid waste waters, environmental pollution are serious, and product separating energy consumption is high, complex operation,
And production is unstable, whole technique is difficult to realize continuous operation.Meanwhile the raw material of hydrogenation reaction again Seeking Truth dehydration after oneself
Acid dimethyl, this aspect separation energy consumption it is big, on the other hand also can not utilize water to hydrogenation reaction product hexylene glycol and
When extract and separate function, cause hydrogenation reaction conversion ratio and selectivity can not all be improved.
The content of the invention
It is an object of the invention to：Solution is industrially existing at present to produce hexylene glycol via adipic acid, methanol and hydrogen
Technology present in problem, there is provided a kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol, technical-constructive design close
Reason, continuous feed reaction and product separation can be realized simultaneously.
The purpose of the present invention is achieved through the following technical solutions：A kind of serialization circulation liquid-phase hydrogenatin produces oneself two
The method of alcohol, it is characterized in that outside battery limit (BL) and after coming from the catalyst and adipic acid liquid joint of No. two pumps, collectively as
The top charging of reactive distillation；Outside battery limit (BL), come from reactive distillation tower top and No. four pumps methanol liquid converge after, then altogether
Fed with the bottom as reactive distillation.In reactive distillation column, part adipic acid and part methanol in the presence of catalyst
React generation dimethyl adipate and water.Wherein, it is lower boiling to discharge from tower top without the methanol reacted and return again
Return in the top charging of reactive distillation, it is high boiling without the adipic acid reacted, catalyst and reaction product adipic acid two
Methyl esters, water, then after discharging from bottom of towe and be pressurized via No.1 pump, the charging as dimethyl adipate recovery tower.In adipic acid
In dimethyl ester recovery tower, high boiling catalyst and solution of adipic acid are discharged from bottom of towe, and after being pressurized via No. two pumps, are returned again
Return in the top charging of reactive distillation, lower boiling dimethyl adipate and water are then discharged from tower top.
From the dimethyl adipate of dimethyl adipate recovery column overhead discharge and the mixed solution of water, increase via No. three pumps
After pressure, mixing liquid does not separate, and is directly entered the shell-side around heat exchange of heat pipe, is come from the high temperature aqueous phase of three phase extraction separator
After heating, with coming from recycle gas compressor and coming from the fresh hydrogen of battery limit (BL), and be pressurized via No. five pumps, come from
After the oil phase of three phase extraction separator converges, collectively as the raw material of hydrogenation reaction, and via feed heater, it is heated to being hydrogenated with
After reacting the temperature needed, it is sent into hydrogenation reactor.In hydrogenation reactor, part dimethyl adipate and hydrogen reaction life
Into hexylene glycol and methanol.After hydrogenation reaction product is converged with the water for coming from hexylene glycol product column overhead, extract collectively as three-phase
Take the charging of separator.
In three phase extraction separator, charging initially enters the leftward space of bottom No.1 dividing plate, then from its bottom through stream
Enter partial gasification device, after partial gasification, return again to the intermediate space of one, No. two dividing plate of three phase extraction separator bottom, wherein vapour
Mutually discharged by the top of three phase extraction separator, liquid phase from the intermediate space of one, No. two dividing plate in bottom, successively via condenser,
Return tank and reflux pump.Circulating hydrogen at the top of return tank is expelled to the entrance of compressor, and the liquid of bottom is then via returning
After flowing pump pressurization, the top of three phase extraction separator is returned to.Meanwhile one, No. two dividing plate of three phase extraction separator bottom
The aqueous phase of the bottom of intermediate space, the shell side around heat exchange of heat pipe is flowed into, then through pressure-reducing valve, after decompression, flow into methanol distillation column；And
Then No. two dividing plates are crossed in overflow to oil phase at the top of it, and hydrogenation is expelled into the rightward space of No. two dividing plates in bottom, then from its bottom
In the charging of reactor.
Come from the aqueous phase of three phase extraction separator bottom, it is low in methanol distillation column as the charging of methanol distillation column
The methanol of boiling point is discharged from tower top via pipeline, and after being pressurizeed via No. four pumps, the bottom for re-entering into reactive distillation column is entered
In material；And high boiling hexylene glycol and water are discharged from bottom of towe and after being pressurized via No. six pumps, as the charging of hexylene glycol product tower,
In hexylene glycol product tower, high boiling hexylene glycol discharges battery limit (BL) from bottom of towe, and lower boiling water is discharged from tower top, partly via seven
After the pressurization of number pump, three phase extraction separator is delivered to, remainder then connects discharge battery limit (BL).
The applicable processing scheme of the present invention has the reactive distillation for separating and becoming one with product that chemically reacts, and will
The molten Hydrochemistry reaction of liquid phase multistage and the technical process of the outer coupling of extract and separate, preferred scheme is to use above-mentioned processing scheme
When, the conversion ratio of reaction raw materials adipic acid can reach more than 99.8wt%, and the selection performance to product hexylene glycol reaches
More than 94.7wt%.
In specific implementation：
Pressure, the temperature of the described catalyst for coming from No. two pumps and adipic acid liquid be 0.4~0.6MPa, 120~
180℃；
Pressure, the temperature of the described Liquid Phase Methanol for coming from reactive distillation column overhead and No. four pumps be respectively 0.1~
0.2MPa, 40~60 DEG C and 0.4~0.6MPa, 40~60 DEG C；
The operating condition of described reactive distillation column is 0.1~0.2MPa, 40~140 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10~0.18MPa, 40~60 DEG C and 0.12~0.22MPa, 80~140 DEG C；
The operating condition of described dimethyl adipate recovery tower is 0.1~0.2MPa, 80~180 DEG C, its tower top and tower
Pressure, the temperature at bottom be respectively 0.10~0.18MPa, 80~120 DEG C and 0.12~0.22MPa, 120~180 DEG C；
In described reactive distillation column and dimethyl adipate recovery tower, the conversion ratio of adipic acid can reach 99.9wt% with
On, the selection performance to product dimethyl adipate reaches more than 96.5wt%；
The pressure of solution after the described supercharging for coming from No. three pumps is 3~7MPa, and it around heat exchange of heat pipe via through adding
The later pressure of heat, temperature are 2.8~6.8MPa, 140~200 DEG C；
Pressure, the temperature of the described hydrogen for coming from recycle gas compressor are 3~7MPa, 220~350 DEG C；
The raw material of described hydrogenation reaction is respectively 150~200 DEG C entering and going out the temperature of the front and rear of feed heater
With 160~260 DEG C；
The operating condition of described hydrogenation reactor is 2.6~6.6MPa, 160~260 DEG C；
The operating condition of described three phase extraction separator is 2.4~6.4MPa, 150~250 DEG C；
It is described via No. five pumps superchargings, come from the pressure of the oil phase of three phase extraction separator, temperature be 3~
7MPa, 150~250 DEG C；
The operating condition of described methanol distillation column is 0.1~0.2MPa, 40~168 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10~0.18MPa, 40~60 DEG C and 0.12~0.22MPa, 120~168 DEG C；
The operating condition of described hexylene glycol product tower is 0.1~0.2MPa, 40~185 DEG C, the pressure of its tower top and bottom of towe
Power, temperature be respectively 0.10~0.18MPa, 40~80 DEG C and 0.12~0.22MPa, 140~185 DEG C；
The water of described hexylene glycol product column overhead discharge, 5~45% deliver to three phase extraction separator, and remainder is then arranged
Go out battery limit (BL)；
In described hydrogenation reactor, three phase extraction separator, methanol distillation column and hexylene glycol product tower, adipic acid diformazan
Ester conversion rate can reach more than 99.9wt%, and the selection performance to product hexylene glycol reaches more than 98.2wt%；
Liquid level on the left of the No.1 dividing plate of described three phase extraction separator is the space among one, No. two dividing plate
1.1~1.8 times；And the liquid level in the space among one, No. two dividing plate is 1.1~2.0 times of No. two rightward spaces of dividing plate 26.
The present invention effect be：The reactive distillation that becomes one is separated with product using that will chemically react, and by liquid
The molten Hydrochemistry reaction of phase multistage and the technical process of the outer coupling of extract and separate, raw material adipic acid, methanol and hydrogen can be simultaneously
Realize the height coupling of continuous feed reaction and the separation of product hexylene glycol.
The effect above solves problems of the prior art, effectively increases the conversion ratio and selectivity of reaction, and
Production process is more environmentally-friendly, energy-conservation and scale are easily amplified.Meanwhile simple to operate, stably, good product quality.So as to serve
Energy-conservation and the purpose for saving plant construction investment.
Brief description of the drawings
The present invention is described in further detail below in conjunction with the accompanying drawings：
Fig. 1 is a kind of schematic diagram of the device of serialization circulation liquid-phase hydrogenatin production hexylene glycol.
1 reactive distillation column, 2,3,5,8,10,15 to 17 one to No. seven pumps, 4 dimethyl adipate recovery towers, 6 exchange heat around pipe
Device, 7 feed heaters, 9 pressure-reducing valves, 11 recycle gas compressors, 12 hydrogenation reactors, 13 three phase extraction separators, 14 methanol return
Receive tower, 16 hexylene glycol product towers, 30~55,71,72 pipelines.
Fig. 2 is the schematic diagram of three phase extraction separator.
21 part vaporizers, 22 reflux pumps, 23 condensers, 24 return tanks, 25 No.1 dividing plates, 26 No. two dividing plates, 59-68 pipes
Road.
Embodiment
Below in conjunction with the accompanying drawings, apparatus and method of the present invention is further described：
Referring to attached Fig. 1 and 2, including reactive distillation column 1, dimethyl adipate recovery tower 4, heat around heat exchange of heat pipe 6, raw material
Device 7, hydrogenation reactor 12, recycle gas compressor 11, three phase extraction separator 13, pressure-reducing valve 9, methanol distillation column 14, hexylene glycol
Product tower 16 and pump.Three phase extraction separator 13 includes two dividing plates 25 and 26, condenser 23, return tank 24, reflux pump 22, portions
Divide vaporizer 21.
Being connected via the catalyst of the connection of pipeline 30 and the mixed solution of adipic acid and via pipeline 33 outside battery limit (BL)
The catalyst come from after the pressurization of No. two pumps of 4 bottom of towe of dimethyl adipate recovery tower and adipic acid liquid hybrid solution converge
Afterwards, the top of reactive distillation column 1 is continuously entered；Outside battery limit (BL) via pipeline 31 connect methanol liquid, via pipeline 32
Connection come from the tower top of reactive distillation column 1 methanol liquid and via pipeline 34 connection come from and the tower top of methanol distillation column 14
The methanol liquid pressurizeed via No. four pumps of pipeline connection, jointly via pipeline 31, the bottom of reactive distillation column 1 is continuously entered,
Two bursts charging between, in the presence of catalyst part adipic acid and part methanol react generation dimethyl adipate and
Water.
It is lower boiling without the methanol reacted in reactive distillation column 1, discharged from tower top via pipeline 32, higher boiling
Then discharged without the adipic acid, catalyst and reaction product dimethyl adipate, water reacted from bottom of towe, and via pipeline 2
No.1 pump is connected to, after pressurization, dimethyl adipate recovery tower 4 is connected to via pipeline 2, in dimethyl adipate recovery tower 4
Interior, high boiling catalyst and solution of adipic acid are discharged via pipeline 35 from bottom of towe, lower boiling dimethyl adipate and water from
Tower top, discharged via pipeline 37.
The mixing liquid of the dimethyl ester and water that come from the tower top of dimethyl adipate recovery tower 4 does not separate, directly via pipe
Road connects No. three pumps, after pressurization, is connected to via pipeline 38 around heat exchange of heat pipe 6, in heat exchange of heat pipe 6, by via pipeline 39
After connection comes from the high temperature aqueous phase liquid heating of the bottom of three phase extraction separator 13, then converge via the connection of pipeline 40 and come from
Circulating hydrogen in the recycle gas compressor 11 connected via pipeline 43, the fresh hydrogen for coming from the battery limit (BL) connected via pipeline 71
Gas and the dimethyl adipate liquid for coming from three phase extraction separator 13 bottom five pump connected via pipeline 42, after mixing
Material, be connected to feed heater 7 via pipeline 40, after being heated to the temperature of hydrogenation reaction needs, then connect via pipeline 41
It is connected to hydrogenation reactor 12.In hydrogenation reactor 12, part dimethyl adipate and hydrogen partial reaction generation hexylene glycol and
Methanol, via pipeline connection 46 and via pipeline 54 connect come from the tower top of hexylene glycol product tower 16 water converge after, then via
Pipeline 72 is connected to three phase extraction separation 13.
In three phase extraction separator 13, charging enters the leftward space of bottom No.1 dividing plate 25 via pipeline 72 first,
Partial gasification device 21 is connected to from its bottom via pipeline 66 again, in partial gasification device 21, is connected via pipeline 67 and 68
Steam heating and partization after, connected via pipeline 65, the intermediate space between the dividing plate 25 and 26 of bottom one, two,
Its vapour phase is discharged from the top of three phase extraction separator 13, is connected to condenser 59 via pipeline 62, in condenser 59, is passed through
After the circulating cooling water cooling connected by pipeline 60 and 61, connected via pipeline 59, into return tank 24, the recycle hydrogen at the top of it
Gas is connected to recycle gas compressor 11 via pipeline 47, its bottom liquid, and reflux pump 22 is connected to via pipeline 63, after pressurization,
The top of three phase extraction separator 13 is connected to via pipeline 64 again.And the dividing plate of the bottom of three phase extraction separator 13 one, two
The top of intermediate space between 25 and 26, then No. two dividing plates 26 are crossed in overflow to oil phase liquid, into the right side of No. two dividing plates 26 in bottom
Side space, then connect and discharge via pipeline 48 from its bottom.
Meanwhile the bottom of the intermediate space between the dividing plate 25 and 26 of the bottom of three phase extraction separator 13 one, two, water
Phase liquid, then it is connected to via pipeline 39 around heat exchange of heat pipe 6, in heat exchange of heat pipe 6, its heat is absorbed, and temperature reduces, then
Pressure-reducing valve 9 is connected to via pipeline 44, after pressure reduces, methanol distillation column 14 is connected to via pipeline 45, in methanol distillation column
In 14, lower boiling methanol is connected to No. four pumps from tower top via pipeline 49, and high boiling hexylene glycol and water are discharged from bottom of towe, and
And No. six pumps are connected to via pipeline 50, after being pressurized, then via pipeline 51 hexylene glycol product tower 16 is connected to, is produced in hexylene glycol
In product tower 16, high boiling hexylene glycol connects discharge battery limit (BL) from bottom of towe via pipeline 52, and lower boiling water is from tower top via pipeline
53 discharges, partly it is connected to via pipeline 54 after No. seven pumps 17 pressurize, then three phase extraction separator 13 is connected to via pipeline 55,
Part connects discharge battery limit (BL) via pipeline 53.
In addition, the liquid level of the leftward space of No.1 dividing plate 25 of the bottom of three phase extraction separator 13, one, No. two higher than bottom
Intermediate space between dividing plate 25 and 26, and the liquid level of intermediate space is higher than every the space on the right side of plate No.2 26.
It is the preferred embodiments of the invention below, the method that the present invention is illustrated by the preferred embodiment, but
The scope of the present invention is defined by scope of the claims, is not limited by the preferred embodiment.
Embodiment 1
A) come from the catalyst of No. two pumps and the pressure of adipic acid liquid, temperature 0.45MPa, 160 DEG C；
B) pressure, the temperature for coming from the Liquid Phase Methanol of reactive distillation column overhead and No. four pumps be respectively 0.1MPa, 45 DEG C
With 0.4MPa, 45 DEG C；
C) operating condition of reactive distillation column be 0.10~0.12MPa, 45~120 DEG C, pressure, the temperature of its tower top and bottom of towe
Degree be respectively 0.10MPa, 45 DEG C and 0.12MPa, 120 DEG C；
D) operating condition of dimethyl adipate recovery tower be 0.1MPa, 90~160 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10MPa, 90 DEG C and 0.12MPa, 160 DEG C；
E) in reactive distillation column and dimethyl adipate recovery tower, the conversion ratio of adipic acid is 99.9wt%, to product oneself
The selectivity of acid dimethyl is 96.5wt%；
F) pressure for coming from the solution after the supercharging of No. three pumps is 4.8MPa, and it is via after around heat exchange of heat pipe heating
Pressure, temperature 4.6MPa, 160 DEG C；
G) come from the pressure of the hydrogen of recycle gas compressor, temperature 4.8MPa, 260 DEG C；
H) raw material of hydrogenation reaction is respectively 171 DEG C and 230 DEG C entering and going out the temperature of the front and rear of feed heater；
I) operating condition of hydrogenation reactor be 4.4~4.6MPa, 230~240 DEG C；
J) operating condition of three phase extraction separator be 4.4MPa, 240 DEG C；
K) via the supercharging of No. five pumps, the pressure of the oil phase of three phase extraction separator, temperature 4.8MPa, 240 are come from
℃；
L) operating condition of methanol distillation column be 0.1~0.12MPa, 45~148 DEG C, pressure, the temperature of its tower top and bottom of towe
Degree be respectively 0.10MPa, 45 DEG C and 0.12MPa, 148 DEG C；
M) operating condition of hexylene glycol product tower be 0.1~0.12MPa, 60~180 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10MPa, 60 DEG C and 0.12MPa, 180 DEG C；
N) water of hexylene glycol product column overhead discharge, 15% delivers to three phase extraction separator, and remainder then discharges battery limit (BL)；
O) in hydrogenation reactor, three phase extraction separator, methanol distillation column and hexylene glycol product tower, dimethyl adipate turns
Rate is 99.9wt%, and the selectivity to product hexylene glycol is 98.2wt%；
P) liquid level on the left of the No.1 dividing plate of three phase extraction separator is 1.3 of the space among one, No. two dividing plate
Times；And the liquid level in the space among one, No. two dividing plate is 1.3 times of No. two dividing plate rightward spaces；
Q) total conversion of reaction raw materials adipic acid is 99.80wt%, and the overall selectivity to product hexylene glycol can be
94.76wt%.
Embodiment 2
A) come from the catalyst of No. two pumps and the pressure of adipic acid liquid, temperature 0.5MPa, 168 DEG C；
B) pressure, the temperature for coming from the Liquid Phase Methanol of reactive distillation column overhead and No. four pumps be respectively 0.12MPa, 55 DEG C
With 0.5MPa, 55 DEG C；
C) operating condition of reactive distillation column be 0.12~0.14MPa, 55~140 DEG C, pressure, the temperature of its tower top and bottom of towe
Degree be respectively 0.12MPa, 55 DEG C and 0.14MPa, 140 DEG C；
D) operating condition of dimethyl adipate recovery tower be 0.1MPa, 95~168 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10MPa, 95 DEG C and 0.12MPa, 168 DEG C；
E) in reactive distillation column and dimethyl adipate recovery tower, the conversion ratio of adipic acid is 99.92wt%, to product oneself
The selectivity of acid dimethyl is 96.8wt%；
F) pressure for coming from the solution after the supercharging of No. three pumps is 5.8MPa, and it is via after around heat exchange of heat pipe heating
Pressure, temperature 5.6MPa, 170 DEG C；
G) come from the pressure of the hydrogen of recycle gas compressor, temperature 5.8MPa, 270 DEG C；
H) raw material of hydrogenation reaction is respectively 181 DEG C and 245 DEG C entering and going out the temperature of the front and rear of feed heater；
I) operating condition of hydrogenation reactor be 5.4~5.6MPa, 245~260 DEG C；
J) operating condition of three phase extraction separator be 5.4MPa, 260 DEG C；
K) via the supercharging of No. five pumps, the pressure of the oil phase of three phase extraction separator, temperature 5.8MPa, 2460 are come from
℃；
L) operating condition of methanol distillation column be 0.12~0.14MPa, 55~150 DEG C, pressure, the temperature of its tower top and bottom of towe
Degree be respectively 0.12MPa, 55 DEG C and 0.14MPa, 150 DEG C；
M) operating condition of hexylene glycol product tower be 0.1~0.12MPa, 80~181 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10MPa, 80 DEG C and 0.12MPa, 181 DEG C；
N) water of hexylene glycol product column overhead discharge, 23% delivers to three phase extraction separator, and remainder then discharges battery limit (BL)；
O) in hydrogenation reactor, three phase extraction separator, methanol distillation column and hexylene glycol product tower, dimethyl adipate turns
Rate is 99.95wt%, and the selectivity to product hexylene glycol is 98.9wt%；
P) liquid level on the left of the dividing plate of three phase extraction separator is 1.5 times of the space among one, No. two dividing plate；And
First, the liquid level in the space among No. two dividing plates is 1.5 times of No. two dividing plate rightward spaces；
Q) total conversion of reaction raw materials adipic acid is 99.87wt%, and the overall selectivity to product hexylene glycol can be
95.73wt%.
Claims (10)
1. a kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol, including chemical reaction is turned into one with product disjoint set
The technical process of the reactive distillation of body, and the technique mistake by the molten Hydrochemistry reaction of liquid phase multistage and the outer coupling of extract and separate
Journey, it is characterised in that：Outside battery limit (BL) and after coming from the catalyst and adipic acid liquid joint of No. two pumps (3), collectively as
The top charging of reactive distillation；Outside battery limit (BL), come from reactive distillation column (1) tower top and the methanol liquid of No. four pumps (8) is converged
After conjunction, then collectively as reactive distillation bottom feed, in reactive distillation column (1) tower, in the presence of catalyst part oneself
Diacid and part methanol react generation dimethyl adipate and water, wherein, it is lower boiling without the methanol reacted from tower
Top row goes out, high boiling without the adipic acid, catalyst and reaction that have reacted in the top charging for backing within reactive distillation
Product dimethyl adipate, water, then after discharging from bottom of towe and be pressurized via No.1 pump (2), as dimethyl adipate recovery tower
(4) charging, in dimethyl adipate recovery tower (4), high boiling catalyst and solution of adipic acid are discharged from bottom of towe, and are passed through
After being pressurized by No. two pumps (2), in the top charging for backing within reactive distillation column, lower boiling dimethyl adipate and water are then
Discharged from tower top；
From the dimethyl adipate of dimethyl adipate recovery tower (4) tower top discharge and the mixed solution of water, via No. three pumps (5)
After supercharging, mixing liquid does not separate, and is directly entered the shell-side around heat exchange of heat pipe (6), is come from three phase extraction separator (13)
High temperature heated aqueous after, with coming from recycle gas compressor (11) and coming from the fresh hydrogen of battery limit (BL), and via No. five
Pump (10) supercharging, come from three phase extraction separator (13) oil phase converge after, collectively as the raw material of hydrogenation reaction, and pass through
By feed heater (7), after being heated to the temperature of hydrogenation reaction needs, it is sent into hydrogenation reactor (12), in hydrogenation reactor
(12) in, part dimethyl adipate and hydrogen reaction generation hexylene glycol and methanol, hydrogenation reaction product is same to come from hexylene glycol
After the water of product column overhead converges, collectively as the charging of three phase extraction separator (13)；
In the three phase extraction separator (13), charging initially enters the leftward space of bottom No.1 dividing plate (25), then from its bottom
Through flowing into part gasifier (21), after partial gasification, the centre of one, No. two dividing plate in three phase extraction separator (13) bottom is returned again to
Space, wherein vapour phase are discharged by the top of three phase extraction separator (13), liquid phase from the intermediate space of one, No. two dividing plate in bottom,
Successively via condenser (23), return tank (24) and reflux pump (22), the circulating hydrogen at the top of return tank (24) is expelled to
The entrance of compressor (11), after the liquid of bottom then pressurizes via reflux pump (22), return to three phase extraction separator (13)
Top, meanwhile, the aqueous phase of the bottom of the intermediate space of one, No. two dividing plate (25/26) in three phase extraction separator (13) bottom, stream
Enter the shell side around heat exchange of heat pipe (6), then through pressure-reducing valve (9), after decompression, flow into methanol distillation column (14)；And the oil phase at the top of it
Then No. two dividing plates (26) are crossed in overflow, and hydrogenation reaction is expelled into the rightward space of No. two dividing plates (26) in bottom, then from its bottom
In the charging of device (12)；
Come from the aqueous phase of three phase extraction separator (13) bottom, as the charging of methanol distillation column (14), in methanol distillation column
(14) in, lower boiling methanol is discharged from tower top via pipeline, and after being pressurizeed via No. four pumps (8), re-enters into reaction essence
In the bottom charging for evaporating tower (1)；And after high boiling hexylene glycol and water are discharged from bottom of towe and is pressurized via No. six pumps (15), as
The charging of hexylene glycol product tower, in hexylene glycol product tower (16), high boiling hexylene glycol discharges battery limit (BL) from bottom of towe, lower boiling
Water is discharged from tower top, after partly being pressurizeed via No. seven pumps (17), delivers to three phase extraction separator (13), the remainder then row of connection
Go out battery limit (BL).
2. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described comes
From be 0.4~0.6MPa in the catalyst of No. two pumps (3) and the pressure of adipic acid liquid, temperature be 120~180 DEG C；Described
The pressure for coming from the solution after the supercharging of No. three pumps (5) is 3~7MPa, and it is via after around heat exchange of heat pipe (6) heating
Pressure, temperature are 2.8~6.8MPa, 140~200 DEG C；It is described via No. five pumps (10) superchargings, come from three phase extraction point
Pressure, temperature from the oil phase of device 13 are 3~7MPa, 150~250 DEG C.
3. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described comes
It is respectively 0.1~0.2MPa, 40~60 from pressure, the temperature in reactive distillation column (1) tower top and the Liquid Phase Methanol of No. four pumps (8)
DEG C and 0.4~0.6MPa, 40~60 DEG C；
The operating condition of described reactive distillation column (1) is 0.1~0.2MPa, 40~140 DEG C, the pressure of its tower top and bottom of towe,
Temperature be respectively 0.10~0.18MPa, 40~60 DEG C and 0.12~0.22MPa, 80~140 DEG C.
4. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described oneself
The operating condition of acid dimethyl recovery tower (4) is 0.1~0.2MPa, 80~180 DEG C, pressure, the temperature of its tower top and bottom of towe
Respectively 0.10~0.18MPa, 80~120 DEG C and 0.12~0.22MPa, 120~180 DEG C.
5. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described comes
Pressure, temperature from the hydrogen in recycle gas compressor (11) are 3~7MPa, 220~350 DEG C.
6. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described adds
Temperature of the raw material of hydrogen reaction before feed heater (7) is entered is 150~200 DEG C, and the temperature after feed heater (7) is gone out is
150~200 DEG C, the operating condition of described hydrogenation reactor (12) is 2.6~6.6MPa, 160~260 DEG C.
7. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described first
The operating condition of alcohol recovery tower (4) is 0.1~0.2MPa, 40~168 DEG C, and pressure, the temperature of its tower top and bottom of towe are respectively
0.10~0.18MPa, 40~60 DEG C and 0.12~0.22MPa, 120~168 DEG C.
8. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described oneself
The operating condition of glycol product tower (16) is 0.1~0.2MPa, 40~185 DEG C, and pressure, the temperature of its tower top and bottom of towe are respectively
0.10~0.18MPa, 40~80 DEG C and 0.12~0.22MPa, 140~185 DEG C.
9. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described oneself
The water of glycol product tower (16) tower top discharge, 5~45% deliver to three phase extraction separator, and remainder then discharges battery limit (BL).
10. the method for serialization circulation liquid-phase hydrogenatin production hexylene glycol as claimed in claim 1, it is characterised in that：Described
The operating condition of three phase extraction separator (13) is 2.4~6.4MPa, 150~250 DEG C；Described three phase extraction separator (13)
No.1 dividing plate (25) on the left of liquid level be 1.1~1.8 times of the space among one, No. two dividing plate；And one, No. two dividing plate
The liquid level in middle space is 1.1~2.0 times of No. two rightward spaces of dividing plate 26.
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| JPH03115237A (en) * | 1989-09-29 | 1991-05-16 | Ube Ind Ltd | Production of 1,6-hexanediol |
| CA2247991A1 (en) * | 1996-03-01 | 1997-09-04 | Basf Aktiengesellschaft | Process for preparing 1,6 hexane diol with a level of purity over 99 % |
| CN101265158A (en) * | 2007-03-12 | 2008-09-17 | 中国石油天然气股份有限公司 | Method for producing 1,6-hexandiol |
| US20110201848A1 (en) * | 2008-10-20 | 2011-08-18 | Hirofumi Ii | High purity 1,6-hexanediol and process for preparing the same |
| CN105061152A (en) * | 2015-08-17 | 2015-11-18 | 抚顺华东能源科技研发有限公司 | Process and device for preparing 1,6-hexanediol |
| CN106905111A (en) * | 2017-01-19 | 2017-06-30 | 大连理工大学 | A kind of method of 1,6 adipic acid continuous esterification hydrogenation, 1,6 hexylene glycols of production |
-
2017
- 2017-08-29 CN CN201710756314.8A patent/CN107337579B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03115237A (en) * | 1989-09-29 | 1991-05-16 | Ube Ind Ltd | Production of 1,6-hexanediol |
| CA2247991A1 (en) * | 1996-03-01 | 1997-09-04 | Basf Aktiengesellschaft | Process for preparing 1,6 hexane diol with a level of purity over 99 % |
| CN101265158A (en) * | 2007-03-12 | 2008-09-17 | 中国石油天然气股份有限公司 | Method for producing 1,6-hexandiol |
| US20110201848A1 (en) * | 2008-10-20 | 2011-08-18 | Hirofumi Ii | High purity 1,6-hexanediol and process for preparing the same |
| CN105061152A (en) * | 2015-08-17 | 2015-11-18 | 抚顺华东能源科技研发有限公司 | Process and device for preparing 1,6-hexanediol |
| CN106905111A (en) * | 2017-01-19 | 2017-06-30 | 大连理工大学 | A kind of method of 1,6 adipic acid continuous esterification hydrogenation, 1,6 hexylene glycols of production |
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