CN111574371A - Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate - Google Patents

Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate Download PDF

Info

Publication number
CN111574371A
CN111574371A CN202010573797.XA CN202010573797A CN111574371A CN 111574371 A CN111574371 A CN 111574371A CN 202010573797 A CN202010573797 A CN 202010573797A CN 111574371 A CN111574371 A CN 111574371A
Authority
CN
China
Prior art keywords
tower
methanol
formaldehyde
mma
unit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010573797.XA
Other languages
Chinese (zh)
Other versions
CN111574371B (en
Inventor
李秀芝
董文威
党伟荣
陈西波
王耀红
张绍岩
张战
高桂余
王朋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Risun Technology Co ltd
Original Assignee
Beijing Risun Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Risun Technology Co ltd filed Critical Beijing Risun Technology Co ltd
Priority to CN202010573797.XA priority Critical patent/CN111574371B/en
Publication of CN111574371A publication Critical patent/CN111574371A/en
Application granted granted Critical
Publication of CN111574371B publication Critical patent/CN111574371B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/40—Extractive distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The embodiment of the invention provides a method and a device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate, wherein the method comprises the following steps: oxidizing methanol to prepare formaldehyde solution; preparing anhydrous gas-phase formaldehyde from the formaldehyde solution by concentration and extractive distillation; reacting anhydrous gas-phase formaldehyde with methyl acetate to prepare a crude methyl acrylate product; concentrating the MA crude product obtained by the reaction through azeotropic distillation and extractive distillation to remove formaldehyde in the MA crude product; the concentrated MA is subjected to hydrogenation reaction and MP separation to prepare methyl propionate, and methanol is recovered and returned to serve as a solvent for reaction of anhydrous gas-phase formaldehyde and methyl acetate; reacting the obtained MP with anhydrous gas-phase formaldehyde prepared from a formaldehyde solution to prepare methyl methacrylate; separating and refining the generated MMA through azeotropic rectification, three-solvent extraction and rectification; wherein, the extractant for the three-solvent extraction comprises a formaldehyde-rich solution obtained by MA concentration. The invention has the advantages of easy feeding, simplified process and low energy consumption.

Description

Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate
Technical Field
The invention relates to the technical field of chemical process and equipment, in particular to a method and a device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate.
Background
Methyl Methacrylate (MMA) is used as an important organic chemical raw material, and the market demand of China is rapidly increased. MMA is used primarily as a polymerizing monomer for producing its polymers and copolymers, the primary downstream product being Polymethylmethacrylate (PMMA), commonly known as plexiglass. Because PMMA has a series of excellent characteristics of excellent light transmission, toughness, chemical stability, corrosion resistance, electrical insulation, easy dyeing, easy processing and the like, PMMA can be widely used in the aspects of vehicles, ships, airplanes, buildings, instruments, stationery, sanitary wares and the like, and can replace glass as a building material which is not easy to break. In addition, the methyl methacrylate is also used in the aspects of coatings, emulsion resins, adhesives, PVC resin modifiers, polymer concrete, acrylic fiber second monomers, textile sizing agents, medical functional materials and the like.
Methyl methacrylate processes are exemplified by the Acetone Cyanohydrin (ACH) process, the isobutylene process, the ethylene process, the methyl vinyl propionate (Alpha) process, the modified acetone cyanohydrin (MGC-ACH) process, and the like. The ACH method has the defects of long process flow, severe toxicity caused by using hydrocyanic acid and the like. The Alpha process is technically advanced, environmentally friendly, and the already-produced devices function well, but the technical availability is low.
The polyvinyl alcohol and terephthalic acid industries produce a large amount of methyl acetate as a by-product. And methyl acetate and formaldehyde are bulk chemicals, the production technology thereof is mature, and the coal-based acetic acid and formaldehyde have surplus capacity in China at present. If the coal-based methyl acetate and formaldehyde are converted into methyl methacrylate with high added value through methyl acrylate and methyl propionate, the raw material source can be expanded for the production of the methyl methacrylate by using the domestic energy structure characteristics, the industrial chain of coal chemical industry can be extended, and the dilemma of excess production of acetic acid and formaldehyde can be relieved.
Methyl Methacrylate (MA) is synthesized by taking methyl acetate and formaldehyde as raw materials, and then Methyl Propionate (MP) is prepared by hydrogenating methyl acrylate, so that Methyl Methacrylate (MMA) with high additional value is prepared. The methyl methacrylate process by the ester aldehyde method has the advantages of cheap and easily obtained raw materials, wide sources and resource advantages according with the Chinese situation. However, the direct use of an inexpensive aqueous formaldehyde solution as a reaction raw material has a very adverse effect on the MA reaction and MMA reaction. And can appear that raw materials cost is high when adopting trioxymethylene, paraformaldehyde to be the formaldehyde raw materials, formaldehyde polymerization, and feeding system easily blocks up, and follow-up separation is difficult, and the whole operation stability of device is poor, economic benefits a great deal of problem such as poor. In addition, in the methyl methacrylate process by the ester-aldehyde method, the conversion rate of methyl acrylate generated by the reaction of methyl acetate and formaldehyde and methyl methacrylate generated by the reaction of methyl propionate and formaldehyde are not high, the crude methyl acrylate product gas and the crude methyl methacrylate product gas both contain more unreacted formaldehyde and methanol solvents and a small amount of by-product components with similar properties, the crude methyl acrylate product gas and the crude methyl methacrylate product gas are respectively separated and purified, the whole process flow is complex, and the energy consumption of the device is high.
Disclosure of Invention
Aiming at the technical problems in the methyl methacrylate process by the ester-aldehyde method, the invention provides a method and a device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate, and the method and the device have the characteristics of easy feeding, simplified process and low energy consumption.
In one aspect, the embodiments of the present invention provide a method for jointly producing anhydrous gaseous formaldehyde and methyl methacrylate, comprising:
oxidizing methanol to prepare formaldehyde solution;
preparing anhydrous gas-phase formaldehyde from the formaldehyde solution by concentration and extractive distillation;
reacting anhydrous gas-phase formaldehyde with methyl acetate to prepare a MA crude product;
concentrating the MA crude product obtained by the reaction through azeotropic distillation and extractive distillation to remove formaldehyde in the MA crude product;
carrying out hydrogenation reaction and MP separation on the concentrated MA crude product to obtain MP, and recovering methanol as a solvent for reacting anhydrous gas-phase formaldehyde with methyl acetate;
reacting the obtained MP with anhydrous gas-phase formaldehyde prepared from a formaldehyde solution to obtain an MMA crude product;
separating and refining the generated MMA crude product through azeotropic rectification, three-solvent extraction and rectification; wherein the extractant for the three-solvent extraction comprises a formaldehyde-rich solution obtained by the MA concentration.
Optionally, the oxidation of methanol to produce a formaldehyde solution comprises:
oxidizing the methanol to prepare crude formaldehyde gas;
performing secondary absorption on the crude formaldehyde gas to obtain a formaldehyde solution, wherein the formaldehyde solution is used as a raw material for preparing anhydrous gas-phase formaldehyde, and an absorbent absorbed by the second stage in the secondary absorption comprises a dilute formaldehyde solution generated by preparing the anhydrous gas-phase formaldehyde;
and separating tail gas of the crude formaldehyde gas after secondary absorption, wherein the separated hydrogen is used as a raw material of the MA hydrogenation reaction.
Optionally, the formaldehyde solution is concentrated and extracted and rectified to prepare anhydrous gas phase formaldehyde, which comprises:
concentrating the formaldehyde solution recovered in the MMA separation and refining process, and mixing with the formaldehyde solution prepared by methanol oxidation;
further concentrating the mixed formaldehyde solution, and performing extractive distillation on the concentrated formaldehyde solution;
the extractant for extractive distillation is polyethylene glycol dimethyl ether, and the anhydrous gas phase formaldehyde distilled by extractive distillation is used as a raw material for preparing MA and MMA;
the extractant polyethylene glycol dimethyl ether is recovered for recycling;
the diluted methanol aqueous solution generated by the recovery of the extracting agent and the acid-containing waste liquid discharged intermittently are subjected to the MMA separation and refining steps for synergistic treatment.
Optionally, the MA crude product is subjected to extractive distillation in the concentration step by azeotropic distillation and extractive distillation;
the recycled washing water recovered by MMA separation and refining is used as an extracting agent.
Optionally, the MA crude product is subjected to a hydrogenation reaction and MP separation to obtain MP, comprising:
carrying out hydrogenation reaction on the concentrated MA to generate MP containing methanol, wherein the hydrogen part is separated from tail gas generated by methanol oxidation;
separating MP from the MP product containing methanol generated by the reaction through differential pressure azeotropic distillation;
combining crude methanol recovered by separating, refining and refining MMA into differential pressure azeotropic distillation for separation;
methanol recovered by differential pressure azeotropic distillation is respectively used as a circulating solvent for preparing MA, a supplementary solvent for preparing MMA and a raw material for preparing formaldehyde by oxidizing the methanol.
Optionally, MMA is separated and refined by azeotropic distillation, three-solvent extraction and distillation, including:
performing lightness removing treatment on the prepared MMA crude product;
extracting and separating the lightened MMA crude product by using water as a first extracting agent, using a formaldehyde-rich solution obtained by MA concentration as a second extracting agent and using MP as a third extracting agent, so as to remove unreacted formaldehyde, a small amount of methanol and trace propionic acid in the MMA crude product, and removing impurities of heavy ester and trace acetic acid by using three-solvent extraction;
carrying out steam stripping treatment on the tower kettle water phase subjected to the three-solvent extraction treatment, recovering a formaldehyde solution in the tower kettle subjected to the steam stripping treatment, and taking the formaldehyde solution as a raw material for preparing anhydrous gas-phase formaldehyde;
rectifying the stripped methanol-rich solution at the tower top, recovering methanol, carrying out differential pressure azeotropic rectification on the distilled methanol and MP generated in the methanol recovery and the MP containing methanol generated in the MA hydrogenation reaction, and recycling tower kettle water generated in the methanol recovery as an extracting agent;
carrying out dehydration treatment on the tower top oil phase subjected to the three-solvent extraction treatment, and returning tower top recovered water subjected to the dehydration treatment to be used as a first extracting agent for the three-solvent extraction;
deeply lightening the dehydrated MMA crude product to obtain crude MMA, recovering MP in the deep lightening treatment to be used as a reaction raw material for preparing MMA, and performing deacidification treatment on a formaldehyde solution in the three-solvent extraction as a third extractant;
and (3) carrying out MMA (methyl methacrylate) refining on the crude MMA after deep light removal to obtain polymer-grade MMA, and separating heavy components generated by MMA refining in a heavy component treatment system.
The embodiment of the invention also provides a device for jointly producing anhydrous gas-phase formaldehyde and methyl methacrylate, which comprises the following components:
a methanol oxidation unit for preparing a formaldehyde solution by methanol oxidation;
the gas-phase formaldehyde unit is connected with the methanol oxidation unit and is used for preparing anhydrous gas-phase formaldehyde by concentrating and extracting and rectifying the formaldehyde solution prepared by the methanol oxidation unit;
the MA reaction unit is connected with the gas-phase formaldehyde unit and is used for reacting the anhydrous gas-phase formaldehyde prepared by the gas-phase formaldehyde unit with methyl acetate to prepare a MA crude product;
the MA concentration unit is connected with the MA reaction unit and is used for concentrating the MA crude product prepared by the MA reaction unit through azeotropic rectification and extractive rectification to remove formaldehyde in the MA crude product;
the hydrogenation reaction and MP separation unit is connected with the MA concentration unit and is used for carrying out hydrogenation reaction and MP separation on the MA crude product after being concentrated by the MA concentration unit to obtain MP, and recovered methanol is used as a solvent to return to the MA reaction unit;
an MMA reaction unit connected with the hydrogenation reaction and MP separation unit and used for reacting the MP prepared by the hydrogenation reaction and MP separation unit with anhydrous gas-phase formaldehyde prepared by the gas-phase formaldehyde unit to prepare MMA;
an MMA separation and purification unit connected to the MMA reaction unit for separating and purifying MMA by azeotropic distillation, three-solvent extraction and distillation; wherein, the extractant adopted by the three-solvent extraction comprises a formaldehyde-rich solution obtained by concentrating the MA crude product by the MA concentration unit.
Optionally, the methanol oxidation unit comprises:
a formaldehyde reaction system for oxidizing methanol to produce a crude formaldehyde gas;
the bottom of the first absorption tower is connected with the formaldehyde reaction system, the first absorption tower is used for carrying out primary absorption on the prepared crude formaldehyde gas, a tower kettle of the first absorption tower outputs formaldehyde solution as a raw material for preparing anhydrous gas-phase formaldehyde, and tower kettle liquid of the first absorption tower circulates to the tower top to be in countercurrent contact with the crude formaldehyde gas;
the bottom of the second absorption tower is connected with the top of the first absorption tower, the second absorption tower is used for carrying out secondary absorption on the crude formaldehyde gas, the tower bottom liquid of the second absorption tower is partially circulated to the middle upper part of the second absorption tower for carrying out secondary absorption, and is partially sent to the first absorption tower for carrying out primary absorption, and the second absorption tower is connected with the gas-phase formaldehyde unit so as to receive the dilute formaldehyde solution generated by the gas-phase formaldehyde unit as a partial absorbent;
and the tail gas treatment system is connected with the top of the second absorption tower and is used for separating hydrogen in the tail gas of the second absorption tower by adopting pressure swing adsorption, and the separated hydrogen is conveyed to the hydrogenation reaction and MP separation unit and is used as a raw material of the hydrogenation reaction.
Optionally, the gas phase formaldehyde unit comprises:
a formaldehyde concentration system which is connected with the methanol oxidation unit and the MMA separation and purification unit respectively and is used for mixing the formaldehyde solution from the MMA separation and purification unit after being concentrated with the formaldehyde solution from the methanol oxidation unit and further concentrating the mixed formaldehyde solution; the formaldehyde concentration system is connected with the methanol oxidation unit so as to convey dilute formaldehyde generated by the formaldehyde concentration system to the methanol oxidation unit as an absorbent;
the formaldehyde rectifying tower is connected with the formaldehyde concentration system and is used for extracting and rectifying the formaldehyde solution which is further concentrated by the formaldehyde concentration system by using polyethylene glycol dimethyl ether as an extracting agent; the formaldehyde rectifying tower is respectively connected with the MA reaction unit and the MMA reaction unit, so that anhydrous gas-phase formaldehyde distilled from the formaldehyde rectifying tower is taken as reaction raw materials and is respectively conveyed to the MA reaction unit and the MMA reaction unit;
and the solvent recovery tower is connected with the formaldehyde rectifying tower and used for recovering the extracting agent and returning the extracting agent to the formaldehyde rectifying tower for recycling, and the solvent recovery tower is connected with the MMA separation and refining unit so as to convey the dilute methanol aqueous solution at the top of the solvent recovery tower and the acid-containing waste liquid intermittently discharged from the tower bottom to the MMA separation and refining unit for synergistic treatment.
Optionally, the MA concentration unit includes:
the MA light component removal tower is connected with the MA reaction unit and used for carrying out azeotropic rectification on the MA crude product from the MA reaction unit, and a distillate containing methyl acetate and methanol at the tower top of the MA light component removal tower is used as a reaction raw material and is returned to the MA reaction unit;
the MA rectifying tower is connected with the tower kettle of the MA light component removing tower and is used for extracting and rectifying tower kettle liquid of the MA light component removing tower; the MA rectifying tower is connected with the MMA separation and refining unit to receive the recycled washing water recovered by the MMA separation and refining unit as an extracting agent; the top of the MA rectifying tower is connected with the hydrogenation reaction and MP separation unit so as to output concentrated MA to the hydrogenation reaction and MP separation unit; and the tower kettle of the MA rectifying tower is connected with the MMA separation and refining unit so as to convey a formaldehyde-rich solution as a second extracting agent to the MMA separation and refining unit.
Optionally, the hydrogenation reaction and MP separation unit comprises:
the hydrogenation reactor is connected with the MA concentration unit and is used for carrying out hydrogenation reaction on the MA concentrated by the MA concentration unit to generate MP; the hydrogenation reactor is connected with the methanol oxidation unit to receive hydrogen separated from tail gas of the methanol oxidation unit as a reaction raw material;
the differential pressure azeotropic distillation system is connected with the hydrogenation reactor and is used for separating the MP generated by the hydrogenation reactor into the MP by differential pressure azeotropic distillation; the differential pressure azeotropic distillation system is connected with the MMA separation and refining unit so as to combine the methanol recovered from the MMA separation and refining unit with the MP for differential pressure azeotropic distillation; the differential pressure azeotropic distillation system is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that recovered methanol is used as a circulating solvent for preparing MA and returned to the MA reaction unit, the recovered methanol is used as a supplementary solvent and returned to the MMA reaction unit, and the recovered methanol is used as a raw material and conveyed to the methanol oxidation unit.
Optionally, the differential pressure azeotropic distillation system includes:
the MP pressurizing tower is connected with the hydrogenation reactor so as to perform pressurized azeotropic rectification on the MP generated by the hydrogenation reactor, and the tower kettle of the MP pressurizing tower is connected with the MMA reaction unit so as to send the MP of the tower kettle to the MMA reaction unit;
an MP pressurizing tower reflux tank which is connected with the MP pressurizing tower so as to take part of the liquid in the MP pressurizing tower reflux tank as reflux to the tower;
a methanol atmospheric tower connected with the MP pressure tower reflux tank so as to enable part of the liquid in the MP pressure tower reflux tank to enter the methanol atmospheric tower for further separation, and the methanol atmospheric tower is also connected with the MMA separation and refining unit so as to carry out atmospheric azeotropic distillation on the ester-containing methanol from the MMA separation and refining unit and the overhead product from the MP pressure tower; the tower kettle of the methanol atmospheric tower is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that the recovered methanol part of the tower kettle is used as a circulating solvent to return to the MA reaction unit, the recovered methanol part of the tower kettle is used as a supplementary solvent to return to the MMA reaction unit, and the recovered methanol part of the tower kettle is used as a raw material to return to the methanol oxidation unit;
a methanol atmospheric tower reboiler connected to the top of the MP pressure tower, for using an azeotrope of MP distilled from the top of the MP pressure tower and methanol as a heat source of the methanol atmospheric tower reboiler;
the MP pressurizing tower water cooler is connected with the methanol atmospheric tower reboiler and used for cooling the overhead azeotrope of the MP pressurizing tower subjected to heat exchange by the methanol atmospheric tower reboiler, and the MP pressurizing tower water cooler is connected with the MP pressurizing tower reflux tank so that the azeotrope cooled by the MP pressurizing tower water cooler enters the MP pressurizing tower reflux tank;
a methanol atmospheric tower air cooler connected to the top of the methanol atmospheric tower to cool the top gas phase of the methanol atmospheric tower;
a methanol atmospheric tower reflux tank connected to the methanol atmospheric tower air cooler to receive the top gas phase of the methanol atmospheric tower cooled by the methanol atmospheric tower air cooler, the methanol atmospheric tower reflux tank being connected to the methanol atmospheric tower to return the condensate in the methanol atmospheric tower reflux tank to the methanol atmospheric tower as reflux;
the methanol atmospheric tower water cooler is connected with the methanol atmospheric tower reflux tank so as to cool the tank top gas of the methanol atmospheric tower reflux tank by water;
a methanol atmospheric tower top tank connected to the methanol atmospheric tower water cooler to receive the top gas of the methanol atmospheric tower reflux tank cooled by the methanol atmospheric tower water cooler, the methanol atmospheric tower top tank connected to the MP pressure column to return tank bottoms condensate to the MP pressure column as a mixture of MP and methanol;
and the tail gas compressor is connected with the methanol normal-pressure tower top tank so as to compress the tank top gas of the methanol normal-pressure tower top tank, and the tail gas compressor is connected with the hydrogenation reactor so as to return the tank top gas compressed by the tail gas compressor to the hydrogenation reactor for cyclic utilization.
Optionally, the differential pressure azeotropic distillation system includes:
a methanol atmospheric tower connected with the hydrogenation reactor, the methanol atmospheric tower being further connected with the MMA separation and refining unit to subject the ester-containing methanol from the MMA separation and refining unit to atmospheric azeotropic distillation together with MA from the hydrogenation reactor; the tower kettle of the methanol atmospheric tower is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that the recovered methanol part of the tower kettle is used as a circulating solvent to return to the MA reaction unit, the recovered methanol part of the tower kettle is used as a supplementary solvent to return to the MMA reaction unit, and the recovered methanol part of the tower kettle is used as a raw material to return to the methanol oxidation unit;
the methanol atmospheric tower reboiler is connected with the methanol atmospheric tower and is used for heating the kettle liquid of the methanol atmospheric tower;
the methanol atmospheric tower air cooler is connected with the top of the methanol atmospheric tower so as to cool the top gas phase of the methanol atmospheric tower;
a methanol atmospheric tower reflux tank connected to the methanol atmospheric tower air cooler to receive the top gas phase of the methanol atmospheric tower cooled by the methanol atmospheric tower air cooler, the methanol atmospheric tower reflux tank being connected to the methanol atmospheric tower to return the condensate of the methanol atmospheric tower reflux tank as reflux to the methanol atmospheric tower;
the methanol atmospheric tower water cooler is connected with the methanol atmospheric tower reflux tank and is used for cooling the tank top gas of the methanol atmospheric tower reflux tank;
a methanol atmospheric tower top tank connected to the methanol atmospheric tower water cooler to receive the top gas of the methanol atmospheric tower reflux tank cooled by the methanol atmospheric tower water cooler;
the tail gas compressor is connected with the methanol atmospheric tower top tank so as to compress the tank top gas of the methanol atmospheric tower top tank, and the tail gas compressor is connected with the hydrogenation reactor so as to return the tank top gas compressed by the tail gas compressor to the hydrogenation reactor for cyclic utilization;
an MP pressurizing tower which is connected with the methanol atmospheric tower top tank and is used for pressurizing and azeotropically rectifying the mixture of the bottom MP of the methanol atmospheric tower top tank and the methanol; the top of the MP pressurized tower is connected with the methanol atmospheric tower reboiler, so that an azeotrope of MP and methanol distilled from the top of the MP pressurized tower is used as a heat source of the methanol atmospheric tower reboiler, and the kettle of the MP pressurized tower is connected with the MMA reaction unit, so that MP in the kettle is sent to the MMA reaction unit;
the MP pressurized tower water cooler is connected with the methanol atmospheric tower reboiler and is used for cooling the overhead azeotrope of the MP pressurized tower after heat exchange of the methanol atmospheric tower reboiler;
and the MP pressurizing tower reflux tank is connected with the MP pressurizing tower water cooler so that the azeotrope cooled by the MP pressurizing tower water cooler enters the MP pressurizing tower reflux tank, and the MP pressurizing tower reflux tank is connected with the MP pressurizing tower and the methanol atmospheric tower so that one part of the liquid in the MP pressurizing tower reflux tank returns to the MP pressurizing tower as reflux and the other part returns to the methanol atmospheric tower.
Optionally, the MMA separation and purification unit comprises:
an MMA-lightness removing column connected to the MMA reaction unit for subjecting the MMA crude product produced by the MMA reaction unit to azeotropic lightness removal, the top of the MMA lightness removing column being connected to the MMA reaction unit to return a distillate containing methyl propionate and methanol at the top as a reaction raw material to the MMA reaction unit;
a three-solvent extraction tower which is connected with a tower kettle of the MMA light component removal tower so as to extract tower kettle liquid of the MMA light component removal tower, wherein the solvent adopted by the three-solvent extraction tower comprises water added from the top of the three-solvent extraction tower, a formaldehyde-rich solution added from the upper part of the three-solvent extraction tower and recovered MP added from the bottom of the three-solvent extraction tower; the three-solvent extraction tower is connected with the MA concentration unit so as to take the formaldehyde-rich solution from the MA concentration unit as an extracting agent and carry out impurity removal treatment for removing heavy esters and trace acetic acid from the formaldehyde-rich solution;
the stripping tower is connected with the three-solvent extraction tower and is used for carrying out stripping treatment on a tower bottom water phase of the three-solvent extraction tower so as to remove methanol and light ester components in a formaldehyde water solution, the stripping tower is provided with a rectifying section and a water washing section positioned at the upper part of the rectifying section, the water washing section adopts an extracting agent to wash a methanol gas phase of the rectifying section of the stripping tower, and a tower bottom of the stripping tower is connected with the gas-phase formaldehyde unit so as to send the formaldehyde solution of the tower bottom of the stripping tower to the gas-phase formaldehyde unit as a raw material for preparing anhydrous gas-phase formaldehyde;
the methanol recovery tower is connected with the tower top of the stripping tower, so that a methanol-rich fraction at the tower top of the stripping tower directly enters the methanol recovery tower to be rectified in a dew point state, the tower top of the methanol recovery tower is connected with the hydrogenation reaction and MP separation unit, so that a distillate containing methanol and MP at the tower top of the methanol recovery tower is sent to a differential pressure azeotropic rectification system of the hydrogenation reaction and MP separation unit to be subjected to synergistic treatment, and tower bottom water of the methanol recovery tower is recycled as an extracting agent;
a dehydration column connected to the top of the three-solvent extraction column to dehydrate the top oil phase of the three-solvent extraction column, wherein the top recovered water of the dehydration column is returned to the three-solvent extraction column as recycled washing water;
the top of the MP recovery tower is respectively connected with the MMA reaction unit and the bottom of the three-solvent extraction tower, so that part of MP recovered from the top of the MP recovery tower is returned to the MMA reaction unit as circulating MP and part of MP is returned to the bottom of the three-solvent extraction tower as a third extraction agent;
an MMA refining column connected with the tower kettle of the MP recovery column to refine the crude MMA of the tower kettle of the MP recovery column, wherein the tower top of the MMA refining column obtains polymerization-grade MMA;
a deacidification tower connected with the tower kettle of the MMA refining tower for further separating the heavy components from the tower kettle of the MMA refining tower, wherein the deacidification tower is connected with the gas-phase formaldehyde unit for cooperatively separating acid-containing waste liquid intermittently discharged from the gas-phase formaldehyde unit;
and the acid separation tower is connected with the tower top of the deacidification tower so as to clearly divide acetic acid and propionic acid components on the tower top of the deacidification tower, the acetic acid is obtained on the tower top of the acid separation tower, and the propionic acid is obtained in a tower kettle.
According to the method and the device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate, provided by the embodiment of the invention, by matching the anhydrous gas-phase formaldehyde process with the ester-aldehyde-method methyl methacrylate process, the problems that methyl acetate and formaldehyde react to prepare methyl acrylate and methyl propionate and formaldehyde react to prepare methyl methacrylate in the process route of the ester-aldehyde-method methyl methacrylate are difficult to feed are thoroughly solved. The methyl methacrylate process of the ester aldehyde method adopts gas-phase formaldehyde as a reaction raw material, and reduces methanol solvents used in the MA reaction and the MMA reaction, thereby reducing the raw material vaporization cost and the subsequent product separation difficulty; the joint production of anhydrous gas-phase formaldehyde and methyl methacrylate by an ester-aldehyde method ensures that byproduct streams and unreacted raw materials of each unit of the joint device are subjected to synergistic separation, impurity removal and utilization, thereby simplifying the device and greatly saving the energy consumption and material consumption in the production process.
Drawings
FIG. 1 is a block flow diagram of a process for the co-production of anhydrous gaseous formaldehyde and methyl methacrylate according to one embodiment of the present invention;
FIG. 2 is a schematic diagram of a methanol oxidation unit in an anhydrous gaseous formaldehyde and methyl methacrylate co-production apparatus according to an embodiment of the present invention;
FIG. 3 is a schematic diagram showing the structure of a vapor-phase formaldehyde unit in an apparatus for the co-production of anhydrous vapor-phase formaldehyde and methyl methacrylate according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of the MA concentration unit of the apparatus for the combined production of anhydrous gaseous formaldehyde and methyl methacrylate according to one embodiment of the present invention;
FIG. 5 is a schematic diagram of the hydrogenation and MP separation unit in an anhydrous gaseous formaldehyde and methyl methacrylate co-production plant according to one embodiment of the present invention;
FIG. 6 is a schematic diagram of the hydrogenation and MP separation unit in a combined anhydrous vapor-phase formaldehyde and methyl methacrylate production plant according to another embodiment of the present invention;
FIG. 7 is a schematic diagram showing the construction of an MMA separation and purification unit in an apparatus for the co-production of anhydrous gaseous formaldehyde and methyl methacrylate provided as an embodiment of the present invention;
in the figure: a 100-methanol oxidation unit; 200-a gas phase formaldehyde unit; a 300-MA reaction unit; 400-MA concentration unit; 500-hydrogenation reaction and MP separation unit; 600-MMA reaction unit; 700-MMA separation and purification unit; t101-a first absorption tower; t102-a second absorption tower; a T201-formaldehyde rectifying tower; t202-solvent recovery column; T401-MA lightness-removing tower; a T402-MA rectifying tower; R501A/S-hydrogenation reactor; T501A/S-MP pressurized column; T502A/S-methanol atmospheric tower; V501A/S-hydrogenation reactor steam pocket; V502A/S-knockout drum; V503A/S-MP pressure column reflux drum; V504A/S-methanol atmospheric tower reflux tank; V505A/S-methanol atmospheric overhead tank; K501A/S-recycle hydrogen compressor; K502A/S-tail gas compressor; T701-MMA light component removal tower; t702-a three-solvent extraction column; t703-stripper; t704-methanol recovery column; t705-dehydration column; T706-MP recovery column; T707-MMA refining column; t708-deacidification column; t709-acid separation column.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings and the detailed description of embodiments of the invention, but is not intended to limit the invention.
Referring to fig. 1, the embodiment of the present invention provides a method for jointly producing anhydrous gas-phase formaldehyde and methyl methacrylate, comprising:
s1, oxidizing the methanol to prepare a formaldehyde solution;
s2, preparing anhydrous gas-phase formaldehyde by concentrating, extracting and rectifying the formaldehyde solution;
s3 anhydrous gas phase formaldehyde reacts with methyl acetate to prepare a crude product of Methyl Acrylate (MA);
concentrating the MA crude product obtained by the reaction of S4 through azeotropic distillation and extractive distillation to remove formaldehyde in the MA crude product;
carrying out hydrogenation reaction and MP separation on the MA crude product after the concentration of S5 to obtain methyl propionate (hereinafter referred to as MP for short), and recovering methanol to return to be used as a solvent for the reaction of anhydrous gas-phase formaldehyde and methyl acetate;
reacting the MP obtained from S6 with anhydrous gas-phase formaldehyde prepared from formaldehyde solution to obtain a crude product of Methyl Methacrylate (MMA);
separating and refining an MMA crude product generated by S7 through azeotropic distillation, three-solvent extraction and distillation; wherein, the extractant for the three-solvent extraction comprises a formaldehyde-rich solution obtained by MA concentration.
In the method for jointly producing anhydrous gas-phase formaldehyde and methyl methacrylate, the anhydrous gas-phase formaldehyde process and the ester-aldehyde-method methyl methacrylate process are matched, so that the problems of methyl acrylate preparation by the reaction of methyl acetate and formaldehyde and methyl methacrylate preparation by the reaction of methyl propionate and formaldehyde in the process route of the ester-aldehyde-method methyl methacrylate are thoroughly solved. The methyl methacrylate process of the ester aldehyde method adopts gas-phase formaldehyde as a reaction raw material, and reduces methanol solvents used in the MA reaction and the MMA reaction, thereby reducing the raw material vaporization cost and the subsequent product separation difficulty; the joint production of anhydrous gas-phase formaldehyde and methyl methacrylate by an ester-aldehyde method ensures that byproduct streams and unreacted raw materials of each unit of the joint device are subjected to synergistic separation, impurity removal and utilization, thereby simplifying the device and greatly saving the energy consumption and material consumption in the production process.
Optionally, the oxidation of methanol to produce a formaldehyde solution comprises:
oxidizing the methanol to prepare crude formaldehyde gas;
performing secondary absorption on the crude formaldehyde gas to obtain a formaldehyde solution, wherein the formaldehyde solution is used as a raw material for preparing anhydrous gas-phase formaldehyde, and an absorbent absorbed by the second stage in the secondary absorption comprises a dilute formaldehyde solution generated by preparing the anhydrous gas-phase formaldehyde;
and separating tail gas of the crude formaldehyde gas after secondary absorption, wherein the separated hydrogen is used as a raw material of the MA hydrogenation reaction.
Optionally, the formaldehyde solution is concentrated and extracted and rectified to prepare anhydrous gas phase formaldehyde, which comprises:
concentrating the formaldehyde solution recovered in the MMA separation and refining process, and mixing with the formaldehyde solution prepared by methanol oxidation;
further concentrating the mixed formaldehyde solution, and performing extractive distillation on the concentrated formaldehyde solution;
the extractant for extractive distillation is polyethylene glycol dimethyl ether, and the anhydrous gas phase formaldehyde distilled by extractive distillation is used as a raw material for preparing MA and MMA;
the extractant polyethylene glycol dimethyl ether is recovered for recycling;
the diluted methanol aqueous solution generated by the recovery of the extracting agent and the acid-containing waste liquid discharged intermittently are subjected to the MMA separation and refining steps for synergistic treatment.
Optionally, the MA crude product is subjected to extractive distillation in the concentration step by azeotropic distillation and extractive distillation;
the recycled washing water recovered by MMA separation and refining is used as an extracting agent.
Optionally, the MA crude product is subjected to a hydrogenation reaction and MP separation to obtain MP, comprising:
carrying out hydrogenation reaction on the concentrated MA to generate MP containing methanol, wherein the hydrogen part is separated from tail gas generated by methanol oxidation;
separating MP from the MP product containing methanol generated by the reaction through differential pressure azeotropic distillation;
the ester-containing methanol (crude methanol) which is recovered by separating, refining and refining MMA is merged into differential pressure azeotropic distillation for separation;
methanol recovered by differential pressure azeotropic distillation is respectively used as a circulating solvent for preparing MA, a supplementary solvent for preparing MMA and a raw material for preparing formaldehyde by oxidizing the methanol.
Optionally, MMA is separated and refined by azeotropic distillation, three-solvent extraction and distillation, including:
performing lightness removing treatment on the prepared MMA crude product;
extracting and separating the lightened MMA crude product by using water as a first extracting agent, using a formaldehyde-rich solution obtained by MA concentration as a second extracting agent and using MP as a third extracting agent, so as to remove unreacted formaldehyde, a small amount of methanol and trace propionic acid in the MMA crude product, and removing impurities of heavy ester and trace acetic acid by using three-solvent extraction;
carrying out steam stripping treatment on the tower kettle water phase subjected to the three-solvent extraction treatment, recovering a formaldehyde solution in the tower kettle subjected to the steam stripping treatment, and taking the formaldehyde solution as a raw material for preparing anhydrous gas-phase formaldehyde;
rectifying the stripped methanol-rich solution at the tower top, recovering methanol, carrying out differential pressure azeotropic rectification on the distilled methanol and MP generated in the methanol recovery and the MP containing methanol generated in the MA hydrogenation reaction, and recycling tower kettle water generated in the methanol recovery as an extracting agent;
carrying out dehydration treatment on the tower top oil phase subjected to the three-solvent extraction treatment, and returning tower top recovered water subjected to the dehydration treatment to be used as a first extracting agent for the three-solvent extraction;
deeply lightening the dehydrated MMA crude product to obtain crude MMA, recovering MP in the deep lightening treatment to be used as a reaction raw material for preparing MMA, and performing deacidification treatment on a formaldehyde solution in the three-solvent extraction as a third extractant;
and (3) carrying out MMA (methyl methacrylate) refining on the crude MMA after deep light removal to obtain polymer-grade MMA, and separating heavy components generated by MMA refining in a heavy component treatment system.
Referring to fig. 2 to 7, an apparatus for co-producing anhydrous gaseous formaldehyde and methyl methacrylate according to an embodiment of the present invention is provided, and the apparatus according to the embodiment of the present invention may be used to perform the method according to the above embodiment. The method of the embodiments of the present invention is used in understanding and explaining the apparatus of the embodiments of the present invention, and the apparatus of the embodiments of the present invention is also used in understanding and explaining the method of the embodiments of the present invention. The device of the embodiment of the invention comprises:
a methanol oxidation unit for preparing a formaldehyde solution by methanol oxidation;
the gas-phase formaldehyde unit is connected with the methanol oxidation unit and is used for preparing anhydrous gas-phase formaldehyde by concentrating and extracting and rectifying the formaldehyde solution prepared by the methanol oxidation unit;
the MA reaction unit is connected with the gas-phase formaldehyde unit and is used for reacting the anhydrous gas-phase formaldehyde prepared by the gas-phase formaldehyde unit with methyl acetate to prepare a MA crude product;
the MA concentration unit is connected with the MA reaction unit and is used for concentrating the MA crude product prepared by the MA reaction unit through azeotropic rectification and extractive rectification to remove formaldehyde in the MA crude product;
the hydrogenation reaction and MP separation unit is connected with the MA concentration unit and is used for carrying out hydrogenation reaction and MP separation on the MA crude product after being concentrated by the MA concentration unit to obtain MP, and recovered methanol is used as a solvent to return to the MA reaction unit;
an MMA reaction unit connected with the hydrogenation reaction and MP separation unit and used for reacting the MP prepared by the hydrogenation reaction and MP separation unit with anhydrous gas-phase formaldehyde prepared by the gas-phase formaldehyde unit to prepare MMA;
an MMA separation and purification unit connected to the MMA reaction unit for separating and purifying MMA by azeotropic distillation, three-solvent extraction and distillation; wherein, the extractant adopted by the three-solvent extraction comprises a formaldehyde-rich solution obtained by concentrating the MA crude product by the MA concentration unit.
Optionally, the methanol oxidation unit comprises:
a formaldehyde reaction system for oxidizing methanol to produce a crude formaldehyde gas;
the bottom of the first absorption tower is connected with the formaldehyde reaction system, the first absorption tower is used for carrying out primary absorption on the prepared crude formaldehyde gas, a tower kettle of the first absorption tower outputs formaldehyde solution as a raw material for preparing anhydrous gas-phase formaldehyde, and tower kettle liquid of the first absorption tower circulates to the tower top to be in countercurrent contact with the crude formaldehyde gas;
the bottom of the second absorption tower is connected with the top of the first absorption tower, the second absorption tower is used for carrying out secondary absorption on the crude formaldehyde gas, the tower bottom liquid of the second absorption tower is partially circulated to the middle upper part of the second absorption tower for carrying out secondary absorption, and is partially sent to the first absorption tower for carrying out primary absorption, and the second absorption tower is connected with the gas-phase formaldehyde unit so as to receive the dilute formaldehyde solution generated by the gas-phase formaldehyde unit as a partial absorbent;
and the tail gas treatment system is connected with the top of the second absorption tower and is used for separating hydrogen in the tail gas of the second absorption tower by adopting pressure swing adsorption, and the separated hydrogen is conveyed to the hydrogenation reaction and MP separation unit and is used as a raw material of the hydrogenation reaction.
Optionally, the gas phase formaldehyde unit comprises:
a formaldehyde concentration system which is connected with the methanol oxidation unit and the MMA separation and purification unit respectively and is used for mixing the formaldehyde solution from the MMA separation and purification unit after being concentrated with the formaldehyde solution from the methanol oxidation unit and further concentrating the mixed formaldehyde solution; the formaldehyde concentration system is connected with the methanol oxidation unit so as to convey dilute formaldehyde generated by the formaldehyde concentration system to the methanol oxidation unit as an absorbent;
the formaldehyde rectifying tower is connected with the formaldehyde concentration system and is used for extracting and rectifying the formaldehyde solution which is further concentrated by the formaldehyde concentration system by using polyethylene glycol dimethyl ether as an extracting agent; the formaldehyde rectifying tower is respectively connected with the MA reaction unit and the MMA reaction unit, so that anhydrous gas-phase formaldehyde distilled from the formaldehyde rectifying tower is taken as reaction raw materials and is respectively conveyed to the MA reaction unit and the MMA reaction unit;
and the solvent recovery tower is connected with the formaldehyde rectifying tower and used for recovering the extracting agent and returning the extracting agent to the formaldehyde rectifying tower for recycling, and the solvent recovery tower is connected with the MMA separation and refining unit so as to convey the dilute methanol aqueous solution at the top of the solvent recovery tower and the acid-containing waste liquid intermittently discharged from the tower bottom to the MMA separation and refining unit for synergistic treatment.
Optionally, the MA concentration unit includes:
the MA light component removal tower is connected with the MA reaction unit and used for carrying out azeotropic rectification on the MA crude product from the MA reaction unit, and a distillate containing methyl acetate and methanol at the tower top of the MA light component removal tower is used as a reaction raw material and is returned to the MA reaction unit;
the MA rectifying tower is connected with the tower kettle of the MA light component removing tower and is used for extracting and rectifying tower kettle liquid of the MA light component removing tower; the MA rectifying tower is connected with the MMA separation and refining unit to receive the recycled washing water recovered by the MMA separation and refining unit as an extracting agent; the top of the MA rectifying tower is connected with the hydrogenation reaction and MP separation unit so as to output concentrated MA to the hydrogenation reaction and MP separation unit; and the tower kettle of the MA rectifying tower is connected with the MMA separation and refining unit so as to convey a formaldehyde-rich solution as a second extracting agent to the MMA separation and refining unit.
Optionally, the hydrogenation reaction and MP separation unit comprises:
the hydrogenation reactor is connected with the MA concentration unit and is used for carrying out hydrogenation reaction on the MA concentrated by the MA concentration unit to generate MP; the hydrogenation reactor is connected with the methanol oxidation unit to receive hydrogen separated from tail gas of the methanol oxidation unit as a reaction raw material;
the differential pressure azeotropic distillation system is connected with the hydrogenation reactor and is used for separating the MP generated by the hydrogenation reactor into the MP by differential pressure azeotropic distillation; the differential pressure azeotropic distillation system is connected with the MMA separation and refining unit so as to combine the methanol recovered from the MMA separation and refining unit with the MP for differential pressure azeotropic distillation; the differential pressure azeotropic distillation system is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that recovered methanol is used as a circulating solvent for preparing MA and returned to the MA reaction unit, the recovered methanol is used as a supplementary solvent and returned to the MMA reaction unit, and the recovered methanol is used as a raw material and conveyed to the methanol oxidation unit.
Optionally, the differential pressure azeotropic distillation system includes:
the MP pressurizing tower is connected with the hydrogenation reactor so as to perform pressurized azeotropic rectification on the MP generated by the hydrogenation reactor, and the tower kettle of the MP pressurizing tower is connected with the MMA reaction unit so as to send the MP of the tower kettle to the MMA reaction unit;
an MP pressurizing tower reflux tank which is connected with the MP pressurizing tower so as to take part of the liquid in the MP pressurizing tower reflux tank as reflux to the tower;
a methanol atmospheric tower connected with the MP pressure tower reflux tank so as to enable part of the liquid in the MP pressure tower reflux tank to enter the methanol atmospheric tower for further separation, and the methanol atmospheric tower is also connected with the MMA separation and refining unit so as to carry out atmospheric azeotropic distillation on the ester-containing methanol from the MMA separation and refining unit and the overhead product from the MP pressure tower; the tower kettle of the methanol atmospheric tower is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that the recovered methanol part of the tower kettle is used as a circulating solvent to return to the MA reaction unit, the recovered methanol part of the tower kettle is used as a supplementary solvent to return to the MMA reaction unit, and the recovered methanol part of the tower kettle is used as a raw material to return to the methanol oxidation unit;
a methanol atmospheric tower reboiler connected to the top of the MP pressure tower, for using an azeotrope of MP distilled from the top of the MP pressure tower and methanol as a heat source of the methanol atmospheric tower reboiler;
the MP pressurizing tower water cooler is connected with the methanol atmospheric tower reboiler and used for cooling the overhead azeotrope of the MP pressurizing tower subjected to heat exchange by the methanol atmospheric tower reboiler, and the MP pressurizing tower water cooler is connected with the MP pressurizing tower reflux tank so that the azeotrope cooled by the MP pressurizing tower water cooler enters the MP pressurizing tower reflux tank;
a methanol atmospheric tower air cooler connected to the top of the methanol atmospheric tower to cool the top gas phase of the methanol atmospheric tower;
a methanol atmospheric tower reflux tank connected to the methanol atmospheric tower air cooler to receive the top gas phase of the methanol atmospheric tower cooled by the methanol atmospheric tower air cooler, the methanol atmospheric tower reflux tank being connected to the methanol atmospheric tower to return the condensate in the methanol atmospheric tower reflux tank to the methanol atmospheric tower as reflux;
the methanol atmospheric tower water cooler is connected with the methanol atmospheric tower reflux tank so as to cool the tank top gas of the methanol atmospheric tower reflux tank by water;
a methanol atmospheric tower top tank connected to the methanol atmospheric tower water cooler to receive the top gas of the methanol atmospheric tower reflux tank cooled by the methanol atmospheric tower water cooler, the methanol atmospheric tower top tank connected to the MP pressure column to return tank bottoms condensate to the MP pressure column as a mixture of MP and methanol;
and the tail gas compressor is connected with the methanol normal-pressure tower top tank so as to compress the tank top gas of the methanol normal-pressure tower top tank, and the tail gas compressor is connected with the hydrogenation reactor so as to return the tank top gas compressed by the tail gas compressor to the hydrogenation reactor for cyclic utilization.
Optionally, the differential pressure azeotropic distillation system includes:
a methanol atmospheric tower connected with the hydrogenation reactor, the methanol atmospheric tower being further connected with the MMA separation and refining unit to subject the ester-containing methanol from the MMA separation and refining unit to atmospheric azeotropic distillation together with MA from the hydrogenation reactor; the tower kettle of the methanol atmospheric tower is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that the recovered methanol part of the tower kettle is used as a circulating solvent to return to the MA reaction unit, the recovered methanol part of the tower kettle is used as a supplementary solvent to return to the MMA reaction unit, and the recovered methanol part of the tower kettle is used as a raw material to return to the methanol oxidation unit;
the methanol atmospheric tower reboiler is connected with the methanol atmospheric tower and is used for heating the kettle liquid of the methanol atmospheric tower;
the methanol atmospheric tower air cooler is connected with the top of the methanol atmospheric tower so as to cool the top gas phase of the methanol atmospheric tower;
a methanol atmospheric tower reflux tank connected to the methanol atmospheric tower air cooler to receive the top gas phase of the methanol atmospheric tower cooled by the methanol atmospheric tower air cooler, the methanol atmospheric tower reflux tank being connected to the methanol atmospheric tower to return the condensate of the methanol atmospheric tower reflux tank as reflux to the methanol atmospheric tower;
the methanol atmospheric tower water cooler is connected with the methanol atmospheric tower reflux tank and is used for cooling the tank top gas of the methanol atmospheric tower reflux tank;
a methanol atmospheric tower top tank connected to the methanol atmospheric tower water cooler to receive the top gas of the methanol atmospheric tower reflux tank cooled by the methanol atmospheric tower water cooler;
the tail gas compressor is connected with the methanol atmospheric tower top tank so as to compress the tank top gas of the methanol atmospheric tower top tank, and the tail gas compressor is connected with the hydrogenation reactor so as to return the tank top gas compressed by the tail gas compressor to the hydrogenation reactor for cyclic utilization;
an MP pressurizing tower which is connected with the methanol atmospheric tower top tank and is used for pressurizing and azeotropically rectifying the mixture of the bottom MP of the methanol atmospheric tower top tank and the methanol; the top of the MP pressurized tower is connected with the methanol atmospheric tower reboiler, so that an azeotrope of MP and methanol distilled from the top of the MP pressurized tower is used as a heat source of the methanol atmospheric tower reboiler, and the kettle of the MP pressurized tower is connected with the MMA reaction unit, so that MP in the kettle is sent to the MMA reaction unit;
the MP pressurized tower water cooler is connected with the methanol atmospheric tower reboiler and is used for cooling the overhead azeotrope of the MP pressurized tower after heat exchange of the methanol atmospheric tower reboiler;
and the MP pressurizing tower reflux tank is connected with the MP pressurizing tower water cooler so that the azeotrope cooled by the MP pressurizing tower water cooler enters the MP pressurizing tower reflux tank, and the MP pressurizing tower reflux tank is connected with the MP pressurizing tower and the methanol atmospheric tower so that one part of the liquid in the MP pressurizing tower reflux tank returns to the MP pressurizing tower as reflux and the other part returns to the methanol atmospheric tower.
Optionally, the MMA separation and purification unit comprises:
an MMA-lightness removing column connected to the MMA reaction unit for subjecting the MMA crude product produced by the MMA reaction unit to azeotropic lightness removal, the top of the MMA lightness removing column being connected to the MMA reaction unit to return a distillate containing methyl propionate and methanol at the top as a reaction raw material to the MMA reaction unit;
a three-solvent extraction tower which is connected with a tower kettle of the MMA light component removal tower so as to extract tower kettle liquid of the MMA light component removal tower, wherein the solvent adopted by the three-solvent extraction tower comprises water added from the top of the three-solvent extraction tower, a formaldehyde-rich solution added from the upper part of the three-solvent extraction tower and recovered MP added from the bottom of the three-solvent extraction tower; the three-solvent extraction tower is connected with the MA concentration unit so as to take the formaldehyde-rich solution from the MA concentration unit as an extracting agent and carry out impurity removal treatment for removing heavy esters and trace acetic acid from the formaldehyde-rich solution;
the stripping tower is connected with the three-solvent extraction tower and is used for carrying out stripping treatment on a tower bottom water phase of the three-solvent extraction tower so as to remove methanol and light ester components in a formaldehyde water solution, the stripping tower is provided with a rectifying section and a water washing section positioned at the upper part of the rectifying section, the water washing section adopts an extracting agent to wash a methanol gas phase of the rectifying section of the stripping tower, and a tower bottom of the stripping tower is connected with the gas-phase formaldehyde unit so as to send the formaldehyde solution of the tower bottom of the stripping tower to the gas-phase formaldehyde unit as a raw material for preparing anhydrous gas-phase formaldehyde;
the methanol recovery tower is connected with the tower top of the stripping tower, so that a methanol-rich fraction at the tower top of the stripping tower directly enters the methanol recovery tower to be rectified in a dew point state, the tower top of the methanol recovery tower is connected with the hydrogenation reaction and MP separation unit, so that a distillate containing methanol and MP at the tower top of the methanol recovery tower is sent to a differential pressure azeotropic rectification system of the hydrogenation reaction and MP separation unit to be subjected to synergistic treatment, and tower bottom water of the methanol recovery tower is recycled as an extracting agent;
a dehydration column connected to the top of the three-solvent extraction column to dehydrate the top oil phase of the three-solvent extraction column, wherein the top recovered water of the dehydration column is returned to the three-solvent extraction column as recycled washing water;
the top of the MP recovery tower is respectively connected with the MMA reaction unit and the bottom of the three-solvent extraction tower, so that part of MP recovered from the top of the MP recovery tower is returned to the MMA reaction unit as circulating MP and part of MP is returned to the bottom of the three-solvent extraction tower as a third extraction agent;
an MMA refining column connected with the tower kettle of the MP recovery column to refine the crude MMA of the tower kettle of the MP recovery column, wherein the tower top of the MMA refining column obtains polymerization-grade MMA;
a deacidification tower which is connected with the tower kettle of the MMA refining tower so as to further separate the heavy components from the tower kettle of the MMA refining tower, and the deacidification tower is connected with the gas-phase formaldehyde unit so as to cooperatively separate the acid-containing waste liquid intermittently discharged from the gas-phase formaldehyde unit;
and the acid separation tower is connected with the tower top of the deacidification tower so as to clearly divide acetic acid and propionic acid components on the tower top of the deacidification tower, the acetic acid is obtained on the tower top of the acid separation tower, and the propionic acid is obtained in a tower kettle.
The scheme and effect of the method and apparatus of the present invention are further described below with reference to specific embodiments.
In some embodiments, as shown in fig. 2, the methanol oxidation unit 100 performs the oxidation reaction by using air 101, methanol 102, and a small amount of byproduct methanol 131 returned from the hydrogenation and MP separation unit 500 as raw materials. The reaction gas enters the bottom of the first absorption tower T101 after being quenched and cooled, and is in countercurrent contact with absorption liquid from the second absorption tower T102 and circulating liquid of the first absorption tower T101, most of formaldehyde gas is absorbed in the first absorption tower T101, and formaldehyde solution 106 with common concentration is extracted from the tower kettle and used as a raw material to be removed to the gas-phase formaldehyde unit 200. The overhead gas of the first absorption tower T101 enters the bottom of the second absorption tower T102, and is contacted with dilute formaldehyde 107 (partially replacing the required desalted water) from the gas-phase formaldehyde unit 200 and desalted water 103 at the top in a counter-current manner to continue absorption. And in the top gas tail gas removal treatment system of the second absorption tower T102, valuable hydrogen 105 is separated by adopting a pressure swing adsorption technology and is used as a raw material of a hydrogenation reaction, and waste gas 104 is discharged.
In some embodiments, the methanol oxidation unit 100 uses the dilute formaldehyde 107 from the gas-phase formaldehyde unit 200 to partially replace the desalted water required by the second absorption tower T102, thereby reducing the consumption of desalted water and finding a way for the byproduct low-concentration formaldehyde. The tail gas generated by the methanol oxidation unit 100 which can only be used as waste gas originally is treated by adopting a pressure swing adsorption technology, and valuable hydrogen is separated to be used as a hydrogenation raw material, so that the hydrogen consumption is reduced, and the economy of the whole device is improved.
In some embodiments, as shown in FIG. 3, the vapor phase formaldehyde unit 200 concentrates the formaldehyde solution 110 from the MMA separation and purification unit 700 and combines it with the common formaldehyde solution 106 from the methanol oxidation unit 100. The mixed formaldehyde solution is further concentrated, so that the formaldehyde enters a formaldehyde rectifying tower T201 at a higher concentration, and the purity of the anhydrous gas-phase formaldehyde is improved. The resulting dilute formaldehyde 107 serves as the absorbent methanol oxidation unit 100. The formaldehyde concentration equipment is preferably a vacuum falling film evaporator; the formaldehyde rectification column T201 is operated under vacuum. The operation pressure is preferably 40-150mmHg, the upper part of the formaldehyde rectifying tower T201 is an extraction section, and the lower part is a rectifying section. The extractant polyethylene glycol dimethyl ether 108 is added from the upper part of the column. The anhydrous gaseous formaldehyde product 109 distilled off from the formaldehyde rectification column T201 was fed as a reaction raw material to the MA reaction unit 300 and the MMA reaction unit 600, respectively. The tower bottom liquid of the formaldehyde rectifying tower T201 is pumped to a solvent recovery tower T202 after being pressurized. The solvent recovery column T202 is also operated under vacuum. The top dilute methanol aqueous solution 111 is sent to a downstream methanol recovery tower T704 for further processing. The tower kettle of the solvent recovery tower T202 is recovered polyethylene glycol dimethyl ether, and the recovered polyethylene glycol dimethyl ether is pumped and pressurized to be used as an extracting agent for recycling. A small amount of the acid-containing waste liquid 112 discharged intermittently from the column bottom of the solvent recovery column T202 is sent to the heavy component treatment system of the MMA separation and purification unit 700.
In some embodiments, the gas-phase formaldehyde unit 200 can continuously obtain stable high-purity formaldehyde gas by extractive distillation with polyethylene glycol dimethyl ether, thereby simplifying the production steps. The produced anhydrous gas-phase formaldehyde can be directly mixed with methyl acetate gas and methyl propionate gas respectively to react to produce methyl acrylate and methyl methacrylate products respectively. Therefore, the problems of easy blockage of equipment, high energy consumption and the like caused by depolymerization and vaporization of paraformaldehyde are avoided. And the adoption of the gas-phase formaldehyde raw material can also reduce the methanol solvent used in the MA reaction and the MMA reaction, thereby reducing the raw material vaporization cost and the subsequent product separation difficulty.
In some embodiments, the dilute methanol solution 111 produced by the gas-phase formaldehyde unit 200 and the formaldehyde solution of the MMA separation and purification unit 700 can be subjected to coupling separation and recovery, thereby simplifying the flow, and reducing the investment and energy consumption of the apparatus; the by-product low-concentration formaldehyde 107 of the gas-phase formaldehyde unit 200 is used as an absorbent to partially replace desalted water required by the second absorption tower T102, and the economy of the combined device is further improved.
In some embodiments, as shown in fig. 1, the MA reaction unit 300 heats and vaporizes the raw material methyl acetate 113, the recycle methanol 117, and the light component 116 returned from the MA concentration unit 400, and then mixes the vaporized raw material with the anhydrous gas phase formaldehyde 114, the mixed raw material is heated to 300-400 ℃ to perform a gas-solid phase reaction to generate methyl acrylate, and the generated MA crude product gas 115 is sent to the downstream MA concentration unit 400 after recovering heat and cooling to a preset temperature.
In some embodiments, as shown in fig. 4, the MA concentration unit 400 performs azeotropic distillation on the MA raw product gas 115 through a MA lightness-removing column T401, and a distillate 116 containing methyl acetate and methanol at the column top is returned to the MA reaction unit 300 as a reaction raw material, and the non-condensable gas 118 is sent out. And (3) feeding the tower bottom liquid of the MA light component removal tower T401 to an MA rectifying tower T402 for extraction and rectification treatment, wherein the extractant adopts circulating washing water 120 recovered by an MMA separation and refining unit 700, and the material flow 119 is fresh water supplement of the extractant. The top of the MA rectifying column T402 is the methanol-containing MA concentrate 121, which is sent to the hydrogenation and MP separation unit 500. The bottom of the MA rectifying column T402 is a formaldehyde-rich solution 122, which is sent as a second extractant to the MMA separation and purification unit 700.
In some embodiments, the gas phase at the top of the MA light component removal tower T401 is cooled to 50-90 ℃ by an air cooler, condensate is returned to the MA light component removal tower T401 as reflux, the gas is cooled to 30-60 ℃ by a water cooler at the top of the MA light component removal tower and enters a top tank of the MA light component removal tower, and condensate at the bottom of the tank is returned to the MA reaction unit as a raw material for recovering methyl acetate. Because the tower top adopts a two-stage condensation scheme, methyl acetate and methanol are mostly condensed in the first stage, most of heat load is concentrated, and the final heat transfer temperature of the first-stage condensation is higher, a more energy-saving air cooling scheme can be adopted, so that the circulating water consumption of a water cooler of the MA light component removal tower is greatly reduced, and the energy consumption of the whole device can be reduced.
In some embodiments, the formaldehyde-rich solution 122 is fed to the MA distillation column T402 from the bottom thereof as the second extractant to the MMA separation and purification unit 700 for cooperative separation, impurity removal and utilization, thereby simplifying the apparatus and greatly saving energy and material consumption in the production process.
In some embodiments, as shown in fig. 5 and 6, the hydrogenation and MP separation unit 500 combines the fresh hydrogen 123 with the recovered hydrogen 105 and the recycle hydrogen, mixes with the enriched MA product 121, and then heats to 200 ℃ via the hydrogenation reactor feed and discharge heat exchangers and the feed heater to perform the hydrogenation reaction in the hydrogenation reactor R501A/S to generate the MP product. The hydrogenation reaction is an exothermic reaction, a tubular reactor of an in-tube reaction is adopted, heat is removed through a forced circulation type hot water generation steam system, the hydrogenation reaction heat can be timely and effectively taken out due to the large heat transfer area of the tubular reactor, a steam-water mixture from the top of the shell side of the tubular reactor enters a hydrogenation reactor steam drum V-501A/S for steam-water separation, a part of generated steam is used for heating raw materials, the other part of the generated steam is taken as byproduct steam 124 to be delivered out, make-up boiler feed water 144 enters the hydrogenation reactor steam drum V-501A/S, and hot water in the hydrogenation reactor steam drum V-501A/S is pumped and then returns to the bottom of the shell side of the hydrogenation reactor R501A/S. MP crude product gas enters a gas-liquid separation tank V502A/S for gas-liquid separation after heat exchange and cooling, the separated hydrogen is compressed to preset pressure by a recycle hydrogen compressor K501A/S and returns to a hydrogenation reactor R501/S for cyclic utilization, purge gas 125 is discharged intermittently, and bottom MP crude product of the gas-liquid separation tank V502A/S enters a differential pressure azeotropic rectification system after being pumped and pressed by a pump.
In some embodiments, as shown in fig. 5, when the mass concentration of methanol in the MA concentrated product is 10 to 40%, the hydrogenation reaction and MP separation unit 500 employs a differential pressure azeotropic distillation process with high pressure first and then normal pressure, and the specific process flow is as follows: the MP crude product from the gas-liquid separation tank V502A is firstly pressurized and azeotropy rectified in an MP pressurizing tower T501A, the operation pressure of the MP pressurizing tower T501A is preferably 500-1200KPa, azeotrope of MP and methanol distilled from the tower top is taken as a heat source of a reboiler of a methanol atmospheric tower, the heat exchange is carried out, then the heat exchange is carried out, the heat exchange is cooled to the preset temperature, the heat exchange is carried out, the heat exchange is sent into a reflux tank V503A of the MP pressurizing tower, one part of liquid in the reflux tank V503A of the MP pressurizing tower is taken as reflux return tower, the other part of liquid is sent into the methanol; the methanol atmospheric tower T502A is used for carrying out atmospheric azeotropic distillation on the overhead distillate from the MP pressure tower T501A, a small amount of ester-containing methanol 126 from the MMA separation and purification unit 700 is merged into the methanol atmospheric tower T502A for synergistic separation, the operating pressure of the methanol atmospheric tower T502A is preferably 100-400KPa, the overhead gas phase of the methanol atmospheric tower T502A is cooled to the preset temperature by a methanol atmospheric tower air cooler and then enters a methanol atmospheric tower reflux tank V504A, the condensate of the methanol atmospheric tower reflux tank V504A is returned to the tower as reflux, the tank top gas of the methanol atmospheric tower reflux tank V504A is cooled to 30-60 ℃ by circulating water and then enters the methanol atmospheric tower top tank V505A, the tank bottom condensate of the methanol atmospheric tower top tank V505A is a mixture of MP and methanol and then is returned to the MP pressure tower T501A; the top gas of the methanol atmospheric tower top tank V505A is compressed to a preset pressure by a tail gas compressor K502A and returns to a hydrogenation reactor R501A for cyclic utilization; the bottom liquid of the methanol atmospheric tower T502A is recovered methanol 127, most of the recovered methanol is returned to the MA reaction unit 300 as a circulating solvent, a small amount of the recovered methanol is returned to the MMA reaction unit 600 as a supplementary solvent, and the remaining small amount of byproduct methanol is used as a raw material methanol removal oxidation unit 100.
In other embodiments, as shown in fig. 6, when the mass concentration of methanol in the MA concentrated product is 30 to 90%, the hydrogenation reaction and MP separation unit 500 adopts a differential pressure azeotropic distillation process with normal pressure first and then high pressure, and the specific process flow is as follows: the MP crude product from the gas-liquid separation tank V502S is subjected to normal pressure azeotropic distillation in a methanol atmospheric tower T502S, a small amount of ester-containing methanol 126 from an MMA separation and refining unit 700 is merged into a methanol atmospheric tower T502S for synergistic separation, the operating pressure of the methanol atmospheric tower T502S is preferably 100-400KPa, the gas phase at the top of the methanol atmospheric tower T502S is cooled to the preset temperature by a methanol atmospheric tower air cooler and then enters a methanol atmospheric tower reflux tank V504S, the condensate of the methanol atmospheric tower reflux tank V504S is returned to the tower as reflux, the gas at the top of the methanol atmospheric tower reflux tank V504S is cooled to 30-60 ℃ by circulating water and then enters a methanol atmospheric tower top tank V505S, the condensate at the bottom of the methanol atmospheric tower top tank V505S is a mixture of MP and methanol and then is sent to a pressurizing MP tower T501S for further separation; the top gas of the methanol atmospheric tower top tank V505S is compressed to a preset pressure by a tail gas compressor K502S and returns to a hydrogenation reactor R501S for cyclic utilization; the tower bottom liquid of the methanol atmospheric tower T502S is recovered methanol 127, most of the recovered methanol is used as a circulating solvent and returns to the MA reaction unit 300, a small amount of the recovered methanol is used as a supplementary solvent and returns to the MMA reaction unit 600, and the remaining small amount of byproduct methanol is used as a raw material to remove methanol oxidation unit 100; the MP pressurizing tower T501S performs pressurizing azeotropic distillation on a mixture of bottom MP from a methanol atmospheric tower top tank V505S and methanol, the operating pressure of the MP pressurizing tower T501S is preferably 500-1200KPa, azeotrope of the overhead MP and the methanol is used as a heat source of a reboiler of the methanol atmospheric tower, the heat is exchanged and then cooled to a preset temperature by circulating water, the heat is sent to a MP pressurizing tower reflux tank V503S, one part of liquid in the tank of the MP pressurizing tower reflux tank V503S is returned to the tower as reflux, and the other part is returned to the methanol atmospheric tower T502S; the bottom of the MP pressure column T501S is MP product 128, which is sent to MMA reaction unit 600.
In some embodiments, the hydrogenation reactor R501A/S in the hydrogenation reaction and MP separation unit 500 is a tubular reactor with in-tube reaction, and heat is removed by a forced circulation hot water generation steam system, which ensures timely and effective removal of hydrogenation reaction heat and realizes comprehensive utilization of device energy due to the large heat transfer area of the tubular reactor.
In some embodiments, the crude MP product of the hydrogenation reaction and MP separation unit 500 mainly contains methanol, and the MP and methanol are pressure-sensitive azeotrope systems, and the Methyl Propionate (MP) and methanol are separated by using a differential pressure azeotropic distillation technology without introducing a third component, and are completely thermally coupled on the basis of the differential pressure azeotropic distillation, i.e. the heat required by the reboiler of the methanol atmospheric tower T502A/S is provided by the cold energy of the condenser of the MP pressurized tower T501A/S, thereby reducing the consumption of utilities of the differential pressure azeotropic distillation system to the maximum extent and saving the energy of the device.
In some embodiments, the top of the methanol atmospheric tower T502A/S in the hydrogenation reaction and MP separation unit 500 employs a two-stage condensation scheme, methyl propionate and methanol are mostly condensed in the first stage, so most of the heat load is concentrated, and the final heat transfer temperature of the first-stage condensation is higher, so that a more energy-saving air cooling scheme can be employed, which greatly reduces the circulating water consumption of the methanol atmospheric tower T502A/S water cooler, thereby further reducing the energy consumption of the whole apparatus.
In some embodiments, the hydrogen feed portion of the hydrogenation and MP separation unit 500 utilizes the hydrogen 105 recovered in the methanol oxidation unit 100 tail gas to improve overall plant economics; a small amount of ester-containing methanol 126 from the MMA separation and refining unit 700 is merged into a differential pressure azeotropic distillation system for synergistic separation, thereby simplifying the flow of the device; the byproduct methanol 130 is used as the raw material methanol removal oxidation unit 100, thereby further improving the economical efficiency of the device.
In some examples, as shown in FIG. 1, an MMA reaction unit 600 heats and vaporizes a raw material methyl propionate 128, a supplemental methanol 129, a light fraction 134 returned from an MMA separation and purification unit 700, and a recycled methyl propionate 137, and then mixes them with anhydrous gaseous formaldehyde 132, the mixed raw material is heated to 300 ℃ and 400 ℃ to carry out a gas-solid phase reaction to produce methyl methacrylate, and a produced MMA crude product gas 133 is subjected to heat recovery and cooling to a predetermined temperature and sent to a downstream MMA separation and purification unit 700.
In some examples, as shown in FIG. 7, an MMA separation and purification unit 700 sends an MMA crude product 133 from an MMA reaction unit 600 to an MMA lightener column T701 for azeotropic lighteness treatment, and a distillate 134 containing methyl propionate and methanol at the column top is returned as a reaction raw material to the MMA reaction unit 600, and a non-condensable gas 135 is sent out; extracting the bottom liquid of an MMA lightness removing tower T701 in a three-solvent extraction tower T702, namely respectively adopting water (added from the top), a formaldehyde-rich solution 122 (added from the middle upper part) and recovered MP (added from the bottom) to perform extraction and liquid separation treatment on a MMA crude product after lightness removing so as to remove unreacted formaldehyde, a small amount of methanol and a trace amount of propionic acid in the MMA product; meanwhile, the three-solvent extraction tower T702 has the impurity removal effect of removing heavy esters and trace acetic acid from the formaldehyde-rich solution 122 (namely, the second extractant) from the MA concentration unit; the dosage (mass) of the first extractant water is 0.2 to 6 times of the feeding dosage (mass), and the dosage (mass) of the third extractant methyl propionate is 0.1 to 5 times of the feeding dosage (mass).
In some embodiments, as shown in fig. 7, a stripping tower T703 performs stripping treatment on a tower bottom water phase of a three-solvent extraction tower T702 to remove methanol and a small amount of light ester components in a formaldehyde aqueous solution, a water washing section is arranged at an upper part of the stripping tower T703, a methanol gas phase at a rectification section of the stripping tower T703 is washed with an extractant (water) to avoid the methanol fraction at the tower top from carrying the formaldehyde components, the amount (mass) of the extractant water is 0.5-10 times of the feeding amount (mass), the stripping tower T703 is preferentially operated at normal pressure, for energy saving and consumption reduction, the methanol-rich fraction at the tower top directly enters a downstream methanol recovery tower T704 in a dew-point state, and a tower bottom of the stripping tower T703 is used for recovering the formaldehyde solution 110 and is sent to the gas-phase formaldehyde unit 200 as a raw material; the methanol recovery tower T704 is used for rectifying the tower top methanol-rich solution of the stripping tower T703, the methanol recovery tower T704 is preferably operated at normal pressure, the tower top distillate 126 is methanol and MP components and is sent to a differential pressure azeotropic rectification system of the hydrogenation and MP separation unit 500 for synergistic treatment, most of tower bottom water of the methanol recovery tower T704 is recycled as an extracting agent, and a small amount of tower bottom water is sent out as waste water 139.
In some embodiments, as shown in fig. 7, the dehydrating column T705 dehydrates the oil phase at the top of the three-solvent extraction column T702, and the water recovered at the top of the dehydrating column T705 is returned to the three-solvent extraction column T702 as recycled washing water; the MP recovery tower T706 carries out deep light removal treatment on the dehydrated MMA crude product, most of MP recovered from the tower top is returned to the MMA reaction unit 600 as recycled methyl propionate 137, the other small part is returned to the bottom of the three-solvent extraction tower T702 as a third extractant, and the tower bottom of the MP recovery tower T706 is a crude methyl methacrylate purification tower T707; the crude methyl methacrylate after deep lightness removal is refined by an MMA refining tower T707 to obtain polymer-grade methyl methacrylate 140 at the tower top, and the heavy component in the tower bottom is removed to an acid removal tower T708 of a heavy component treatment system.
In some embodiments, as shown in fig. 7, the deacidification tower T708 further separates the tower bottom heavy component from the MMA refining tower T707, the acid-containing waste liquid 112 intermittently discharged from the gas-phase formaldehyde unit 200 is combined to the deacidification tower T708 for synergistic separation, the acetic acid and propionic acid components are at the tower top of the deacidification tower T708 and are sent to the acid separation tower T709, and the tower bottom heavy component 141 of the deacidification tower T708 is sent out; the acid separation tower T709 carries out clear segmentation treatment on the acetic acid and propionic acid components from the acid removal tower T708, the acetic acid component 142 is obtained at the tower top, and the propionic acid component 143 is obtained at the tower bottom.
In some embodiments, the three-solvent extraction column T702 respectively uses water, the formaldehyde-rich solution 122, and recovered MP to perform extraction and liquid separation treatment on the crude MMA after light component removal, which can not only achieve the purpose of removing unreacted formaldehyde, a small amount of methanol, and a small amount of propionic acid in the MMA product, but also reduce the usage of extractant water; meanwhile, the methyl acrylate crude product gas and the methyl methacrylate crude product gas both contain more unreacted formaldehyde and methanol solvents and a small amount of by-product components with similar properties, so that the synergistic separation and impurity removal among units of the device become possible; the three-solvent extraction tower T702 has double effects of removing heavy esters and trace acetic acid on the formaldehyde-rich solution 122 from the MA concentration unit 400, and also has the function of coupling and recovering the formaldehyde solution, so that the whole device avoids the separation and impurity removal processes of the formaldehyde-rich solution 122 newly built in the MA concentration unit 400, thereby simplifying the process and reducing the energy consumption and material consumption of the device; in addition, a third extractant MP is added from the lower part of the three-solvent extraction tower T702, so that the deacidification effect of the lower-section water phase is further ensured.
In some embodiments, the methanol-rich fraction at the top of the stripping tower T703 directly enters the downstream methanol recovery tower T704 in a dew point state, so as to achieve the effects of energy saving and consumption reduction; the tower bottom formaldehyde solution 110 of the stripping tower T703 is used as a raw material for preparing anhydrous gas-phase formaldehyde, the tower top fraction 126 of the methanol recovery tower T704 is sent to a differential pressure azeotropic distillation system of a hydrogenation reaction and MP separation unit 500 for synergistic treatment, most of the tower bottom water of the methanol recovery tower is recycled as an extracting agent, and the acid-containing waste liquid 112 intermittently discharged from the gas-phase formaldehyde unit 200 is merged into an acid removal tower T708 for synergistic separation, and the above material flows also realize the synergistic separation, impurity removal and utilization among the units of the device, thereby further simplifying the flow and reducing the material consumption and energy consumption of the device.
In some embodiments, when the byproduct methanol 131 is used as a raw material and the impurity content thereof cannot meet the specification of the methanol oxidation unit 100, the byproduct methanol 130 is purified by adding a methanol purification system a to meet the raw material specification of the methanol oxidation unit 100, and the methanol purification system a is operated continuously or intermittently according to the production of the byproduct methanol 130.
The above description is intended to be illustrative and not restrictive. For example, the above-described examples (or one or more versions thereof) may be used in combination with each other. For example, other embodiments may be used by those of ordinary skill in the art upon reading the above description. In addition, in the above-described embodiments, various features may be grouped together to streamline the disclosure. This should not be interpreted as an intention that a disclosed feature not claimed is essential to any claim. Rather, inventive subject matter may lie in less than all features of a particular disclosed embodiment. Thus, the following claims are hereby incorporated into the detailed description as examples or embodiments, with each claim standing on its own as a separate embodiment, and it is contemplated that these embodiments may be combined with each other in various combinations or permutations. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.

Claims (14)

1. A process for the co-production of anhydrous gaseous formaldehyde and methyl methacrylate comprising:
oxidizing methanol to prepare formaldehyde solution;
preparing anhydrous gas-phase formaldehyde from the formaldehyde solution by concentration and extractive distillation;
reacting anhydrous gas-phase formaldehyde with methyl acetate to prepare a MA crude product;
concentrating the MA crude product obtained by the reaction through azeotropic distillation and extractive distillation to remove formaldehyde in the MA crude product;
carrying out hydrogenation reaction and MP separation on the concentrated MA crude product to obtain MP, and recovering methanol as a solvent for reacting anhydrous gas-phase formaldehyde with methyl acetate;
reacting the obtained MP with anhydrous gas-phase formaldehyde prepared from a formaldehyde solution to obtain an MMA crude product;
separating and refining the generated MMA crude product through azeotropic rectification, three-solvent extraction and rectification; wherein the extractant for the three-solvent extraction comprises a formaldehyde-rich solution obtained by the MA concentration.
2. The method of claim 1, wherein the oxidation of methanol to produce a formaldehyde solution comprises:
oxidizing the methanol to prepare crude formaldehyde gas;
performing secondary absorption on the crude formaldehyde gas to obtain a formaldehyde solution, wherein the formaldehyde solution is used as a raw material for preparing anhydrous gas-phase formaldehyde, and an absorbent absorbed by the second stage in the secondary absorption comprises a dilute formaldehyde solution generated by preparing the anhydrous gas-phase formaldehyde [ t1 ];
and separating tail gas of the crude formaldehyde gas after secondary absorption, wherein the separated hydrogen is used as a raw material of the MA hydrogenation reaction.
3. The process according to claim 1, wherein the formaldehyde solution is subjected to concentration and extractive distillation to produce anhydrous gaseous formaldehyde comprising:
concentrating the formaldehyde solution recovered in the MMA separation and refining process, and mixing with the formaldehyde solution prepared by methanol oxidation;
further concentrating the mixed formaldehyde solution, and performing extractive distillation on the concentrated formaldehyde solution;
the extractant for extractive distillation is polyethylene glycol dimethyl ether, and the anhydrous gas phase formaldehyde distilled by extractive distillation is used as a raw material for preparing MA and MMA;
the extractant polyethylene glycol dimethyl ether is recovered for recycling;
the diluted methanol aqueous solution generated by the recovery of the extracting agent and the acid-containing waste liquid discharged intermittently are subjected to the MMA separation and refining steps for synergistic treatment.
4. The process according to claim 1, wherein the MA crude product is subjected to extractive distillation of the concentration step by azeotropic distillation and extractive distillation;
the recycled washing water recovered by MMA separation and refining is used as an extracting agent.
5. The process of claim 1, wherein the MA crude product is subjected to hydrogenation and MP separation to obtain MP, comprising:
carrying out hydrogenation reaction on the concentrated MA to generate MP containing methanol, wherein the hydrogen part is separated from tail gas generated by methanol oxidation;
separating MP from the MP product containing methanol generated by the reaction through differential pressure azeotropic distillation;
combining crude methanol recovered by separating, refining and refining MMA into differential pressure azeotropic distillation for separation;
methanol recovered by differential pressure azeotropic distillation is respectively used as a circulating solvent for preparing MA, a supplementary solvent for preparing MMA and a raw material for preparing formaldehyde by oxidizing the methanol.
6. The process of claim 1, wherein MMA is separated and refined by azeotropic distillation, three-solvent extraction and distillation, comprising:
performing lightness removing treatment on the prepared MMA crude product;
extracting and separating the lightened MMA crude product by using water as a first extracting agent, using a formaldehyde-rich solution obtained by MA concentration as a second extracting agent and using MP as a third extracting agent, so as to remove unreacted formaldehyde, a small amount of methanol and trace propionic acid in the MMA crude product, and removing impurities of heavy ester and trace acetic acid by using three-solvent extraction;
carrying out steam stripping treatment on the tower kettle water phase subjected to the three-solvent extraction treatment, recovering a formaldehyde solution in the tower kettle subjected to the steam stripping treatment, and taking the formaldehyde solution as a raw material for preparing anhydrous gas-phase formaldehyde;
rectifying the stripped methanol-rich solution at the tower top, recovering methanol, carrying out differential pressure azeotropic rectification on the distilled methanol and MP generated in the methanol recovery and the MP containing methanol generated in the MA hydrogenation reaction, and recycling tower kettle water generated in the methanol recovery as an extracting agent;
carrying out dehydration treatment on the tower top oil phase subjected to the three-solvent extraction treatment, and returning tower top recovered water subjected to the dehydration treatment to be used as a first extracting agent for the three-solvent extraction;
deeply lightening the dehydrated MMA crude product to obtain crude MMA, recovering MP in the deep lightening treatment to be used as a reaction raw material for preparing MMA, and performing deacidification treatment on a formaldehyde solution in the three-solvent extraction as a third extractant;
and (3) carrying out MMA (methyl methacrylate) refining on the crude MMA after deep light removal to obtain polymer-grade MMA, and separating heavy components generated by MMA refining in a heavy component treatment system.
7. An apparatus for the co-production of anhydrous gaseous formaldehyde and methyl methacrylate, comprising:
a methanol oxidation unit for preparing a formaldehyde solution by methanol oxidation;
the gas-phase formaldehyde unit is connected with the methanol oxidation unit and is used for preparing anhydrous gas-phase formaldehyde by concentrating and extracting and rectifying the formaldehyde solution prepared by the methanol oxidation unit;
the MA reaction unit is connected with the gas-phase formaldehyde unit and is used for reacting the anhydrous gas-phase formaldehyde prepared by the gas-phase formaldehyde unit with methyl acetate to prepare a MA crude product;
the MA concentration unit is connected with the MA reaction unit and is used for concentrating the MA crude product prepared by the MA reaction unit through azeotropic rectification and extractive rectification to remove formaldehyde in the MA crude product;
the hydrogenation reaction and MP separation unit is connected with the MA concentration unit and is used for carrying out hydrogenation reaction and MP separation on the MA crude product after being concentrated by the MA concentration unit to obtain MP, and recovered methanol is used as a solvent to return to the MA reaction unit;
an MMA reaction unit connected with the hydrogenation reaction and MP separation unit and used for reacting the MP prepared by the hydrogenation reaction and MP separation unit with anhydrous gas-phase formaldehyde prepared by the gas-phase formaldehyde unit to prepare MMA;
an MMA separation and purification unit connected to the MMA reaction unit for separating and purifying MMA by azeotropic distillation, three-solvent extraction and distillation; wherein, the extractant adopted by the three-solvent extraction comprises a formaldehyde-rich solution obtained by concentrating the MA crude product by the MA concentration unit.
8. The apparatus of claim 7, wherein the methanol oxidation unit comprises:
a formaldehyde reaction system for oxidizing methanol to produce a crude formaldehyde gas;
the bottom of the first absorption tower is connected with the formaldehyde reaction system, the first absorption tower is used for carrying out primary absorption on the prepared crude formaldehyde gas, a tower kettle of the first absorption tower outputs formaldehyde solution as a raw material for preparing anhydrous gas-phase formaldehyde, and tower kettle liquid of the first absorption tower circulates to the tower top to be in countercurrent contact with the crude formaldehyde gas;
the bottom of the second absorption tower is connected with the top of the first absorption tower, the second absorption tower is used for carrying out secondary absorption on the crude formaldehyde gas, the tower bottom liquid of the second absorption tower is partially circulated to the middle upper part of the second absorption tower for carrying out secondary absorption, and is partially sent to the first absorption tower for carrying out primary absorption, and the second absorption tower is connected with the gas-phase formaldehyde unit so as to receive the dilute formaldehyde solution generated by the gas-phase formaldehyde unit as a partial absorbent;
and the tail gas treatment system is connected with the top of the second absorption tower and is used for separating hydrogen in the tail gas of the second absorption tower by adopting pressure swing adsorption, and the separated hydrogen is conveyed to the hydrogenation reaction and MP separation unit and is used as a raw material of the hydrogenation reaction.
9. The apparatus of claim 7, wherein the gas phase formaldehyde unit comprises:
a formaldehyde concentration system which is connected with the methanol oxidation unit and the MMA separation and purification unit respectively and is used for mixing the formaldehyde solution from the MMA separation and purification unit after being concentrated with the formaldehyde solution from the methanol oxidation unit and further concentrating the mixed formaldehyde solution; the formaldehyde concentration system is connected with the methanol oxidation unit so as to convey dilute formaldehyde generated by the formaldehyde concentration system to the methanol oxidation unit as an absorbent;
the formaldehyde rectifying tower is connected with the formaldehyde concentration system and is used for extracting and rectifying the formaldehyde solution which is further concentrated by the formaldehyde concentration system by using polyethylene glycol dimethyl ether as an extracting agent; the formaldehyde rectifying tower is respectively connected with the MA reaction unit and the MMA reaction unit, so that anhydrous gas-phase formaldehyde distilled from the formaldehyde rectifying tower is taken as reaction raw materials and is respectively conveyed to the MA reaction unit and the MMA reaction unit;
and the solvent recovery tower is connected with the formaldehyde rectifying tower and used for recovering the extracting agent and returning the extracting agent to the formaldehyde rectifying tower for recycling, and the solvent recovery tower is connected with the MMA separation and refining unit so as to convey the dilute methanol aqueous solution at the top of the solvent recovery tower and the acid-containing waste liquid intermittently discharged from the tower bottom to the MMA separation and refining unit for synergistic treatment.
10. The apparatus of claim 7, wherein the MA concentration unit comprises:
the MA light component removal tower is connected with the MA reaction unit and used for carrying out azeotropic rectification on the MA crude product from the MA reaction unit, and a distillate containing methyl acetate and methanol at the tower top of the MA light component removal tower is used as a reaction raw material and is returned to the MA reaction unit;
the MA rectifying tower is connected with the tower kettle of the MA light component removing tower and is used for extracting and rectifying tower kettle liquid of the MA light component removing tower; the MA rectifying tower is connected with the MMA separation and refining unit to receive the recycled washing water recovered by the MMA separation and refining unit as an extracting agent; the top of the MA rectifying tower is connected with the hydrogenation reaction and MP separation unit so as to output concentrated MA to the hydrogenation reaction and MP separation unit; and the tower kettle of the MA rectifying tower is connected with the MMA separation and refining unit so as to convey a formaldehyde-rich solution as a second extracting agent to the MMA separation and refining unit.
11. The apparatus of claim 7, wherein the hydrogenation reaction and MP separation unit comprises:
the hydrogenation reactor is connected with the MA concentration unit and is used for carrying out hydrogenation reaction on the MA concentrated by the MA concentration unit to generate MP; the hydrogenation reactor is connected with the methanol oxidation unit to receive hydrogen separated from tail gas of the methanol oxidation unit as a reaction raw material;
the differential pressure azeotropic distillation system is connected with the hydrogenation reactor and is used for separating the MP generated by the hydrogenation reactor into the MP by differential pressure azeotropic distillation; the differential pressure azeotropic distillation system is connected with the MMA separation and refining unit so as to combine the methanol recovered from the MMA separation and refining unit with the MP for differential pressure azeotropic distillation; the differential pressure azeotropic distillation system is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that recovered methanol is used as a circulating solvent for preparing MA and returned to the MA reaction unit, the recovered methanol is used as a supplementary solvent and returned to the MMA reaction unit, and the recovered methanol is used as a raw material and conveyed to the methanol oxidation unit.
12. The apparatus of claim 11, wherein the differential pressure azeotropic distillation system comprises:
the MP pressurizing tower is connected with the hydrogenation reactor so as to perform pressurized azeotropic rectification on the MP generated by the hydrogenation reactor, and the tower kettle of the MP pressurizing tower is connected with the MMA reaction unit so as to send the MP of the tower kettle to the MMA reaction unit;
an MP pressurizing tower reflux tank which is connected with the MP pressurizing tower so as to take part of the liquid in the MP pressurizing tower reflux tank as reflux to the tower;
a methanol atmospheric tower connected with the MP pressure tower reflux tank so as to enable part of the liquid in the MP pressure tower reflux tank to enter the methanol atmospheric tower for further separation, and the methanol atmospheric tower is also connected with the MMA separation and refining unit so as to carry out atmospheric azeotropic distillation on the ester-containing methanol from the MMA separation and refining unit and the overhead product from the MP pressure tower; the tower kettle of the methanol atmospheric tower is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that the recovered methanol part of the tower kettle is used as a circulating solvent to return to the MA reaction unit, the recovered methanol part of the tower kettle is used as a supplementary solvent to return to the MMA reaction unit, and the recovered methanol part of the tower kettle is used as a raw material to return to the methanol oxidation unit;
a methanol atmospheric tower reboiler connected to the top of the MP pressure tower, for using an azeotrope of MP distilled from the top of the MP pressure tower and methanol as a heat source of the methanol atmospheric tower reboiler;
the MP pressurizing tower water cooler is connected with the methanol atmospheric tower reboiler and used for cooling the overhead azeotrope of the MP pressurizing tower subjected to heat exchange by the methanol atmospheric tower reboiler, and the MP pressurizing tower water cooler is connected with the MP pressurizing tower reflux tank so that the azeotrope cooled by the MP pressurizing tower water cooler enters the MP pressurizing tower reflux tank;
a methanol atmospheric tower air cooler connected to the top of the methanol atmospheric tower to cool the top gas phase of the methanol atmospheric tower;
a methanol atmospheric tower reflux tank connected to the methanol atmospheric tower air cooler to receive the top gas phase of the methanol atmospheric tower cooled by the methanol atmospheric tower air cooler, the methanol atmospheric tower reflux tank being connected to the methanol atmospheric tower to return the condensate in the methanol atmospheric tower reflux tank to the methanol atmospheric tower as reflux;
the methanol atmospheric tower water cooler is connected with the methanol atmospheric tower reflux tank so as to cool the tank top gas of the methanol atmospheric tower reflux tank by water;
a methanol atmospheric tower top tank connected to the methanol atmospheric tower water cooler to receive the top gas of the methanol atmospheric tower reflux tank cooled by the methanol atmospheric tower water cooler, the methanol atmospheric tower top tank connected to the MP pressure column to return tank bottoms condensate to the MP pressure column as a mixture of MP and methanol;
and the tail gas compressor is connected with the methanol normal-pressure tower top tank so as to compress the tank top gas of the methanol normal-pressure tower top tank, and the tail gas compressor is connected with the hydrogenation reactor so as to return the tank top gas compressed by the tail gas compressor to the hydrogenation reactor for cyclic utilization.
13. The apparatus of claim 11, wherein the differential pressure azeotropic distillation system comprises:
a methanol atmospheric tower connected with the hydrogenation reactor, the methanol atmospheric tower being further connected with the MMA separation and refining unit to subject the ester-containing methanol from the MMA separation and refining unit to atmospheric azeotropic distillation together with MA from the hydrogenation reactor; the tower kettle of the methanol atmospheric tower is connected with the MA reaction unit, the MMA reaction unit and the methanol oxidation unit, so that the recovered methanol part of the tower kettle is used as a circulating solvent to return to the MA reaction unit, the recovered methanol part of the tower kettle is used as a supplementary solvent to return to the MMA reaction unit, and the recovered methanol part of the tower kettle is used as a raw material to return to the methanol oxidation unit;
the methanol atmospheric tower reboiler is connected with the methanol atmospheric tower and is used for heating the kettle liquid of the methanol atmospheric tower;
the methanol atmospheric tower air cooler is connected with the top of the methanol atmospheric tower so as to cool the top gas phase of the methanol atmospheric tower;
a methanol atmospheric tower reflux tank connected to the methanol atmospheric tower air cooler to receive the top gas phase of the methanol atmospheric tower cooled by the methanol atmospheric tower air cooler, the methanol atmospheric tower reflux tank being connected to the methanol atmospheric tower to return the condensate of the methanol atmospheric tower reflux tank as reflux to the methanol atmospheric tower;
the methanol atmospheric tower water cooler is connected with the methanol atmospheric tower reflux tank and is used for cooling the tank top gas of the methanol atmospheric tower reflux tank;
a methanol atmospheric tower top tank connected to the methanol atmospheric tower water cooler to receive the top gas of the methanol atmospheric tower reflux tank cooled by the methanol atmospheric tower water cooler;
the tail gas compressor is connected with the methanol atmospheric tower top tank so as to compress the tank top gas of the methanol atmospheric tower top tank, and the tail gas compressor is connected with the hydrogenation reactor so as to return the tank top gas compressed by the tail gas compressor to the hydrogenation reactor for cyclic utilization;
an MP pressurizing tower which is connected with the methanol atmospheric tower top tank and is used for pressurizing and azeotropically rectifying the mixture of the bottom MP of the methanol atmospheric tower top tank and the methanol; the top of the MP pressurized tower is connected with the methanol atmospheric tower reboiler, so that an azeotrope of MP and methanol distilled from the top of the MP pressurized tower is used as a heat source of the methanol atmospheric tower reboiler, and the kettle of the MP pressurized tower is connected with the MMA reaction unit, so that MP in the kettle is sent to the MMA reaction unit;
the MP pressurized tower water cooler is connected with the methanol atmospheric tower reboiler and is used for cooling the overhead azeotrope of the MP pressurized tower after heat exchange of the methanol atmospheric tower reboiler;
and the MP pressurizing tower reflux tank is connected with the MP pressurizing tower water cooler so that the azeotrope cooled by the MP pressurizing tower water cooler enters the MP pressurizing tower reflux tank, and the MP pressurizing tower reflux tank is connected with the MP pressurizing tower and the methanol atmospheric tower so that one part of the liquid in the MP pressurizing tower reflux tank returns to the MP pressurizing tower as reflux and the other part returns to the methanol atmospheric tower.
14. The apparatus of claim 7, wherein the MMA separation and purification unit comprises:
an MMA-lightness removing column connected to the MMA reaction unit for subjecting the MMA crude product produced by the MMA reaction unit to azeotropic lightness removal, the top of the MMA lightness removing column being connected to the MMA reaction unit to return a distillate containing methyl propionate and methanol at the top as a reaction raw material to the MMA reaction unit;
a three-solvent extraction tower which is connected with a tower kettle of the MMA light component removal tower so as to extract tower kettle liquid of the MMA light component removal tower, wherein the solvent adopted by the three-solvent extraction tower comprises water added from the top of the three-solvent extraction tower, a formaldehyde-rich solution added from the upper part of the three-solvent extraction tower and recovered MP added from the bottom of the three-solvent extraction tower; the three-solvent extraction tower is connected with the MA concentration unit so as to take the formaldehyde-rich solution from the MA concentration unit as an extracting agent and carry out impurity removal treatment for removing heavy esters and trace acetic acid from the formaldehyde-rich solution;
the stripping tower is connected with the three-solvent extraction tower and is used for carrying out stripping treatment on a tower bottom water phase of the three-solvent extraction tower so as to remove methanol and light ester components in a formaldehyde water solution, the stripping tower is provided with a rectifying section and a water washing section positioned at the upper part of the rectifying section, the water washing section adopts an extracting agent to wash a methanol gas phase of the rectifying section of the stripping tower, and a tower bottom of the stripping tower is connected with the gas-phase formaldehyde unit so as to send the formaldehyde solution of the tower bottom of the stripping tower to the gas-phase formaldehyde unit as a raw material for preparing anhydrous gas-phase formaldehyde;
the methanol recovery tower is connected with the tower top of the stripping tower, so that a methanol-rich fraction at the tower top of the stripping tower directly enters the methanol recovery tower to be rectified in a dew point state, the tower top of the methanol recovery tower is connected with the hydrogenation reaction and MP separation unit, so that a distillate containing methanol and MP at the tower top of the methanol recovery tower is sent to a differential pressure azeotropic rectification system of the hydrogenation reaction and MP separation unit to be subjected to synergistic treatment, and tower bottom water of the methanol recovery tower is recycled as an extracting agent;
a dehydration column connected to the top of the three-solvent extraction column to dehydrate the top oil phase of the three-solvent extraction column, wherein the top recovered water of the dehydration column is returned to the three-solvent extraction column as recycled washing water;
the top of the MP recovery tower is respectively connected with the MMA reaction unit and the bottom of the three-solvent extraction tower, so that part of MP recovered from the top of the MP recovery tower is returned to the MMA reaction unit as circulating MP and part of MP is returned to the bottom of the three-solvent extraction tower as a third extraction agent;
an MMA refining column connected with the tower kettle of the MP recovery column to refine the crude MMA of the tower kettle of the MP recovery column, wherein the tower top of the MMA refining column obtains polymerization-grade MMA;
a deacidification tower connected with the tower kettle of the MMA refining tower for further separating the heavy components from the tower kettle of the MMA refining tower, wherein the deacidification tower is connected with the gas-phase formaldehyde unit for cooperatively separating acid-containing waste liquid intermittently discharged from the gas-phase formaldehyde unit;
and the acid separation tower is connected with the tower top of the deacidification tower so as to treat the acetic acid and propionic acid components on the tower top of the deacidification tower, the acetic acid is obtained on the tower top of the acid separation tower, and the propionic acid is obtained in the tower kettle.
CN202010573797.XA 2020-06-22 2020-06-22 Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate Active CN111574371B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010573797.XA CN111574371B (en) 2020-06-22 2020-06-22 Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010573797.XA CN111574371B (en) 2020-06-22 2020-06-22 Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate

Publications (2)

Publication Number Publication Date
CN111574371A true CN111574371A (en) 2020-08-25
CN111574371B CN111574371B (en) 2023-02-24

Family

ID=72118056

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010573797.XA Active CN111574371B (en) 2020-06-22 2020-06-22 Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate

Country Status (1)

Country Link
CN (1) CN111574371B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112374989A (en) * 2020-11-25 2021-02-19 西南化工研究设计院有限公司 Separation method of mixture containing formaldehyde and methanol
CN112409178A (en) * 2020-11-25 2021-02-26 西南化工研究设计院有限公司 Method for preparing methyl methacrylate by taking methyl acetate as raw material
CN112457193A (en) * 2020-11-25 2021-03-09 西南化工研究设计院有限公司 Method for preparing methyl propionate by taking methyl acetate as raw material
CN113651695A (en) * 2021-08-17 2021-11-16 天津天南同创科技发展有限公司 Separation and refining method for preparing methyl acetate from industrial tail gas
CN114292186A (en) * 2022-01-14 2022-04-08 万华化学集团股份有限公司 Preparation method of high-purity MMA
CN115246773A (en) * 2021-04-26 2022-10-28 上海浦景化工技术股份有限公司 System for separating MMA from aldol condensation product
CN115246773B (en) * 2021-04-26 2024-05-10 上海浦景化工技术股份有限公司 System for separating MMA from aldol condensation product

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104311418A (en) * 2014-11-06 2015-01-28 旭阳化学技术研究院有限公司 Azeotropic distillation separating and treatment method for methanol and methyl acrylate mixture
CN104513163A (en) * 2014-12-16 2015-04-15 北京旭阳化工技术研究院有限公司 Method for producing methyl methacrylate by methyl acetate and formaldehyde
CN110981727A (en) * 2019-12-06 2020-04-10 西南化工研究设计院有限公司 Methyl methacrylate synthesis process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104311418A (en) * 2014-11-06 2015-01-28 旭阳化学技术研究院有限公司 Azeotropic distillation separating and treatment method for methanol and methyl acrylate mixture
CN104513163A (en) * 2014-12-16 2015-04-15 北京旭阳化工技术研究院有限公司 Method for producing methyl methacrylate by methyl acetate and formaldehyde
CN110981727A (en) * 2019-12-06 2020-04-10 西南化工研究设计院有限公司 Methyl methacrylate synthesis process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112374989A (en) * 2020-11-25 2021-02-19 西南化工研究设计院有限公司 Separation method of mixture containing formaldehyde and methanol
CN112409178A (en) * 2020-11-25 2021-02-26 西南化工研究设计院有限公司 Method for preparing methyl methacrylate by taking methyl acetate as raw material
CN112457193A (en) * 2020-11-25 2021-03-09 西南化工研究设计院有限公司 Method for preparing methyl propionate by taking methyl acetate as raw material
CN115246773A (en) * 2021-04-26 2022-10-28 上海浦景化工技术股份有限公司 System for separating MMA from aldol condensation product
CN115246773B (en) * 2021-04-26 2024-05-10 上海浦景化工技术股份有限公司 System for separating MMA from aldol condensation product
CN113651695A (en) * 2021-08-17 2021-11-16 天津天南同创科技发展有限公司 Separation and refining method for preparing methyl acetate from industrial tail gas
CN113651695B (en) * 2021-08-17 2024-02-06 天津天南同创科技发展有限公司 Separation and refining method for preparing methyl acetate from industrial tail gas
CN114292186A (en) * 2022-01-14 2022-04-08 万华化学集团股份有限公司 Preparation method of high-purity MMA

Also Published As

Publication number Publication date
CN111574371B (en) 2023-02-24

Similar Documents

Publication Publication Date Title
CN111574371B (en) Method and device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate
CN111574370B (en) Method and equipment for producing methyl acrylate by anhydrous gaseous formaldehyde
HUE029355T2 (en) Improved ethylene oxide recovery process
CN109232232B (en) Refining method of acrylic acid
CN112209830B (en) Method for producing vinyl acetate
CN111574375A (en) Separation method and separation equipment for methyl acrylate crude product gas
CN104557511B (en) A kind of method of acrylic acid from vinylformic acid sour water
CN102344353A (en) Method for dehydrating acetic acid
CN103788026A (en) Method of purifying propylene epoxide
CN212335080U (en) Device for joint production of anhydrous gas-phase formaldehyde and methyl methacrylate
CN105130742B (en) Method for separating mixture of tert-butyl alcohol and benzene through pressure swing distillation
CN109534998A (en) Variable-pressure rectification separating acetic acid ethyl ester-ethyl alcohol energy saving technique with side take-off
CN103739486A (en) Production method for ethyl acetate crude product
CN102887816A (en) Method for preparing dichloropropanol with chemical reaction-pervaporation coupling method
CN212532808U (en) Methyl acrylate crude product gas separation equipment
CN102516119B (en) Continuous low-energy consumption acetonitrile refining process
CN105669445A (en) Production technology of ethyl acetate
CN102452925B (en) Method for separating acetic acid from water
CN109232166A (en) A kind of carbonated hydrogen chloride gas produces monochloro methane Processes and apparatus
CN115304475A (en) Method and system for purifying acrylic acid
CN212532807U (en) Equipment for producing methyl acrylate by anhydrous gas-phase formaldehyde
CN106278896B (en) The method of separating dimethyl carbonate during synthesizing dimethyl oxalate
CN111574374B (en) Separation method and separation equipment for methyl methacrylate crude product
CN113416133A (en) Method for continuously producing (methyl) acrylic polyol ester
CN102452926B (en) Method for separating acetic acid and water

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant