CN113717032B - Process and device for controlling methanol rectifying acid removal and PH value - Google Patents

Process and device for controlling methanol rectifying acid removal and PH value Download PDF

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Publication number
CN113717032B
CN113717032B CN202111094935.7A CN202111094935A CN113717032B CN 113717032 B CN113717032 B CN 113717032B CN 202111094935 A CN202111094935 A CN 202111094935A CN 113717032 B CN113717032 B CN 113717032B
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tower
groove
condenser
reflux
tail gas
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CN113717032A (en
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孙津生
刘道岩
王家豪
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Tianjin University
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Tianjin University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound

Abstract

The invention discloses a process and a device for controlling methanol rectification acid removal and PH value. The pre-tower reflux tank is provided with a left tank position and a right tank position, a methanol rectifying pre-tower ejects materials to a first condenser, a first condenser vapor phase product is connected with a second condenser, and a first condenser liquid phase product is connected with the pre-tower reflux tank left tank; the vapor phase product of the second condenser enters the tail gas washing tower, and the liquid phase product of the second condenser is connected with the left groove of the reflux groove of the pre-tower; water is used as an extractant, light components in raw material liquid are absorbed and then are extracted as non-condensing steam through a non-condensing steam pipe, a liquid-phase product of a tail gas washing tower is connected with a right groove of a pre-tower reflux groove, a small amount of alkali liquor is introduced into the middle section of the tail gas washing tower and is connected, and a side-line extracted product is connected with the left groove of the pre-tower reflux groove; and the product in the left groove of the pre-tower reflux groove is used as reflux to the methanol rectifying pre-tower, and the product in the right groove of the pre-tower reflux groove mainly contains methanol oil and flows out of the system. The invention can accurately control the pH value of the system and effectively improve the treatment effect of removing the rectifying acid of the methanol.

Description

Process and device for controlling methanol rectifying acid removal and PH value
Technical Field
The invention belongs to the technical field of methanol rectification, and particularly relates to a process and a device for controlling methanol rectification acid removal and PH value.
Background
Methanol is a chemical basic raw material with wide application, is applied to various fields of fine chemical industry, high polymer, pesticide, medicine, energy source and the like, and has important position in the international chemical market.
The existing crude methanol pre-rectification process is mainly completed in a pre-tower, and the pre-rectification aims at removing low-boiling components such as dimethyl ether, methyl formate and the like contained in the crude methanol and non-condensing light components dissolved in the crude methanol, and the components have great influence on the quality of subsequent rectification products of the methanol.
At present, extraction water of a rectifying system is fed along with crude methanol, and is added into a pre-tower from the middle upper section of the pre-tower, so that impurity azeotropes accumulated in the top of the pre-tower and reflux liquid cannot be effectively separated, and the reflux liquid reaches the tower bottom, so that more crude alcohol impurities enter a subsequent refining process, and the product quality is affected seriously.
The esterification reaction is more dominant than the hydrolysis reaction in the pre-tower, when we add extract water, the balance is changed to generate acid, the acid enrichment position is at the top of the pre-tower and at the bottom of the tail gas washing tower, and it is notable that the acidity is critical to the influence of the product quality.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a process and a device for controlling removal of methanol rectifying acid and PH value.
The technical scheme of the invention is a process for controlling removal of methanol rectifying acid and PH value, comprising the following steps:
1) The vapor phase at the top of the methanol rectification pre-tower T1 flows to a first condenser C1, the vapor phase condensed by the first condenser C1 flows to a second condenser C2, and the liquid phase of the first condenser C1 flows into a left groove V1L of a pre-tower reflux groove;
2) The vapor phase of the second condenser C2 is taken as raw material liquid to enter a tail gas washing tower T2, and the liquid phase of the second condenser C2 flows into a left groove V1L of a pre-tower reflux groove;
3) Water is used as an extractant, light components in raw material liquid are absorbed and then are extracted as non-condensing water, a tower bottom of a tail gas washing tower T2 flows into a right groove V1R of a pre-tower reflux groove, a small amount of alkali liquor is introduced into the middle section of the tail gas washing tower, and side line extraction is carried out and output to a left groove V1L of the pre-tower reflux groove; the left groove V1L of the pre-tower reflux groove is used for collecting a product outflow system which is mainly used for methanol oil and is used as reflux liquid to flow back to the top of the methanol rectifying pre-tower T1, and the right groove V1R of the pre-tower reflux groove.
Further, the tail gas washing tower T2 adopts a two-section structure:
the upper section of the tail gas washing tower T2 adopts extraction water to wash methanol in the tail gas, so that the methanol yield is increased;
the hydrolysis reaction of esters is enhanced at the lower section of the tail gas washing tower T2, so that the esters form high-concentration acid solution.
Further, a small amount of alkaline aqueous solution is adopted in the tail gas washing tower T2 to react with esters in non-condensing steam, so that the acid enrichment process and the ester neutralization reaction are synchronously carried out, and the enriched acid is discharged from the system along with methanol oil through a right groove V1R of a pre-tower reflux groove.
The second technical scheme of the invention is a device for removing acid and PH value in methanol preparation rectification based on the process, which comprises a methanol rectification pre-tower T1, a first condenser C1, a second condenser C2, a pre-tower reflux tank V1, a tail gas washing tower T2 and a DCS control system.
The pre-tower reflux groove V1 is provided with a left groove and a right groove, which are a left groove V1L of the pre-tower reflux groove and a right groove V1R of the pre-tower reflux groove.
The top discharge of the methanol rectification pre-tower T1 is connected with a first condenser C1 through a pipeline S1, a vapor phase product of the first condenser C1 is connected with a second condenser C2, and a liquid phase product of the first condenser C1 is connected with a left groove V1L of a pre-tower reflux groove; the vapor phase product of the second condenser C2 is taken as raw material liquid to enter a tail gas washing tower T2, and the liquid phase product of the second condenser C2 is connected with a left groove V1L of a pre-tower reflux groove; water is used as an extractant, light components in raw material liquid are absorbed and then are extracted as non-condensing steam through a non-condensing steam piping S5, a liquid-phase product of a tail gas washing tower T2 is connected with a right groove V1R of a pre-tower reflux groove through a pipeline S2, a small amount of alkali liquor is connected with the middle section of the tail gas washing tower through an alkali liquor piping, and a side-line extracted product is connected with a left groove V1L of the pre-tower reflux groove through a pipeline VI; the product in the left groove V1L of the pre-tower reflux groove is used as reflux liquid to be connected with the methanol rectification pre-tower T1 through a pipeline S3, and the product which is mainly methanol oil in the right groove V1R of the pre-tower reflux groove flows out of the system through a pipeline S4.
The pipeline S1 is provided with a flowmeter FL, the pipeline S3 and the pipeline S4 are provided with a liquid level meter LG1 and a liquid level meter LG2, and the flowmeter FL, the liquid level meter LG1 and the liquid level meter LG2 are connected with a DCS control system.
The scheme is characterized in that:
1. the tail gas washing tower adopts a two-stage structure, and the upper section of the tail gas washing tower adopts extraction water to wash methanol in the tail gas, so that the yield of the methanol is increased; the hydrolysis reaction of the esters is enhanced at the lower section, so that the esters form a high-concentration acid solution;
2. the pre-tower reflux groove V1 is provided with a left groove position and a right groove position which are separated by a baffle plate;
3. introducing a small amount of alkaline aqueous solution into the lower section of the tail gas washing tower to strengthen the hydrolysis reaction of esters, synchronously carrying out an acid enrichment process and an ester neutralization reaction, and discharging the enriched acid along with methanol oil through a pipeline S2 and a pre-tower reflux tank right tank V1R;
4. the non-condensing piping S5 is provided with a condensate backflow preventing structure; the reflux system of the pre-rectifying tower is upgraded by adopting SUS304 materials.
Advantageous effects
1. The tail gas washing tower adopts a two-stage absorption method, and can increase the methanol yield through physical absorption; then strengthening the hydrolysis reaction of esters through chemical reaction, so that the acid enrichment effect can be better achieved.
2. By arranging the baffle plate in the pre-tower reflux tank, acid enriched at the bottom of the tail gas absorption tower and crude methanol to be refluxed can be effectively separated, and then the treatment effect of methanol rectifying acid removal can be effectively improved.
3. The PH value of the methanol rectifying pre-tower system can be effectively controlled to 7-9 by controlling the addition of the alkaline aqueous solution and the monitoring of the liquid level of the reflux tank of the pre-tower by the liquid level meter, so that the quality of methanol products is improved.
4. The addition of the condensate backflow prevention structure enables the non-condensing treatment to be more effective, and has important influence on the treatment effect of removing the methanol rectifying acid.
5. After the invention is put into use, the technical problems that the prior acid enters the pressurizing tower from the bottom of the tower and is esterified at high temperature, the quality of the methanol product is seriously affected are thoroughly solved, and the qualification rate of the methanol product is greatly improved.
Drawings
FIG. 1 is a schematic diagram of a methanol rectification acid removal and pH control apparatus;
wherein: the methanol rectifying pre-tower-T1, the first condenser-C1, the second condenser-C2, the pre-tower reflux tank-V1, the tail gas washing tower-T2, the pre-tower reflux tank left tank-V1L, the pre-tower reflux tank right tank-V1R, the pipeline I-S1, the pipeline II-S2, the pipeline III-S3, the pipeline IV-S4, the non-condensing piping-S5, the pipeline VI-S6, the flowmeter-FL, the liquid level meter I-LG 1 and the liquid level meter II-LG 2.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
example 1
As shown in fig. 1, the pre-tower reflux tank V1 is provided with a left tank and a right tank, which are a pre-tower reflux tank left tank V1L and a pre-tower reflux tank right tank V1R.
The process flow of the invention comprises the following steps: the top discharge of the methanol rectifying pre-tower T1 is connected with a first condenser C1 through a pipeline S1, a vapor phase product of the first condenser C1 is connected with a second condenser C2, and a liquid phase product of the first condenser C1 is connected with a left groove V1L of a pre-tower reflux groove; the vapor phase product of the second condenser C2 is taken as raw material liquid to enter a tail gas washing tower T2, and the liquid phase product of the second condenser C2 is connected with a left groove V1L of a pre-tower reflux groove; water is used as an extractant, light components in raw material liquid are absorbed and then are extracted as non-condensing steam through a non-condensing steam piping S5, a liquid-phase product of a tail gas washing tower T2 is connected with a right groove V1R of a pre-tower reflux groove through a pipeline S2, a small amount of alkali liquor is connected with the middle section of the tail gas washing tower through an alkali liquor piping, and a side-line extracted product is connected with a left groove V1L of the pre-tower reflux groove through a pipeline VI; the product in the left groove V1L of the pre-tower reflux groove is used as reflux liquid to be connected with the methanol rectification pre-tower T1 through a pipeline S3, and the product which is mainly methanol oil in the right groove V1R of the pre-tower reflux groove flows out of the system through a pipeline S4.
The pipeline S1 is provided with a flowmeter FL, the pipeline S3 and the pipeline S4 are provided with a liquid level meter LG1 and a liquid level meter LG2, and the flowmeter FL, the liquid level meter LG1 and the liquid level meter LG2 are connected with a DCS control system.
The tail gas washing tower T2 adopts a two-stage structure, and the upper section of the tail gas washing tower T2 adopts extraction water to wash methanol in the tail gas, so that the methanol yield can be increased; the hydrolysis reaction of esters is enhanced at the lower section of the tail gas washing tower T2, so that the esters form high-concentration acid solution, and the acid enrichment effect can be better achieved.
A small amount of alkaline aqueous solution is adopted in the tail gas washing tower to react with esters in non-condensing steam, so that the acid enrichment process and the ester neutralization reaction are synchronously carried out, and the enriched acid is discharged along with the methanol oil through a pipeline S2 and a pre-tower reflux tank right tank V1R.
The non-condensing piping S5 is provided with a condensate backflow preventing structure; the addition of the condensate backflow prevention structure enables the non-condensing treatment to be more effective, and has important influence on the treatment effect of removing the methanol rectifying acid. The reflux system of the pre-rectifying tower is upgraded by adopting SUS304 materials. The tail gas washing tower adopts a two-stage absorption method, and can increase the methanol yield through physical absorption; then strengthening the hydrolysis reaction of esters through chemical reaction, so that the acid enrichment effect can be better achieved. By arranging the baffle plate in the pre-tower reflux tank, acid enriched at the bottom of the tail gas absorption tower and crude methanol to be refluxed can be effectively separated, and then the treatment effect of methanol rectifying acid removal can be effectively improved. The PH value of the methanol rectifying pre-tower system can be effectively controlled by controlling the addition of the alkaline aqueous solution and the monitoring of the liquid level of the reflux tank of the pre-tower by the liquid level meter, so that the quality of methanol products is improved.

Claims (4)

1. A process for controlling methanol rectification acid removal and PH comprising the steps of:
1) The vapor phase at the top of the methanol rectification pre-tower (T1) is fed into a first condenser (C1), the vapor phase condensed by the first condenser (C1) is fed into a second condenser (C2), and the liquid phase of the first condenser (C1) flows into a left groove (V1L) of a reflux groove of the pre-tower;
2) The vapor phase of the second condenser (C2) is taken as raw material liquid to enter a tail gas washing tower (T2), and the liquid phase of the second condenser (C2) flows into a left groove (V1L) of a pre-tower reflux groove;
3) Water is used as an extractant, light components in raw material liquid are absorbed and then are extracted as non-condensing water, the bottom of a tail gas washing tower (T2) flows into a pre-tower reflux groove right groove (V1R), a small amount of alkali liquor is introduced into the middle section of the tail gas washing tower, and side line extraction is output to the pre-tower reflux groove left groove (V1L); the method comprises the steps that a left groove (V1L) of a pre-tower reflux groove is used for collecting a reflux liquid to be refluxed to the top of a methanol rectifying pre-tower (T1), and a product which is in the right groove (V1R) of the pre-tower reflux groove and is mainly composed of methanol oil flows out of a system;
a small amount of alkaline aqueous solution is adopted in the tail gas washing tower (T2) to react with esters in non-condensing steam, so that the acid enrichment process and the ester neutralization reaction are synchronously carried out, and the enriched acid is discharged out of the system along with methanol oil through a right groove (V1R) of a pre-tower reflux groove;
the PH value of the methanol rectification pre-tower system is effectively controlled to 7-9 by controlling the addition of alkali liquor and monitoring the liquid level of a reflux tank of the pre-tower by a liquid level meter;
the tail gas washing tower (T2) adopts a two-section structure:
the upper section of the tail gas washing tower (T2) adopts extraction water to wash methanol in the tail gas, so that the yield of the methanol is increased;
the hydrolysis reaction of esters is enhanced at the lower section of the tail gas washing tower (T2), so that the esters form high-concentration acid solution;
the adopted process device comprises a methanol rectification pre-tower (T1), a first condenser (C1), a second condenser (C2), a pre-tower reflux tank (V1), a tail gas washing tower (T2) and a DCS control system;
the pre-tower reflux groove (V1) is provided with a left groove and a right groove, which are respectively a left groove (V1L) of the pre-tower reflux groove and a right groove (V1R) of the pre-tower reflux groove;
the top discharge of the methanol rectification pre-tower (T1) is connected with a first condenser (C1) through a pipeline I (S1), a vapor phase outlet of the first condenser (C1) is connected with a second condenser (C2), and a liquid phase outlet of the first condenser (C1) is connected with a left groove (V1L) of a pre-tower reflux groove; a vapor phase outlet of the second condenser (C2) is used as raw material liquid to enter the tail gas washing tower (T2), and a liquid phase outlet of the second condenser (C2) is connected with a left groove (V1L) of a pre-tower reflux groove;
the non-condensing liquid is extracted through a non-condensing pipe (S5), a liquid phase outlet of a tail gas washing tower (T2) is connected with a right groove (V1R) of a pre-tower reflux groove through a pipeline II (S2), a small amount of alkali liquor is connected with the middle section of the tail gas washing tower through an alkali liquor pipe, and a side-line extracted product is connected with a left groove (V1L) of the pre-tower reflux groove through a pipeline VI (S6); the reflux liquid in the left groove (V1L) of the reflux groove of the pre-tower is connected with the pre-tower (T1) for rectifying the methanol through a pipeline III (S3), and the product outlet at the bottom of the right groove (V1R) of the reflux groove of the pre-tower flows out;
the pipeline I (S1) is provided with a Flowmeter (FL), the pipeline III (S3) and the pipeline IV (S4) are provided with a liquid level meter I (LG 1) and a liquid level meter II (LG 2), and the Flowmeter (FL), the liquid level meter I (LG 1) and the liquid level meter II (LG 2) are connected with a DCS control system;
the left groove and the right groove of the pre-tower reflux groove (V1) are separated by a baffle plate.
2. The apparatus of the process of claim 1, comprising a methanol rectification pre-tower (T1), a first condenser (C1), a second condenser (C2), a pre-tower reflux drum (V1), a tail gas scrubber (T2), and a DCS control system;
the pre-tower reflux groove (V1) is provided with a left groove and a right groove, which are respectively a left groove (V1L) of the pre-tower reflux groove and a right groove (V1R) of the pre-tower reflux groove;
the top discharge of the methanol rectification pre-tower (T1) is connected with a first condenser (C1) through a pipeline I (S1), a vapor phase outlet of the first condenser (C1) is connected with a second condenser (C2), and a liquid phase outlet of the first condenser (C1) is connected with a left groove (V1L) of a pre-tower reflux groove; a vapor phase outlet of the second condenser (C2) is used as raw material liquid to enter the tail gas washing tower (T2), and a liquid phase outlet of the second condenser (C2) is connected with a left groove (V1L) of a pre-tower reflux groove;
the non-condensing liquid is extracted through a non-condensing pipe (S5), a liquid phase outlet of a tail gas washing tower (T2) is connected with a right groove (V1R) of a pre-tower reflux groove through a pipeline II (S2), a small amount of alkali liquor is connected with the middle section of the tail gas washing tower through an alkali liquor pipe, and a side-line extracted product is connected with a left groove (V1L) of the pre-tower reflux groove through a pipeline VI (S6); the reflux liquid in the left groove (V1L) of the reflux groove of the pre-tower is connected with the pre-tower (T1) for rectifying the methanol through a pipeline III (S3), and the product outlet at the bottom of the right groove (V1R) of the reflux groove of the pre-tower flows out;
the pipeline I (S1) is provided with a Flowmeter (FL), the pipeline III (S3) and the pipeline IV (S4) are provided with a liquid level meter I (LG 1) and a liquid level meter II (LG 2), and the Flowmeter (FL), the liquid level meter I (LG 1) and the liquid level meter II (LG 2) are connected with a DCS control system;
the left groove and the right groove of the pre-tower reflux groove (V1) are separated by a baffle plate.
3. The apparatus according to claim 2, wherein the non-condensing piping (S5) is provided with a condensate backflow preventing structure.
4. The device of claim 2, wherein the device is constructed of SUS304 upgrade material.
CN202111094935.7A 2021-09-17 2021-09-17 Process and device for controlling methanol rectifying acid removal and PH value Active CN113717032B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN204815742U (en) * 2015-07-29 2015-12-02 兖矿国宏化工有限责任公司 Methyl alcohol rectifier unit
CN106478370A (en) * 2016-10-11 2017-03-08 东华工程科技股份有限公司 A kind of method for reclaiming methyl alcohol in improved methanol rectification periodic off-gases
CN107522593A (en) * 2017-08-10 2017-12-29 青海盐湖工业股份有限公司 A kind of pre- distillation system of methanol
CN107778143A (en) * 2017-09-19 2018-03-09 中建安装工程有限公司 A kind of low-temp methanol washes the device and method of recycle methanol dividing plate extractive distillation column desulfurization
CN208166887U (en) * 2018-03-30 2018-11-30 山西焦化股份有限公司 A kind of methanol rectification pre-tower backflash extraction equipment
CN109134196A (en) * 2018-07-31 2019-01-04 东华工程科技股份有限公司 The system of methanol is recycled in a kind of improved methanol rectification periodic off-gases

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN204815742U (en) * 2015-07-29 2015-12-02 兖矿国宏化工有限责任公司 Methyl alcohol rectifier unit
CN106478370A (en) * 2016-10-11 2017-03-08 东华工程科技股份有限公司 A kind of method for reclaiming methyl alcohol in improved methanol rectification periodic off-gases
CN107522593A (en) * 2017-08-10 2017-12-29 青海盐湖工业股份有限公司 A kind of pre- distillation system of methanol
CN107778143A (en) * 2017-09-19 2018-03-09 中建安装工程有限公司 A kind of low-temp methanol washes the device and method of recycle methanol dividing plate extractive distillation column desulfurization
CN208166887U (en) * 2018-03-30 2018-11-30 山西焦化股份有限公司 A kind of methanol rectification pre-tower backflash extraction equipment
CN109134196A (en) * 2018-07-31 2019-01-04 东华工程科技股份有限公司 The system of methanol is recycled in a kind of improved methanol rectification periodic off-gases

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