CN105061152A - Process and device for preparing 1,6-hexanediol - Google Patents
Process and device for preparing 1,6-hexanediol Download PDFInfo
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- 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
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention relates to a process and a device for preparing 1,6-hexanediol, and belongs to the technical field of 1,6-hexanediol preparation. The process comprises the following steps: A, esterification reaction; B, alkalinity adjustment; C, distillation; D, hydrogenation reduction; E, hydrogen recycle; F, distillation. The device for preparing 1,6-hexanediol comprises an esterification reaction device and a hydrogenation reaction device. According to the process and the device for preparing 1,6-hexanediol, firstly, 1,6-hexanedioic acid and methanol are used as raw materials, and are subjected to esterification reaction in the esterification reaction device to obtain dimethyl adipate, then dimethyl adipate and hydrogen are subjected to reduction reaction in the hydrogenation reaction device to finally obtain 1,6-hexanediol, the chromatogram content of 1,6-hexanediol is greater than 99.5%, and the industrialized production of 1,6-hexanediol is realized.
Description
Technical field
The invention belongs to the preparing technical field of 1,6-hexylene glycol, be specifically related to a kind of technique for the preparation of 1,6-hexylene glycol and device.
Background technology
Along with the develop rapidly of petrochemical complex, Fine Chemical and apparel industry, constantly expand by the range of application of 1,6-hexylene glycol synthesis product innovation, the demand of China to 1,6-hexylene glycol increases fast, and annual import volume increases with the ratio of more than 15%.
The hexylene glycol market in the current whole world is by BASF Aktiengesellschaft (BASF), Lanxess Corporation (former Beyer Co., Ltd) and Ube company monopolizing.The throughput that BASF Aktiengesellschaft has in Texas ,Usa free port and Ludwigshafen, Germany has reached 50,000 tons/year.There is 1,6-hexylene glycol product line device of ton in the Yu Bu company of Japan in Spain's construction, and Eastern Europe, South East Asia and China all never have the manufacturing enterprise forming mass-producing.China is 1, the production technology of 6-hexylene glycol is in open position always, and 1, the 6-hexylene glycol product that market needs all relies on from external import, based on brands such as Baeyer, German BASF (BASF) and Japanese space portions, annual import volume 3000-5000 ton.This will be that China faces important problem.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the invention provides a kind of technique for the preparation of 1,6-hexylene glycol and device, to realize the suitability for industrialized production of 1,6-hexylene glycol.
The technical solution adopted in the present invention is:
A kind of technique for the preparation of 1,6-hexylene glycol, comprises the following steps:
A. esterification: by 1,6-hexanodioic acid, methyl alcohol, catalyst for esterification reaction and gac join in esterifier, described activated carbon dosage is 0.05 ~ 0.2% of raw material gross weight, carry out esterification under agitation, temperature of reaction is 115 ~ 118 DEG C, reaction pressure is 0.3 ~ 0.5Mpa, and the reaction times is more than 8 hours, obtains the reaction solution of raw material reaction completely containing dimethyl adipate;
B. alkali tune degree: the reaction solution containing dimethyl adipate obtained in steps A is joined in neutralization reactor, and carries out neutralization reaction with alkaline solution, obtain the reaction solution that pH value is 6.5 ~ 7;
C. distill: be that the reaction solution of 6.5 ~ 7 is successively by separating methanol distillation tower, dehydration distillation tower and de-ester distillation tower by the pH value obtained in step B, methyl alcohol is recycled through the distillation of separating methanol distillation tower, water is recycled through dehydration distillation tower, obtain dimethyl adipate through de-ester distillation tower distillation, content is more than 99.5%;
D. hydrogenating reduction: after the dimethyl adipate obtained in step C is mixed with dissolve with methanol, through metering supercharging and hydrogen mixing, enter in hydrogenator after interchanger heats up again, under reducing catalyst effect, reduction reaction occurs, and temperature of reaction is 180 ~ 210 DEG C, and reaction pressure is 18 ~ 22MPa, obtain the reaction solution containing 1,6-hexylene glycol;
E. recover hydrogen: by the reaction solution containing 1,6-hexylene glycol obtained in step D successively by being separated in high-pressure separator and light pressure separator, being separated and obtaining hydrogen and mixed solution; Described hydrogen returns in step D and mixes with raw material after circulating hydrogen compressor supercharging, reuses;
F. distill: by the mixed solution that obtains after being separated in step e successively through the first distillation tower and second column, be recycled methyl alcohol by the first distillation tower distillation, obtain 1,6-hexylene glycol by after-fractionating column distillation.
Make 1,6-hexanodioic acid and methyl alcohol, under the effect of catalyst for esterification reaction and gac, esterification occur by steps A, produce dimethyl adipate.
After steps A reaction, in reaction solution, part acid can be remained, therefore, adopt alkaline solution adjust ph to 6.5-7 by step B, remove residual acid and stopped reaction.Above-mentioned alkaline solution is inorganic alkali solution, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution etc.
The reaction solution after basicity will be regulated through step B successively by separating methanol distillation tower, dehydration distillation tower and de-ester distillation tower by step C.Boiling point due to methyl alcohol is 64.7 DEG C, the boiling point of water is 100 DEG C, and the boiling point of dimethyl adipate is 109-110 DEG C, therefore by separating methanol distillation tower, methyl alcohol distillation is removed, by dehydration distillation tower, water is gone out, by de-ester distillation tower, dimethyl adipate is being distilled, obtaining pure higher hexanodioic acid and methyl esters.Meanwhile, the first alcohol and water distilled reclaims, and wherein reclaims methyl alcohol and can return steps A and reuse, thus cost-saving, avoids the wasting of resources and environmental pollution.
The dimethyl adipate and methanol mixed that obtain will be distilled in step C by step D, then through heating, heat up after and hydrogen enter in hydrogenator, and under the effect of reducing catalyst, dimethyl adipate, by hydrogen reducing, obtains 1,6-hexylene glycol.
Pass through step e, reacted reaction solution in step D is separated with residual hydrogen, and residual hydrogen is reclaimed, thus while the potential safety hazard avoiding the remaining hydrogen band of gas, the hydrogen of collection can also be returned in step D through circulating hydrogen compressor supercharging and reduce dimethyl adipate and being reused, avoid the wasting of resources, cost-saving.
By step F, the mixed solution in step e after being separated is passed through the first distillation tower and second column successively, due to 1, the boiling point of 6-hexylene glycol, higher than methyl alcohol and dimethyl adipate, therefore, removes remaining methyl alcohol and dimethyl adipate by the first distillation tower, by second column by 1,6-hexylene glycol distills, and collects and obtains 1,6-hexylene glycol, and obtain 1,6-oneself and the chromatographic content of alcohol is greater than 99.5%.The methyl alcohol distill out the first distillation tower and dimethyl adipate are collected respectively, are recycled methyl alcohol, and it can return in steps A, reuses; The recovery dimethyl adipate obtained as the raw material of reduction reaction, can return in step D and continues and hydrogen reaction, thus, save cost, avoid waste and the environmental pollution of dimethyl adipate.
Further, the weight ratio of 1,6-hexanodioic acid and described methyl alcohol described in steps A is 1:1.
Further, the recovery methyl alcohol obtained in step C and step D returns in steps A, reuses.
Further, the tower top temperature in the described separating methanol distillation tower in step C is 65 ~ 68 DEG C, and pressure is normal pressure.
Further, the described de-ester distillation tower in step C adopts underpressure distillation, and the tower top temperature in described de-ester distillation tower is 105 ~ 110 DEG C, and vacuum pressure is 2800 ~ 3000pa; Described second column in step F adopts underpressure distillation, and the tower top temperature of described second column is 130 ~ 140 DEG C, and vacuum pressure is 2000 ~ 2500pa.
For the ease of reducing distillation temperature, convenient operation and raising dimethyl adipate and 1, the distilling effect of 6 hexylene glycols, de-ester distillation tower and second column all adopt the method for underpressure distillation.Reduced the boiling point of dimethyl adipate and 1,6-hexylene glycol by underpressure distillation, thus just dimethyl adipate and 1,6-hexylene glycol can be distilled without the need to high temperature, reduce energy consumption.
The invention provides a kind of technique for the preparation of 1,6-hexylene glycol, to be applicable to the above-mentioned technique for the preparation of 1,6-hexylene glycol, it comprises: esterification device and hydrogenation reaction device;
Described esterification device comprise connect successively in order mixture tank, the first fresh feed pump, esterifier, in and pump, neutralization reactor, the first separating methanol pump, separating methanol distillation tower, dehydration pump, dehydration distillation tower, de-ester pump and de-ester distillation tower; The top of described separating methanol distillation tower is provided with the first condenser being connected with methyl alcohol holding tank, described dehydration distillation tower top is provided with the second condenser being connected with water collecting tank, and the top of described de-ester distillation tower is provided with the 3rd condenser being connected with ester holding tank;
Described hydrogenation reaction device comprise connect successively in order test tank, volume pump, hydrogen and material mixer, high pressure heat exchanger, hydrogenator, high-pressure separator, light pressure separator, the first water cooler, hold-up vessel, the second fresh feed pump, the first distillation tower, dealcoholysis pump and second column; Described test tank is connected with described ester holding tank;
Described hydrogenation reaction device also comprises make-up hydrogen compressor, circulating hydrogen compressor, methanol tank, dimethyl adipate storage tank and 1,6-hexylene glycol storage tank; Described separator is connected with described circulating hydrogen compressor, and described circulating hydrogen compressor is connected with described hydrogenation charging mixture tank; The top of described first distillation tower is provided with the second water cooler, described second water cooler is connected with described methanol tank and described dimethyl adipate storage tank respectively by sparger, the top of described second column is provided with the 3rd water cooler, described 3rd water cooler and described 1,6-hexylene glycol storage tank connect.
During use, by 1,6-hexanodioic acid and methyl alcohol are mixed with mixed solution by than row in mixture tank, then by the first fresh feed pump, the mixed solution prepared is made a gift to someone in esterifier, and esterification is there is under the effect of catalyst for esterification reaction and gac, obtain the reaction solution containing dimethyl adipate.Preferably, the consumption of gac accounts for 0.1% of raw material gross weight.
Reaction solution containing dimethyl adipate is pumped in neutralization reactor by neutralization, and in alkaline solution generation neutralization reaction, makes the basicity value that the reaction solution containing dimethyl adipate reaches suitable.The reaction solution containing dimethyl adipate regulating basicity value is pumped into separating methanol distillation tower by the first separating methanol, through the distillment of separating methanol distillation tower, is distilled away by methyl alcohol from tower top, and is collected in methyl alcohol holding tank through the effect of the first condenser.Bottom separating methanol distillation tower, remaining reaction solution is sent in dehydration distillation tower by dehydration pump, is distilled away at the top of water from dehydration distillation tower, and is collected in water collecting tank through the effect of the second condenser.Bottom dehydration distillation tower, remaining reaction solution is pumped in de-ester distillation tower by de-ester, dimethyl adipate becomes steam and steams from the top of de-ester distillation tower, then the effect through the 3rd condenser is collected in ester holding tank, thus obtains the higher dimethyl adipate of purity.
Passed in test tank by the dimethyl adipate prepared by esterification device, and prepare in proportion with methyl alcohol, be preferably, the weight ratio of dimethyl adipate and methyl alcohol is 1:1.
Mixed solution is by mixing with material mixer by hydrogen with the hydrogen after pressurization after volume pump boosting, then after high pressure heat exchanger heat temperature raising, hydrogenator is entered, issue raw reduction reaction in the effect of reducing catalyst, obtain the reaction solution containing 1,6-hexylene glycol.Hydrogen after pressurization, derives from through the new hydrogen of make-up hydrogen compressor pressurization and the recover hydrogen through circulating hydrogen compressor pressurization.
Containing 1, the reaction solution of 6-hexylene glycol makes residual hydrogen be separated with reaction solution through high-pressure separator and the effect of light pressure separator, to residual hydrogen recovery and by sending into the reaction continuing on for reduction dimethyl adipate in hydrogenation charging mixture tank after circulating hydrogen compressor pressurization.
Reaction solution after separation enters in hold-up vessel after the first water cooler cooling, then send in the first distillation tower by the second fresh feed pump, by the distillment of the first distillation tower, methyl alcohol and dimethyl adipate are steamed respectively from the top of the first distillation tower, and being collected in respectively in methanol tank and dimethyl adipate storage tank by sparger after cooling under the effect of the second water cooler, so that recycling.
Bottom first distillation tower, remaining reaction solution is pumped in second column by dealcoholysis, under the effect of second column, by 1,6-hexylene glycol distills from the tower top of second column, and be collected in 1,6-hexylene glycol storage tank after the 3rd water cooler cooling, obtain finished product.
Further, the agitator of described esterifier adopts grid agitator.
By grid agitator, 1,6-hexanodioic acid, methyl alcohol and 0.1% gac and catalyzer are fully stirred, thus be conducive to the carrying out of esterification.
Further, described methyl alcohol holding tank and described mixture tank, described methanol tank and described mixture tank, described dimethyl adipate storage tank is all connected by transferpump with between described test tank.
Recovery methyl alcohol in methyl alcohol holding tank is sent in mixture tank by transferpump, recovery methyl alcohol in methanol tank is sent in mixture tank by transferpump, recovery dimethyl adipate in dimethyl adipate storage tank is sent in test tank by transferpump, thus recovery methyl alcohol and dimethyl adipate are reused.
Further, the top of described de-ester distillation tower is provided with the first vacuum pump; The top of described second column is also provided with the second vacuum pump.
Reduce the pressure in de-ester vacuum column by the first vacuum pump, make the boiling point lowering of dimethyl adipate, thus be convenient to be distilled.Reduce the pressure in second column by the second vacuum pump, make the boiling point lowering of 1,6-hexylene glycol, thus be convenient to 1,6-hexylene glycol to distill.
Beneficial effect of the present invention is:
The present invention, by the technique for the preparation of 1,6-hexylene glycol that provides and device, is first that raw material carries out esterification in esterification device with 1,6-hexanodioic acid and methyl alcohol, obtains dimethyl adipate; Then dimethyl adipate and hydrogen carry out reduction reaction in hydrogenation reaction device, finally obtain 1,6-hexylene glycol, and the chromatographic content of 1,6-hexylene glycol is greater than 99.5%, achieve the suitability for industrialized production of 1,6-hexylene glycol.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device for the preparation of 1,6-hexylene glycol described in embodiment 2.
Be labeled as in figure:
Mixture tank 101, first fresh feed pump 102, in and pump 103, neutralization reactor 104, first separating methanol pump 105, dehydration pump 106, de-ester pump 107, de-ester distillation tower 108, ester holding tank 109, first vacuum pump 110, 3rd condenser 111, water collecting tank 112, second condenser 113, dehydration distillation tower 114, methyl alcohol holding tank 115, first condenser 116, separating methanol distillation tower 117, esterifier 118, volume pump 119, hydrogen and material mixer 120, high pressure heat exchanger 121, first water cooler 122, hold-up vessel 123, second fresh feed pump 124, dealcoholysis pump 125, methanol tank 126, dimethyl adipate storage tank 127, second column 128, 1, 6-hexylene glycol storage tank 129, second vacuum pump 130, 3rd water cooler 131, sparger 132, second water cooler 133, first distillation tower 134, light pressure separator 135, high-pressure separator 136, hydrogenator 137, test tank 138, make-up hydrogen compressor 139, circulating hydrogen compressor 140.
Embodiment
Embodiment 1
Present embodiments provide a kind of technique for the preparation of 1,6-hexylene glycol, comprise the following steps:
A. esterification: by 1,6-hexanodioic acid and methyl alcohol by weight 1:1 with prepare after join in esterifier, under the effect of catalyst for esterification reaction and gac, there is esterification; The consumption of gac is 0.05 ~ 0.2% of raw material gross weight, is preferably 0.1%; Temperature of reaction is 115 ~ 118 DEG C, and reaction pressure is 0.3 ~ 0.5Mpa, and the reaction times is 8 hours, after raw material reaction is complete, obtains the reaction solution containing dimethyl adipate;
B. alkali tune degree: the reaction solution containing dimethyl adipate obtained in steps A is joined in neutralization reactor, and carries out neutralization reaction with alkaline solution, obtain the reaction solution that pH value is 6.5 ~ 7;
C. distill: be that the reaction solution of 6.5 ~ 7 is successively by separating methanol distillation tower, dehydration distillation tower and de-ester distillation tower by the pH value obtained in step B, methyl alcohol is recycled through the distillation of separating methanol distillation tower, water is recycled through dehydration distillation tower, obtain dimethyl adipate through de-ester distillation tower distillation, content is more than 99.5%;
D. hydrogenating reduction: after the dimethyl adipate obtained in step C is mixed with dissolve with methanol, through metering supercharging and hydrogen mixing, enter in hydrogenator after interchanger heats up again, under reducing catalyst effect, reduction reaction occurs, and temperature of reaction is 180 ~ 210 DEG C, and reaction pressure is 18-22MPa, obtain the reaction solution containing 1,6-hexylene glycol;
E. recover hydrogen: by the reaction solution containing 1,6-hexylene glycol obtained in step D successively by being separated in high-pressure separator and light pressure separator, being separated and obtaining hydrogen and mixed solution; Described hydrogen returns in step D and mixes with raw material after circulating hydrogen compressor supercharging, reuses;
F. distill: by the mixed solution that obtains after being separated in step e successively through the first distillation tower and second column, be recycled methyl alcohol by the first distillation tower distillation, obtain 1,6-hexylene glycol by after-fractionating column distillation.
The recovery methyl alcohol obtained in above-mentioned steps C and step F returns in steps A, make methyl alcohol as raw material and solvent again with the reaction of 1,6-hexanodioic acid so that make methyl alcohol be reused.
As a kind of preferred version in the present embodiment, the tower top temperature in the separating methanol distillation tower in above-mentioned steps C is 65 ~ 68 DEG C, and pressure is normal pressure; De-ester distillation tower in step C adopts underpressure distillation, and the tower top temperature in de-ester distillation tower is 105 ~ 110 DEG C, and vacuum pressure is 2800 ~ 3000pa; Second column in step F adopts underpressure distillation, and the tower top temperature of second column is 130 ~ 140 DEG C, and vacuum pressure is 2000 ~ 2500pa.
Embodiment 2
As shown in Figure 1, provide a kind of device for the preparation of 1,6-hexylene glycol in the present embodiment, to be applicable to the technique for the preparation of 1,6-hexylene glycol in embodiment 1, it comprises: esterification device and hydrogenation reaction device.
Esterification device comprise connect successively in order mixture tank 101, first fresh feed pump 102, esterifier 118, in and pump 103, neutralization reactor 104, first separating methanol pump 105, separating methanol distillation tower 117, dehydration pump 106, dehydration distillation tower 114, de-ester pump 107 and de-ester distillation tower 108; The top of separating methanol distillation tower 117 is provided with the first condenser 116 being connected with methyl alcohol holding tank 115, dehydration distillation tower 114 top is provided with the second condenser 113 being connected with water collecting tank 112, and the top of de-ester distillation tower 108 is provided with the 3rd condenser 111 being connected with ester holding tank 109; Esterifier 118 adopts grid agitator.
Hydrogenation reaction device comprise connect successively in order test tank 138, volume pump 119, hydrogen and material mixer 120, high pressure heat exchanger 121, hydrogenator 137, high-pressure separator 136, light pressure separator 135, first water cooler 122, hold-up vessel 123, second fresh feed pump 124, first distillation tower 134, dealcoholysis pump 125 and second column 128; Test tank 138 is connected with ester holding tank 109.
Hydrogenation reaction device also comprises make-up hydrogen compressor 139, circulating hydrogen compressor 140, methanol tank 126, dimethyl adipate storage tank 127 and 1,6-hexylene glycol storage tank 129; High-pressure separator 136 is all connected with circulating hydrogen compressor 140 with light pressure separator 135, and make-up hydrogen compressor 139 is all connected with material mixer 120 with hydrogen with circulating hydrogen compressor 140; The top of the first distillation tower 134 is provided with the second water cooler 133, second water cooler 133 is connected with methanol tank 126 and dimethyl adipate storage tank 127 respectively by sparger 132, the top of second column 128 is provided with the 3rd water cooler 131,3rd water cooler 131 and 1,6-hexylene glycol storage tank 129 connect.
For the ease of the recovery methyl alcohol in methyl alcohol holding tank 115 and methanol tank 126 is delivered in mixture tank 101, the dimethyl adipate in dimethyl adipate storage tank 127 is convenient to deliver in test tank 138, methyl alcohol holding tank 115 and mixture tank 101, methanol tank 126 and mixture tank 101, dimethyl adipate storage tank 127 is all connected by transferpump with test tank 138, therefore, directly transportation work is completed by transferpump.
As a kind of preferred version of the present embodiment, the top of de-ester distillation tower 108 is provided with the first vacuum pump 110; The top of second column 128 is also provided with the second vacuum pump 130.
Above-mentioned volume pump 119 is plunger type metering pump.
The present invention is not limited to above-mentioned preferred forms; anyone can draw other various forms of products under enlightenment of the present invention; no matter but any change is done in its shape or structure; every have identical with the application or akin technical scheme, all drops within protection scope of the present invention.
Claims (9)
1. one kind for the preparation of the technique of 1,6-hexylene glycol, it is characterized in that, comprise the following steps:
A. esterification: by 1,6-hexanodioic acid, methyl alcohol, catalyst for esterification reaction and gac join in esterifier, described activated carbon dosage is 0.05 ~ 0.2% of raw material gross weight, esterification is carried out under mechanical agitation, temperature of reaction is 115 ~ 118 DEG C, reaction pressure is 0.3 ~ 0.5Mpa; Reaction times is more than 8 hours, obtains the reaction solution of raw material reaction completely containing dimethyl adipate;
B. alkali tune degree: the reaction solution containing dimethyl adipate obtained in steps A is joined in neutralization reactor, and carries out neutralization reaction with alkaline solution, obtain the reaction solution that pH value is 6.5 ~ 7;
C. distill: be that the reaction solution of 6.5 ~ 7 is successively by separating methanol distillation tower, dehydration distillation tower and de-ester distillation tower by the pH value obtained in step B, methyl alcohol is recycled through the distillation of separating methanol distillation tower, water is recycled through dehydration distillation tower, obtain dimethyl adipate through de-ester distillation tower distillation, content is more than 99.5%;
D. hydrogenating reduction: after the dimethyl adipate obtained in step C is mixed with dissolve with methanol, with hydrogen mixing after metering supercharging, enter in hydrogenator after interchanger heats up again, under reducing catalyst effect, reduction reaction occurs, and temperature of reaction is 180 ~ 210 DEG C, and reaction pressure is 18 ~ 22MPa, obtain the reaction solution containing 1,6-hexylene glycol;
E. recover hydrogen: by the reaction solution containing 1,6-hexylene glycol obtained in step D successively by being separated in high-pressure separator and light pressure separator, being separated and obtaining hydrogen and mixed solution; Described hydrogen returns in step D and mixes with raw material after circulating hydrogen compressor supercharging, reuses;
F. distill: by the mixed solution that obtains after being separated in step e successively through the first distillation tower and second column, be recycled methyl alcohol by the first distillation tower distillation, obtain 1,6-hexylene glycol by after-fractionating column distillation.
2. the technique for the preparation of 1,6-hexylene glycol according to claim 1, is characterized in that, the weight ratio of 1,6-hexanodioic acid and described methyl alcohol described in steps A is 1:1.
3. the technique for the preparation of 1,6-hexylene glycol according to claim 1, is characterized in that, the recovery methyl alcohol obtained in step C and step F returns in steps A, reuses.
4. the technique for the preparation of 1,6-hexylene glycol according to any one of claim 1-3, is characterized in that, the tower top temperature in the described separating methanol distillation tower in step C is 65 ~ 68 DEG C, and pressure is normal pressure.
5. according to any one of claim 1-3 for the preparation of 1, the technique of 6-hexylene glycol, is characterized in that, the described de-ester distillation tower in step C adopts underpressure distillation, tower top temperature in described de-ester distillation tower is 105 ~ 110 DEG C, and vacuum pressure is 2800 ~ 3000Pa; Described second column in step F adopts underpressure distillation, and the tower top temperature of described second column is 130 ~ 140 DEG C, and vacuum pressure is 2000 ~ 2500Pa.
6. the device for the preparation of 1,6-hexylene glycol, for the technique for the preparation of 1,6-hexylene glycol described in any one of claim 1-5, is characterized in that, comprising: esterification device and hydrogenation reaction device;
Described esterification device comprise connect successively in order mixture tank, the first fresh feed pump, esterifier, in and pump, neutralization reactor, the first separating methanol pump, separating methanol distillation tower, dehydration pump, dehydration distillation tower, de-ester pump and de-ester distillation tower; The top of described separating methanol distillation tower is provided with the first condenser being connected with methyl alcohol holding tank, described dehydration distillation tower top is provided with the second condenser being connected with water collecting tank, and the top of described de-ester distillation tower is provided with the 3rd condenser being connected with ester holding tank;
Described hydrogenation reaction device comprise connect successively in order test tank, volume pump, hydrogen and material mixer, high pressure heat exchanger, hydrogenator, high-pressure separator, light pressure separator, the first water cooler, hold-up vessel, the second fresh feed pump, the first distillation tower, dealcoholysis pump and second column; Described test tank is connected with described ester holding tank;
Described hydrogenation reaction device also comprises make-up hydrogen compressor, circulating hydrogen compressor, methanol tank, dimethyl adipate storage tank and 1,6-hexylene glycol storage tank; Described high-pressure separator, described light pressure separator are all connected with described circulating hydrogen compressor, and described make-up hydrogen compressor, described circulating hydrogen compressor are all connected with material mixer with described hydrogen; The top of described first distillation tower is provided with the second water cooler, described second water cooler is connected with described methanol tank and described dimethyl adipate storage tank respectively by sparger, the top of described second column is provided with the 3rd water cooler, described 3rd water cooler and described 1,6-hexylene glycol storage tank connect.
7. the device for the preparation of 1,6-hexylene glycol according to claim 6, is characterized in that, the agitator of described esterifier adopts grid agitator.
8. according to claim 6 for the preparation of 1, the device of 6-hexylene glycol, is characterized in that, described methyl alcohol holding tank and described mixture tank, described methanol tank and described mixture tank, described dimethyl adipate storage tank is all connected by transferpump with between described test tank.
9. the device for the preparation of 1,6-hexylene glycol according to claim 6, is characterized in that, the top of described de-ester distillation tower is provided with the first vacuum pump; The top of described second column is also provided with the second vacuum pump.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106748645A (en) * | 2016-12-10 | 2017-05-31 | 山东元利科技股份有限公司 | The method that one kind improves 1,6 hexylene glycol purity |
| CN107337579A (en) * | 2017-08-29 | 2017-11-10 | 华陆工程科技有限责任公司 | A kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol |
| CN108503511A (en) * | 2018-05-28 | 2018-09-07 | 中溶科技股份有限公司 | By dimethyl adipate Hydrogenation 1, the distillation system and method for 6- hexylene glycols |
| CN110156562A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | A kind of synthesis technology of 1,6-HD |
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| CN1594252A (en) * | 2004-06-21 | 2005-03-16 | 沈阳工业大学 | Method for producing 1,6-hexanediol |
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