CN101357890B - Methyl carbonate synthesis and refining technique using heat pump technique and apparatus thereof - Google Patents
Methyl carbonate synthesis and refining technique using heat pump technique and apparatus thereof Download PDFInfo
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Abstract
The invention discloses a process and a device of the synthesis and refinement of dimethyl carbonate by adopting the heat pump technology and comprises a reactive distillation column, a pressure distillation column and a methanol recovery distillation column; wherein, steam materials of the three column tops are introduced into a compressor and are pumped into a column bottom reboiler after being pressurized and heated to heat liquid materials from the column bottom; no condenser is needed to be arranged at the column top and no boiler heating steam is needed to be introduced into the bottom reboiler; after being treated by the compressor, the steam of the top of the pressure distillation column can not only meet the requirement of the bottom reboiler of the column, and part of the steam is used for preheating the incoming material of the column at the same time; the redundant part of the top steam of the reactive distillation column and the methanol recovery distillation column can be cooled by cooling water or the solutions of the bottom of the distillation columns in other process sections. The whole material flow system is operated in a completely closed way; the process can complete the heat self-balance except for that little electric energy is needed for maintaining the operation of the compressor; the production energy consumption of per unit of the dimethyl carbonate is reduced, and no boiler is needed to be heated, and the consumption of the cooling water is reduced, thus achieving the dual-purpose of saving the energy and protecting the environment.
Description
Technical field
The invention belongs to the production field of Chemicals-methylcarbonate, relate to the production technique and the device of methylcarbonate, particularly a kind of methylcarbonate synthetic and process for refining and device thereof that adopts heat pump techniques
Background technology
Methylcarbonate (being called for short DMC) is the environment-friendly Chemicals that are subjected to domestic and international extensive concern in recent years.Since contain in its molecule CH3-, CH3O-, CH3-CO-,-multiple functional groups such as CO-, thereby have a good reaction activity, can substitute that severe toxicity such as phosgene, methyl-sulfate (DM) s, methyl chloride and methyl-chloroformate or carcinogens carry out hydroxylation, methylate at numerous areas, reactions such as esterification and transesterify generate multiple important Chemicals.With DMC be raw material can polycarbonate synthesis, the fine chemicals of multiple high added values such as isocyanic ester, carbamate, obtain widespread use in fields such as high property resin, medicine, agricultural chemicals, synthetic materials, dyestuff, lubricating oil additive, foodstuff additive, electronic chemical products.Methylcarbonate has good solubility property, and not only the intermiscibility with other solvents is good, also has characteristics such as higher vaporization temperature and velocity of evaporation be fast, can be used as low poison solvent, the solvent of using as paint solvent and pharmaceutical industries etc.Oxygen level in the DMC molecule is up to 53%, have boosting of octane rating, do not have be separated, character such as low toxicity and fast degraded biologically.Therefore, DMC will become one of the most potential gasoline dope that substitutes MTBE.DMC in 1992 have passed through the registration of non-toxic chemicals in Europe, belong to nontoxic or little chemical product that poisons.Therefore, DMC is described as " new foundation stone " and " the green chemical industry product " of 21 century organic synthesis, will be with a wide range of applications.
At present the large-scale industrialization method of producing DMC mainly contains 3 kinds of phosgenations, ester-interchange method, oxidative carbonylation of methanol method.In addition, the synthesis technique of DMC also has methyl alcohol Wyler's process, carbonic acid gas methyl alcohol method etc., but still is in the laboratory study stage at present.
Phosgenation is the method for suitability for industrialized production DMC the earliest, and it is to make methyl-chloroformate earlier by phosgene and methyl alcohol reaction, and methyl-chloroformate further makes DMC with the methyl alcohol reaction.This method mature production technology, but the operational cycle is long, because phosgene belongs to hypertoxic raw material, a large amount of byproduct hydrogen-chloride etching pipe-line equipments, product cl content height, second-rate, produce dangerously, cause personal injury and environmental pollution easily.Improve though there are many people that this method has been carried out research, because the inherent defect of this method itself, this method is just progressively replaced by other non-phosgene synthetic routes at present.
Oxidative carbonylation of methanol method is to be raw material with carbon monoxide, oxygen and methyl alcohol, directly synthetic DMC under catalyst action.According to manufacturing condition, it can be divided into methanol solution phase oxidation carbonylation method and 2 kinds of production technique of methanol gas-phase oxidation/carbonylation method again.Although the oxidative carbonylation of methanol method development prospect is wide, its shortcoming is also very outstanding: 1. the used raw material of methanol oxidation carbonylation production DMC is highly purified carbon monoxide and oxygen; The production of high-purity CO is by coal gas generation water-gas, through desulfurization, copper wash, technological process such as decarburization, transformation absorption.The source of raw material oxygen needs a cover air separation facility.The investment of whole technology gas making equipment is 2～3 times of methanol oxidation carbonylating process flow path device.2. oxidation carbonylation often carries out in the limits of explosion zone of its raw material, and therefore safety and the automatization control to equipment requires than higher.3. in the oxidation carbonylation process acidic by-products production is arranged, equipment corrosion is serious.Ester-interchange method is to be raw material with methyl alcohol, epoxy third (second) alkane and carbonic acid gas, under catalyst action, epoxy third (second) alkane and carbon dioxide reaction synthesize carbonic acid third (second) alkene ester earlier, carbonic acid third (second) alkene ester carries out transesterification reaction with methyl alcohol again and obtains DMC subsequently, simultaneously by-product third (second) glycol.Ester-interchange method took the lead in realizing suitability for industrialized production by company of U.S. Texaco (Texcao) in 1992.Ester-interchange method DMC production technology but has very tempting prospect: 1. producing used raw material essence is methyl alcohol and carbonic acid gas, and epoxy third (second) alkane is the raw material carrier as joint product third (second) glycol fully.2. it can make full use of the carbonic acid gas in the exhaust gas discharged such as chemical plant, brewery, Lime Factory, has both turned waste into wealth, and can reduce Greenhouse effect again, and environment purification is green environmentally friendly technology.3. equipment is not had corrosion (equipment material is a carbon steel), the whole production totally closed operation does not have " three wastes " discharging substantially, and production process safety is easily controlled, and is easy to operate.4. 2 kinds of products of a kind of technology coproduction simultaneously, and gross investment is than the methanol oxidation carbonylating process of producing single product DMC or to produce epoxy third (second) the alkane hydrating process of third (second) glycol all little, and production cost is also low, and it is a kind of efficient coupling of many reactions.
By above production technology analysis to DMC with relatively be not difficult to find out on no matter ester-interchange method DMC production technology still is economic benefit from social benefit, all to have obvious advantages.At present, China DMC output about 90% all is to adopt this technology to produce.Methyl alcohol all can not transform fully when adopting transesterify to produce DMC, the binary azeotrope that in reactor, generates for DMC and methyl alcohol, under normal pressure, the constant boiling point of this binary azeotrope is 64 degree, at this moment DMC accounts for 30% (weight meter), methyl alcohol accounts for 70% (weight meter), and conventional method is difficult to DMC is separated purification efficiently.Separation method at present commonly used has the crystallizing process under low temperature, extraction fractional distillation, alkane azeotropic method, compression rectification method, membrane separation process etc., and wherein that is that all right is ripe for membrane separation technique, does not see the industrialization report.The crystallizing process under low temperature is characteristics of utilizing the DMC zero pour higher than methyl alcohol, selects suitable temperature to make the DMC crystallization, and redistillation gets DMC behind the fractional crystallization.This method DMC yield can reach 95%～96%, but energy consumption is big, and azeotrope will be-35～-30 ℃ of following crystallizations, and then the intensification second distillation, operational difficulty.
Adopt extractive distillation, the extraction agent consumption is big, reclaims the energy consumption height of extraction agent, and the yield of DMC is low.The alkane azeotropic method is to add alkane or naphthenic hydrocarbon etc. in methyl alcohol-DMC binary azeotrope, hydrocarbon and methyl alcohol are formed and the original different new azeotrope of temperature, utilize the difference of two azeotrope azeotropic temperature, methyl alcohol-alkane azeotrope is steamed, obtain the DMC product, though this method has superior part than extractive distillation, but the nonvariant boiling reagent loss is arranged inevitably also, the quality of product DMC is difficult to guarantee that operating process is long that control unit is many.Therefore the pressure distillation isolation technique is arisen at the historic moment, it has avoided many inadvisable parts in extractive distillation, the azeotropic distillation isolation technique, formed self simple and convenient characteristic, made on DMC quality product that ester-interchange method produces, the material consumption energy consumption level a new step.Chinese patent 00107115.7 " a kind of method of pressurize separation of methanol and dimethyl carbonate azeotrope " has reported that a kind of material self that utilizes produces the pressurize method of separation of methanol and dimethyl carbonate azeotrope of pressure.Document " the technical study of dimethyl carbonate production by transesterification, University Of Tianjin's master thesis, 2004 " ester-interchange method is synthetic to adopting, the compression rectification separation studies in great detail, though result of study shows that this method technology is simple, the equipment maturation, though the optimization by technical process can be saved the part heat, but still there is a big fatal shortcoming of energy consumption, adjustment along with China's energy structure, coal, oil equal energy source price go up year by year, the reinforcement of environmental protection policy in addition, the competitive power of this technology descends.
Summary of the invention
The objective of the invention is to solve that traditional transesterify is synthetic, in the compression rectification process for separating dimethyl carbonate power consumption high, the big shortcoming of cooling quantities, heat pump techniques is organically incorporated in the traditional technology, thereby provide a kind of methylcarbonate of energy-saving and environmental protection to synthesize and process for refining and device thereof.
The objective of the invention is to solve by the following technical programs:
Synthetic and the refining plant of the methylcarbonate of this employing heat pump techniques, the cat head methyl alcohol of its reaction fractionating tower 1, compression rectification tower 2 and methanol distillation column 3 and methylcarbonate binary azeotrope steam are introduced the suction side of first compressor 4, second compressor 5 and the 3rd compressor 6 respectively by pipeline;
The exhaust side of first compressor 4 is communicated with first reboiler, 7 hot side entrance ends at the bottom of reaction fractionating tower 1 tower and first interchanger, 10 hot side entrance ends by pipeline; Second compressor, 5 exhaust sides are communicated with second reboiler, 8 hot side entrance ends at the bottom of compression rectification tower 2 towers and material inlet preheater 11 hot side entrance ends by pipeline; The 3rd compressor 6 exhaust sides are communicated with the 3rd reboiler 9 hot side entrance ends at the bottom of methanol distillation column 3 towers and second interchanger, 12 hot side entrance ends by pipeline;
First reboiler, 7 hot side outlet ends reflux to hold by pipeline and force (forcing) pump 13 inlet ends and reaction fractionating tower 1 top and are communicated with; Material inlet preheater 11 cold sides inlet is communicated with mixing of materials surge tank 14 exit end by pipeline, and the outlet of material inlet preheater 11 cold sides is communicated with compression rectification tower 2 material inlet ends by pipeline; Second reboiler, 8 hot side outlets are communicated with by pipeline and compression rectification tower 2 backflow ends, methanol distillation column 3 intermediate material inlet ends and reducing valve 15 inlet ends; The 3rd reboiler 9 hot side outlets are communicated with by pipeline and methanol distillation column 3 backflow ends, second interchanger, 12 hot side outlet ends and recycle pump 16 inlet ends;
Force (forcing) pump 13 exit end are communicated with mixing of materials surge tank 14 inlet ends by pipeline; Recycle pump 16 exit end are communicated with mixing of materials surge tank 14 inlet ends by pipeline; Reducing valve 15 exit end are communicated with methanol distillation column 3 material inlet ends by pipeline.
Above-mentioned first compressor 4, second compressor 5 and the 3rd compressor 6 are the heat pump Pistonless compressor; Wherein first compressor 4, second compressor 5 and the 3rd compressor 6 can all or part ofly be arranged in the device.
First and second above-mentioned interchanger 10,12 is water cooling heat exchanger or rectifying tower tower bottom reboiler.
A kind of synthetic and process for refining of methylcarbonate that utilizes said apparatus and adopt heat pump techniques, it is characterized in that: after reaction fractionating tower 1 cat head binary azeotrope steam pressurizes by first compressor 4, be divided into two-way, one the tunnel accounts for 70%～90% of total mass flow rate is introduced into first reboiler, 7 hot side condensation and release of heat at the bottom of the tower, this heat is as the thermal source of first reboiler 7, be used to heat from the bottom of the tower and the solution of first reboiler, 7 cold sides of flowing through, become liquid after the release of heat simultaneously, another road accounts for 30%～10% of total mass flow rate and is introduced into first interchanger, 10 hot side release of heat and becomes liquid; After the liquid mixing from first interchanger, 10 hot side outlet ends and reboiler 7 hot side outlet ends, according to the reflux ratio scope is 2～5, part turns back in the reaction fractionating tower 1 as phegma, flows into mixing of materials surge tank 14 behind remaining liquid process force (forcing) pump 13 adherence pressures;
After compression rectification tower 2 cat head binary azeotrope steams pressurize by second compressor 5, a part accounts for 10%～20% of total mass flow rate and is introduced into preheater 11 hot sides, heating is from mixing of materials surge tank 14 exit end and enter the binary azeotropic solution of compression rectification tower 2 middle part material inlets, a part accounts for 90%～80% of total mass flow rate and is introduced into reboiler 8 hot sides in addition, the solution of heating at the bottom of from tower, after two-way condensed fluid after the release of heat mixes, according to the reflux ratio scope is 2.5～3.5, part is returned in the compression rectification tower 2 as phegma, and rest solution enters the tower middle part material inlet of methanol distillation column 3 as raw material;
Methanol rectification column overhead binary azeotrope steam is by after the 3rd compressor pressurizes, be divided into two-way, one the tunnel accounts for 75%～85% of total mass flow rate is introduced into the 3rd reboiler 9 hot side condensation and release of heat at the bottom of the tower, this heat is as the thermal source of the 3rd reboiler 9, be used to heat from the bottom of the tower and the solution of the 3rd reboiler 9 cold sides of flowing through, another road accounts for 25%～15% of total mass flow rate and is introduced into interchanger 12 hot side release of heat and becomes liquid; After the liquid mixing from second interchanger, 12 hot side outlet ends and the 3rd reboiler 9 hot side outlet ends, be 3～5 according to the reflux ratio scope, part turns back in the methanol rectifying tower 3, and remaining liquid carries the back to flow into mixing of materials surge tank 14 through recycle pump 16;
The raw material of above-mentioned reaction fractionating tower 1 is methyl alcohol and propylene carbonate, and reaction fractionating tower 1 cat head is methyl alcohol and methylcarbonate binary azeotropic steam, and solution is methyl alcohol and propylene glycol binary azeotropic solution at the bottom of the tower; The cat head of compression rectification tower 2 and methanol distillation column 3 is methyl alcohol and methylcarbonate binary azeotropic steam, is methyl alcohol and methylcarbonate binary azeotropic solution at the bottom of the tower;
Above-mentioned first and second interchanger 10, the heat-eliminating medium that 12 cold side flows through is a rectifying Tata bottom outlet solution in water coolant or and each process section that its front and back of process for refining link to each other synthetic for methylcarbonate, and solution is lower than reaction fractionating tower 1 and methanol distillation column 3 cat head binary azeotropic vapor temperatures at the bottom of the described rectifying Tata;
In above-mentioned technology, wherein first compressor 4, second compressor 5 or the 3rd compressor 6 can independent control and independent operatings.
The methylcarbonate of employing heat pump techniques of the present invention synthetic and process for refining and device thereof, wherein whole logistics system totally closed operation, after the normal operation, can be reboiler by the binary azeotrope steam after the compressor pressurizes intensification heating heat is provided, need not extraneous boiler or other modes heat, the unnecessary heat of steam can use water coolant after compressor pressurizes heated up simultaneously, derive by interchanger, perhaps be used to heat the solution at the bottom of other process section towers, also need not to be provided with condenser at cat head, therefore saved the condensation water consumption, carried out the synthetic and purified energy consumption of methylcarbonate with ester-interchange method and reduce greatly.Owing to reduced boiler heat exhaustion in the production process, therefore not only energy-conservation have environmental benefit simultaneously.In addition, the compressor among the present invention can be according to independent control and operations such as industrial scale, energy-conservation requirements.
Description of drawings
Fig. 1 is the synthetic and refining methylcarbonate schema of producing of compression rectification of ester-interchange method in the prior art;
Fig. 2 is a process flow sheet of the present invention;
Fig. 3 is the process flow sheet that interchanger adopts water quench;
Fig. 4 is an interchanger with solution refrigerative process flow sheet at the bottom of the propylene glycol fore-running Tata.
Wherein: 1 is reaction fractionating tower; 2 is the compression rectification tower; 3 is methanol distillation column; 4 is that first compressor, 5 is that second compressor and 6 is the 3rd compressor; 7 first reboilers, 8 are that second reboiler, 9 is that the 3rd reboiler and 29 is the 4th reboiler; 10 is that first interchanger and 12 is second interchanger; 11 is the material inlet preheater; 13 is force (forcing) pump; 14 is the mixing of materials surge tank; 15 is pressurizing valve; 16 is recycle pump; 17 is cooling tower; 18 is cooling water circulating pump; 19 is the propylene glycol primary tower; 20 is that first condenser, 21 is that second condenser, 22 the 3rd condensers and 23 are the 4th condenser; 24 is that first solution pump, 25 is that second solution pump, 26 is that the 3rd solution pump, 27 is that the 4th solution pump and 28 is the 5th solution pump.
Embodiment
Below in conjunction with accompanying drawing the present invention is done and to describe in further detail:
Fig. 1 is synthetic and process for refining and a device schema of a kind of existing common methylcarbonate, and it mainly is made up of four rectifying tower, is respectively reaction fractionating tower 1, compression rectification tower 2, methanol distillation column 3 and propylene glycol primary tower 19.The cat head of each tower has condenser 20,21, and 22 or 23, reboiler 7,8 is arranged, 9 or 29 at the bottom of the tower; Extraneous water coolant enters the condenser cold side, cooling is from the binary azeotropic steam of cat head, the binary azeotropic liquid that the hot side outlet of condenser is condensed is at first, second and third, under five solution pumps 24,25,26 and 28 the effect, partly flow into the backflow end of corresponding cat head according to certain reflux ratio, rest parts enters in other towers as discharging according to certain requirement; Feed heating steam or other thermals source in the reboiler at the bottom of the tower, part is returned in the corresponding tower after the hot side evaporation of reboiler from the material at the bottom of the tower.As seen from the figure, the hot side of overhead condenser need discharge heat, and the tower bottom reboiler cold side need absorb heat, therefore needs to consume a large amount of water coolant and heating steam.
Referring to Fig. 2, the cat head of reaction fractionating tower 1 of the present invention is communicated with by the suction side of pipeline with heat pump first compressor 4, and the exhaust side of heat pump first compressor 4 is connected with first reboiler, 7 hot side entrance ends at the bottom of reaction fractionating tower 1 tower and first interchanger, 10 hot side entrance ends by pipeline; The cat head of compression rectification tower 2 is communicated with by the suction side of pipeline with heat pump compressor 5, and the exhaust side of heat pump compressor 5 is communicated with second reboiler, 8 hot side entrance ends at the bottom of compression rectification tower 2 towers and this tower material inlet preheater 11 hot side entrance ends by pipeline; The cat head of methanol distillation column 3 is communicated with by the suction side of pipeline with heat pump the 3rd compressor 6, and the 3rd compressor 6 exhaust sides are communicated with the 3rd reboiler 9 hot side entrance ends at the bottom of methanol distillation column 3 towers and interchanger 12 hot side entrance ends by pipeline; First reboiler, 7 hot side outlet ends reflux to hold by pipeline and force (forcing) pump 13 inlet ends, interchanger 12 hot side outlet ends and reaction fractionating tower 1 top and are communicated with at the bottom of reaction fractionating tower 1 tower; Reaction fractionating tower 1 material inlet preheater 11 cold sides inlet is communicated with mixing of materials surge tank 14 exit end by pipeline; The outlet of reaction fractionating tower 1 material inlet preheater 11 cold sides is communicated with compression rectification tower 2 material inlet ends by pipeline; Compression rectification tower 2 reboilers 8 hot side outlets are communicated with by pipeline and compression rectification tower 2 backflow ends, methanol distillation column 3 intermediate material inlet ends, material inlet preheater 11 hot side outlets and reducing valve inlet end; The 3rd reboiler 9 hot side outlets are communicated with by pipeline and methanol distillation column 1 backflow end, exchanger heat side outlet end and recycle pump 16 inlet ends at the bottom of methanol distillation column 3 towers; Force (forcing) pump 13 exit end are communicated with mixing of materials surge tank 14 inlet ends by pipeline; Reducing valve 15 exit end are communicated with methanol distillation column 3 material inlet ends by pipeline; Recycle pump 16 exit end are communicated with mixing of materials surge tank 14 inlet ends by pipeline.
Principle of work of the present invention is as follows:
Methyl alcohol and propylene carbonate that preorder technology generates enter in the reaction fractionating tower 1 according to certain ratio (as: methyl alcohol and propylene carbonate molar ratio 4: 1), under normal pressure, according to reacting (as: 65～67 ℃ of temperature of reaction) under certain condition, generate methylcarbonate, simultaneously because refinery distillation, the methylcarbonate that produces is distilled out from mixing solutions, form methyl alcohol and methylcarbonate binary azeotropic steam (as: under the normal pressure at cat head, 64 ℃ of azeotropic temperatures, methylcarbonate weight percent 25%), this steam is by heat pump first compressor, 4 pressurization backs (as: pressurization pressure ratio 2.2), be divided into two-way, first reboiler, 7 hot sides were carried out condensation and release of heat at the bottom of one tunnel (as: accounting for total mass flow rate 82.5%) introduced tower, this heat is as the thermal source of first reboiler 7, be used to heat from the bottom of the tower and the methyl alcohol of first reboiler, 7 cold sides of flowing through and propylene glycol binary azeotropic pressure solution (as: under the normal pressure, 70 ℃ of azeotropic temperatures, propylene glycol weight percent 25%), steam becomes liquid after the release of heat simultaneously, and another road (as: accounting for total mass flow rate 17.5%) introduced first interchanger, 10 hot side release of heat and become liquid; After the liquid mixing from first reboiler, 7 hot side outlet ends at the bottom of first interchanger, 10 hot side outlet ends and the reactive distillation Tata, according to certain reflux ratio (as: reflux ratio 2), under the conveying effect of first compressor 4, part turns back in the reaction fractionating tower 1 as phegma, flows into mixing of materials surge tank 14 behind remaining liquid process force (forcing) pump 13 adherence pressures; Methyl alcohol after the pressurization and methylcarbonate binary solution at first flow into material inlet preheater 11 cold sides inlet from 14 outlets of mixing of materials surge tank, after promoting temperature, being re-used as raw material flows in the compression rectification tower 2, because the lifting of pressure, azeotropic point improves, most of methyl alcohol distills from solution with the steam form, and concentration of dimethyl carbonate solution residual in the solution obtains enrichment.Compression rectification tower 2 cat head methyl alcohol and methylcarbonate binary azeotrope steam (as: gauge pressure 1.5MPa, 153 ℃ of azeotropic temperatures, methyl alcohol weight percent 91.5%), by heat pump second compressor, 5 pressurization backs (as: pressurization pressure ratio 1.8), a part (as: accounting for total mass flow rate 12.5%) is introduced compression rectification tower 2 material inlet preheaters 11 hot sides and is same as methyl alcohol and the dimethyl ester binary solution of heating from mixing of materials surge tank 14, a part (as: accounting for total mass flow rate 87.5%) is introduced second reboiler, 8 hot sides at the bottom of compression rectification tower 2 towers in addition, methyl alcohol and methylcarbonate binary azeotropic solution (as: the gauge pressure 1.5MPa of heating at the bottom of from tower, 170 ℃ of azeotropic temperatures, methyl alcohol weight percent 0.5%), after condensed fluid after the release of heat mixes, according to certain reflux ratio (as: reflux ratio 3), part is returned in the compression rectification tower 2 as phegma, and rest solution reduces pressure (as: reducing to normal pressure) back by reducing valve 16 and enters methanol distillation column 3 centre entrances as raw material; Methanol rectifying tower 3 cat head methyl alcohol and methylcarbonate binary azeotrope steam (as: normal pressure, 64 ℃ of azeotropic temperatures, methylcarbonate weight percent 75%), by heat pump second compressor, 5 pressurization backs (as: the pressurization pressure ratio is 1.9), be divided into two-way, the 3rd reboiler 9 hot side condensation and release of heat at the bottom of one tunnel (as: accounting for total mass flow rate 83.5%) the introducing tower, this heat as methanol rectifying tower 3 towers at the bottom of the thermal source of the 3rd reboiler 9, be used to heat from methyl alcohol and methylcarbonate binary azeotropic solution (as: normal pressure at the bottom of the tower and that flow through the 3rd reboiler 9 cold sides, 65 ℃ of azeotropic temperatures, methyl alcohol weight percent 99%), another road (as: accounting for total mass flow rate 16.5%) introduced second interchanger, 12 hot side release of heat and become liquid; After the liquid mixing from second interchanger, 12 hot side outlet ends and the 3rd reboiler 9 hot side outlet ends, according to certain reflux ratio (as: reflux ratio 4.5), part turns back in the methanol rectifying tower 3, and remaining liquid carries the back to flow into mixing of materials surge tank 14 through recycle pump 16.
Referring to Fig. 1, compare with the refining methylcarbonate device of producing of compression rectification with existing ester-interchange method is synthetic, omitted the condenser of original reaction fractionating tower, compression rectification tower and Methanol Recovery column overhead in the technical scheme of the present invention, increased by 3 heat pump compressors; Compare with existing technology, because therefore cat head frozen-free device need not the steam of extraneous water quench from cat head, simultaneously, steam after heating up through compressor pressurizes is enough to heat the solution at the bottom of the tower of reboiler of flowing through, and need not extraneous heating steam (or other heating energy source).
Embodiment 1: interchanger water quench scheme
Referring to Fig. 3, in this embodiment, cooling tower 17 and cooling water circulating pump 18 have been increased in the device; Handle the water coolant of back cooling carries through cooling water circulating pump 18 through cooling tower 17, be divided into two-way and flow into first interchanger 10 and second interchanger, 12 cold sides inlet respectively, water coolant is after first interchanger 10 and the 12 absorption heats intensifications of second interchanger, flow out and compile from cold side outlet and turn back to the cooling tower, finish circulation.
Production technique is as follows:
Is to enter in reaction fractionating tower 1 at 3: 1 methyl alcohol and propylene carbonate according to molar ratio, under normal pressure, temperature of reaction is 65～67 ℃, generate methylcarbonate, simultaneously because refinery distillation, the methylcarbonate that produces is distilled out from mixing solutions, form methyl alcohol and methylcarbonate binary azeotropic steam (as: under the normal pressure at cat head, 64 ℃ of azeotropic temperatures, methylcarbonate weight percent 25%), this steam is by heat pump compressor 4 pressurizations, the pressure ratio of wherein pressurizeing is 2.2, the binary azeotropic steam is divided into two-way then, first reboiler, 7 hot sides were carried out condensation and release of heat at the bottom of the binary azeotropic steam that accounts for total mass flow rate 85% was introduced into tower, this heat is as the thermal source of first reboiler 7, be used to heat from the bottom of the tower and the methyl alcohol of first reboiler, 7 cold sides of flowing through and propylene glycol binary azeotropic pressure solution (as: under the normal pressure, 70 ℃ of azeotropic temperatures, propylene glycol weight percent 25%), steam becomes liquid after the release of heat simultaneously, and the binary azeotropic steam that another road accounts for total mass flow rate 15% is introduced into first interchanger, 10 hot side release of heat and becomes liquid; After the liquid mixing from first reboiler, 7 hot side outlet ends at the bottom of first interchanger, 10 hot side outlet ends and the reactive distillation Tata, with reflux ratio is 3, under the conveying effect of first compressor 4, part turns back in the reaction fractionating tower 1 as phegma, flows into mixing of materials surge tank 14 behind remaining liquid process force (forcing) pump 13 adherence pressures; Methyl alcohol after the pressurization and methylcarbonate binary solution at first flow into material inlet preheater 11 cold sides inlet from 14 outlets of mixing of materials surge tank, after promoting temperature, being re-used as raw material flows in the compression rectification tower 2, because the lifting of pressure, azeotropic point improves, most of methyl alcohol distills from solution with the steam form, and concentration of dimethyl carbonate solution residual in the solution obtains enrichment.Compression rectification tower 2 cat head methyl alcohol and methylcarbonate binary azeotrope steam (as: gauge pressure 1.5MPa, 153 ℃ of azeotropic temperatures, methyl alcohol weight percent 91.5%), by 5 pressurizations of heat pump second compressor, the pressure ratio of wherein pressurizeing is 1.8,15% of total mass flow rate binary azeotrope steam is introduced into the hot side of compression rectification tower 2 material inlet preheaters and is same as methyl alcohol and the dimethyl ester binary solution of heating from mixing of materials surge tank 14 then, the part binary azeotrope steam that accounts for total mass flow rate 85% is introduced into second reboiler, 8 hot sides at the bottom of compression rectification tower 2 towers in addition, methyl alcohol and methylcarbonate binary azeotropic solution (as: the gauge pressure 1.5MPa of heating at the bottom of from tower, 170 ℃ of azeotropic temperatures, methyl alcohol weight percent 0.5%), after condensed fluid after the release of heat mixes, with reflux ratio is 3.5, part is returned in the compression rectification tower 2 as phegma, and rest solution reduces pressure (as: reducing to normal pressure) back by reducing valve 16 and enters methanol distillation column 3 centre entrances as raw material; Methanol rectifying tower 3 cat head methyl alcohol and methylcarbonate binary azeotrope steam (as: normal pressure, 64 ℃ of azeotropic temperatures, methylcarbonate weight percent 75%), by heat pump second compressor 5 with pressure ratio 1.9 pressurization after, be divided into two-way, one the tunnel accounts for 85% of total mass flow rate is introduced into the 3rd reboiler 9 hot side condensation and release of heat at the bottom of the tower, this heat as methanol rectifying tower 3 towers at the bottom of the thermal source of the 3rd reboiler 9, be used to heat from methyl alcohol and methylcarbonate binary azeotropic solution (as: normal pressure at the bottom of the tower and that flow through the 3rd reboiler 9 cold sides, 65 ℃ of azeotropic temperatures, methyl alcohol weight percent 99%), another road (as: accounting for total mass flow rate 15%) introduced second interchanger, 12 hot side release of heat and become liquid; After the liquid mixing from second interchanger, 12 hot side outlet ends and the 3rd reboiler 9 hot side outlet ends, according to certain reflux ratio (as: reflux ratio 4.5), part turns back in the methanol rectifying tower 3, and remaining liquid carries the back to flow into mixing of materials surge tank 14 through recycle pump 16.
Embodiment 2: solution cooled off at the bottom of interchanger was used propylene glycol fore-running Tata
Referring to Fig. 4, in this embodiment, first interchanger 10 and second interchanger 12 are as the tower bottom reboiler of propylene glycol primary tower 19; Part methyl alcohol after heat pump compressor 4 pressurizations heat up and methylcarbonate binary azeotropic steam flow are through first interchanger 10, methyl alcohol and the propylene glycol binary mixing solutions of hot spots at the bottom of from propylene glycol primary tower 19 towers, equally, part methyl alcohol after heating up from heat pump compressor pressurization and methylcarbonate binary azeotropic steam flow be through first interchanger 12, heats other methyl alcohol and propylene glycol binary mixing solutionss at the bottom of from propylene glycol primary tower 19 towers.
Production technique is as follows:
Is to enter in reaction fractionating tower 1 at 5: 1 methyl alcohol and propylene carbonate according to molar ratio, under normal pressure, temperature of reaction is 65～67 ℃, generate methylcarbonate, simultaneously because refinery distillation, the methylcarbonate that produces is distilled out from mixing solutions, form methyl alcohol and methylcarbonate binary azeotropic steam (as: under the normal pressure at cat head, 64 ℃ of azeotropic temperatures, methylcarbonate weight percent 25%), this steam is by heat pump compressor 4 pressurizations, the pressure ratio of wherein pressurizeing is 2.2, the binary azeotropic steam is divided into two-way then, first reboiler, 7 hot sides were carried out condensation and release of heat at the bottom of the binary azeotropic steam that accounts for total mass flow rate 75% was introduced into tower, this heat is as the thermal source of first reboiler 7, be used to heat from the bottom of the tower and the methyl alcohol of first reboiler, 7 cold sides of flowing through and propylene glycol binary azeotropic pressure solution (as: under the normal pressure, 70 ℃ of azeotropic temperatures, propylene glycol weight percent 25%), steam becomes liquid after the release of heat simultaneously, and the binary azeotropic steam that another road accounts for total mass flow rate 25% is introduced into first interchanger, 10 hot side release of heat and becomes liquid; After the liquid mixing from first reboiler, 7 hot side outlet ends at the bottom of first interchanger, 10 hot side outlet ends and the reactive distillation Tata, with reflux ratio is 2.5, under the conveying effect of first compressor 4, part turns back in the reaction fractionating tower 1 as phegma, flows into mixing of materials surge tank 14 behind remaining liquid process force (forcing) pump 13 adherence pressures; Methyl alcohol after the pressurization and methylcarbonate binary solution at first flow into material inlet preheater 11 cold sides inlet from 14 outlets of mixing of materials surge tank, after promoting temperature, being re-used as raw material flows in the compression rectification tower 2, because the lifting of pressure, azeotropic point improves, most of methyl alcohol distills from solution with the steam form, and concentration of dimethyl carbonate solution residual in the solution obtains enrichment.Compression rectification tower 2 cat head methyl alcohol and methylcarbonate binary azeotrope steam (as: gauge pressure 1.5MPa, 153 ℃ of azeotropic temperatures, methyl alcohol weight percent 91.5%), by 5 pressurizations of heat pump second compressor, the pressure ratio of wherein pressurizeing is 1.8,12.5% of total mass flow rate binary azeotrope steam is introduced into compression rectification tower 2 material inlet preheaters 11 hot sides and is same as methyl alcohol and the dimethyl ester binary solution of heating from mixing of materials surge tank 14 then, the part binary azeotrope steam that accounts for total mass flow rate 87.5% is introduced into second reboiler, 8 hot sides at the bottom of compression rectification tower 2 towers in addition, methyl alcohol and methylcarbonate binary azeotropic solution (as: the gauge pressure 1.5MPa of heating at the bottom of from tower, 170 ℃ of azeotropic temperatures, methyl alcohol weight percent 0.5%), after condensed fluid after the release of heat mixes, with reflux ratio is 3, part is returned in the compression rectification tower 2 as phegma, and rest solution reduces pressure (as: reducing to normal pressure) back by reducing valve and enters methanol distillation column 3 centre entrances as raw material; Methanol rectifying tower 3 cat head methyl alcohol and methylcarbonate binary azeotrope steam (as: normal pressure, 64 ℃ of azeotropic temperatures, methylcarbonate weight percent 75%), by heat pump second compressor 5 with pressure ratio 1.9 pressurization after, be divided into two-way, one the tunnel accounts for 80% of total mass flow rate introduces the 3rd reboiler 9 hot side condensation and release of heat at the bottom of the tower, this heat as methanol rectifying tower 3 towers at the bottom of the thermal source of the 3rd reboiler 9, be used to heat from methyl alcohol and methylcarbonate binary azeotropic solution (as: normal pressure at the bottom of the tower and that flow through the 3rd reboiler 9 cold sides, 65 ℃ of azeotropic temperatures, methyl alcohol weight percent 99%), another road (as: accounting for total mass flow rate 25%) introduced second interchanger, 12 hot side release of heat and become liquid; After the liquid mixing from second interchanger, 12 hot side outlet ends and reboiler 9 hot side outlet ends, according to certain reflux ratio (as: reflux ratio 5), part turns back in the methanol rectifying tower 3, and remaining liquid carries the back to flow into mixing of materials surge tank 14 through recycle pump 16.Methyl alcohol at the bottom of propylene glycol primary tower 19 towers and propylene glycol binary azeotropic solution (as: normal pressure, 80 ℃ of azeotropic temperatures, methyl alcohol weight percent 50%) is divided into two-way, one the tunnel, the binary azeotropic solution that accounts for total mass flow rate 55% is introduced interchanger 10 cold sides inlet absorption heat, other one tunnel (as: accounting for total mass flow rate 45%) introduced second interchanger, 12 cold sides inlet, this two-way binary azeotropic solution absorbs heat respectively and is evaporated to methyl alcohol and propylene glycol binary azeotropic steam in first interchanger 10 and second interchanger 12, and after first interchanger 10 and second interchanger, 12 cold sides outlet mixing, be back at the bottom of propylene glycol primary tower 19 towers.
Compare with Fig. 3, in the present embodiment, steam heat after pressurization heats up through heat pump compressor can fully use, need not extraneous water coolant, simultaneously for the propylene glycol primary tower, because first interchanger 10 and second interchanger 12 have substituted the reboiler in the former tower, need not to adopt steam-heated cal(l)andria at the bottom of the propylene glycol fore-running Tata, have further saved energy expenditure.
The preferred specific embodiment of described in conjunction with the accompanying drawings above the present invention only is used to illustrate embodiments of the present invention; rather than as restriction to aforementioned goal of the invention and appended claims content and scope; every foundation technical spirit of the present invention all still belongs to the technology of the present invention and rights protection category to any simple modification, equivalent variations and modification that above embodiment did.
Claims (9)
1. one kind is adopted the methylcarbonate of heat pump techniques to synthesize and refining plant, and it is characterized in that: the cat head methyl alcohol of reaction fractionating tower (1), compression rectification tower (2) and methanol distillation column (3) and methylcarbonate binary azeotrope steam are introduced the suction side of first compressor (4), second compressor (5) and the 3rd compressor (6) respectively by pipeline;
The exhaust side of first compressor (4) is communicated with first reboiler (7) hot side entrance end at the bottom of reaction fractionating tower (1) tower and the hot side entrance of first interchanger (10) end by pipeline; Second compressor (5) exhaust side is communicated with second reboiler (8) hot side entrance end at the bottom of compression rectification tower (2) tower and the hot side entrance of material inlet preheater (11) end by pipeline; The 3rd compressor (6) exhaust side is communicated with the 3rd reboiler (9) hot side entrance end at the bottom of methanol distillation column (3) tower and the hot side entrance of second interchanger (12) end by pipeline;
The hot side outlet end of first reboiler (7) refluxes to hold by pipeline and force (forcing) pump (13) inlet end and reaction fractionating tower (1) top and is communicated with; Material inlet preheater (11) cold side inlet is communicated with mixing of materials surge tank (14) exit end by pipeline, and the outlet of material inlet preheater (11) cold side is communicated with compression rectification tower (2) material inlet end by pipeline; The hot side outlet of second reboiler (8) is communicated with by pipeline and compression rectification tower (2) backflow end, methanol distillation column (3) intermediate material inlet end and reducing valve (15) inlet end; The hot side outlet of the 3rd reboiler (9) is communicated with by pipeline and methanol distillation column (3) backflow end, the hot side outlet end of second interchanger (12) and recycle pump (16) inlet end;
Force (forcing) pump (13) exit end is communicated with mixing of materials surge tank (14) inlet end by pipeline; Recycle pump (16) exit end is communicated with mixing of materials surge tank (14) inlet end by pipeline; Reducing valve (15) exit end is communicated with methanol distillation column (3) material inlet end by pipeline.
2. the synthetic and refining plant of the methylcarbonate of employing heat pump techniques according to claim 1, it is characterized in that: described first compressor (4), second compressor (5) and the 3rd compressor (6) are the heat pump Pistonless compressor.
3. the synthetic and refining plant of the methylcarbonate of employing heat pump techniques according to claim 1 is characterized in that: described first compressor (4), second compressor (5) and all or part of being arranged in the device of the 3rd compressor (6).
4. the synthetic and refining plant of the methylcarbonate of employing heat pump techniques according to claim 1, it is characterized in that: described first and second interchanger (10,12) is water cooling heat exchanger or rectifying tower tower bottom reboiler.
5. one kind is adopted the methylcarbonate of heat pump techniques to synthesize and process for refining, the device of described technology utilization claim 1, it is characterized in that: after reaction fractionating tower (1) cat head binary azeotrope steam pressurizes by first compressor (4), be divided into two-way, the binary azeotrope steam that accounts for total mass flow rate 70%～90% is introduced into hot side condensation of first reboiler (7) and release of heat at the bottom of the tower, this heat is as the thermal source of first reboiler (7), be used for heating from the bottom of the tower and the solution of first reboiler (7) cold side of flowing through, become liquid after the release of heat simultaneously, the binary azeotrope steam that another road accounts for total mass flow rate 30%～10% is introduced into the hot side release of heat of first interchanger (10) and becomes liquid; After the liquid mixing from hot side outlet end of first interchanger (10) and the hot side outlet end of first reboiler (7), according to the reflux ratio scope: 2～5, part turns back in the reaction fractionating tower (1) as phegma, flows into mixing of materials surge tank (14) behind remaining liquid process force (forcing) pump (13) adherence pressure;
After compression rectification tower (2) cat head binary azeotrope steam pressurizes by second compressor (5), 10%～20% the cat head binary azeotrope steam that wherein accounts for total mass flow rate is introduced into the hot side of preheater (11), heating is from mixing of materials surge tank (14) exit end and enter the binary azeotropic solution of compression rectification tower (2) middle part material inlet, account for total mass flow rate in addition and be 90%～80% cat head binary azeotrope steam and be introduced into the hot side of second reboiler (8), the solution of heating at the bottom of from tower, after two-way condensed fluid after the release of heat mixes, according to the reflux ratio scope is 2.5～3.5, part is returned in the compression rectification tower (2) as phegma, and rest solution enters the tower middle part material inlet of methanol distillation column (3) as raw material;
After methanol rectifying tower (3) cat head binary azeotrope steam pressurizes by the 3rd compressor (6), be divided into two-way, one the tunnel to account for total mass flow rate be 75%～85% to be introduced into hot side condensation of the 3rd reboiler (9) and release of heat at the bottom of the tower, this heat is as the thermal source of the 3rd reboiler (9), be used for heating from the bottom of the tower and the solution of the 3rd reboiler (9) cold side of flowing through, it is 25%～15% to be introduced into the hot side release of heat of second interchanger (12) and to become liquid that another road accounts for total mass flow rate; After the liquid mixing from hot side outlet end of second interchanger (12) and the hot side outlet end of the 3rd reboiler (9), according to reflux ratio is 3～5, part turns back in the methanol rectifying tower (3), and remaining liquid carries the back to flow into mixing of materials surge tank (14) through recycle pump (16).
6. the synthetic and process for refining of the methylcarbonate of employing heat pump techniques according to claim 5, it is characterized in that: the raw material of reaction fractionating tower (1) is methyl alcohol and propylene carbonate, reaction fractionating tower (1) cat head is methyl alcohol and methylcarbonate binary azeotropic steam, and solution is methyl alcohol and propylene glycol binary azeotropic solution at the bottom of the tower; The cat head of compression rectification tower (2) and methanol distillation column (3) is methyl alcohol and methylcarbonate binary azeotropic steam, is methyl alcohol and methylcarbonate binary azeotropic solution at the bottom of the tower.
7. the synthetic and process for refining of the methylcarbonate of employing heat pump techniques according to claim 5, it is characterized in that: the heat-eliminating medium that first and second interchanger (10,12) cold side flows through is a water coolant.
8. the synthetic and process for refining of the methylcarbonate of employing heat pump techniques according to claim 5, it is characterized in that: first and second interchanger (10,12) heat-eliminating medium that flows through of cold side for its before and after rectifying Tata bottom outlet solution in each process section of linking to each other, and described rectifying Tata bottom outlet solution is lower than reaction fractionating tower (1) and methanol distillation column (3) cat head binary azeotropic vapor temperature.
9. the synthetic and process for refining of the methylcarbonate of employing heat pump techniques according to claim 5 is characterized in that: first compressor (4), second compressor (5) or the 3rd compressor (6) independent control and operation.
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| CN102134196A (en) * | 2010-12-30 | 2011-07-27 | 山东德普化工科技有限公司 | Residual heat utilization device used in methyl carbonate production |
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| CN103626656A (en) * | 2012-08-27 | 2014-03-12 | 亚申科技研发中心（上海）有限公司 | Method for separating dimethyl carbonate and methanol through pressure-swing distillation of heat pump, and apparatus thereof |
| CN102908796A (en) * | 2012-10-17 | 2013-02-06 | 李毅 | Multi-effect rectifying system |
| CN103408428B (en) * | 2013-08-14 | 2015-07-08 | 上海戊正工程技术有限公司 | Process for producing dimethyl carbonate from industrial synthetic gas |
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| TWI642660B (en) * | 2017-07-19 | 2018-12-01 | 國立清華大學 | Manufacturing methods and manufacturing apparatuses of propylene carbonate and dimethyl carbonate |
| CN110105216B (en) * | 2019-04-12 | 2024-02-27 | 天津乐科节能科技有限公司 | Self-backheating rectification method and device |
| CN110156603A (en) * | 2019-04-12 | 2019-08-23 | 天津乐科节能科技有限公司 | A kind of method and device of dimethyl carbonate from backheat rectifying |
| CN110845334B (en) * | 2019-11-15 | 2022-04-22 | 胜华新能源科技(东营)有限公司 | Device and method for producing battery-grade ethyl methyl carbonate by using dimethyl carbonate and ethanol |
| CN113769427B (en) * | 2021-09-26 | 2024-05-28 | 上海交通大学 | System and method for co-producing dimethyl carbonate and dihydric alcohol |
| CN114984603B (en) * | 2022-05-16 | 2024-02-27 | 上海蕙黔新材料科技有限公司 | Distillation separation equipment for gas-phase oxo-synthesis process of dimethyl carbonate |
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