CN108083984A - For glyphosate solvent and the method for by-product recovery - Google Patents
For glyphosate solvent and the method for by-product recovery Download PDFInfo
- Publication number
- CN108083984A CN108083984A CN201711466028.4A CN201711466028A CN108083984A CN 108083984 A CN108083984 A CN 108083984A CN 201711466028 A CN201711466028 A CN 201711466028A CN 108083984 A CN108083984 A CN 108083984A
- Authority
- CN
- China
- Prior art keywords
- methanol
- tower
- light component
- passed
- compressor
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The present invention relates to a kind of methods for being used for glyphosate solvent and by-product recovery, by the heat source of tower reboiler and refining methanol tower reboiler being refined after the pressurized raising energy grade of methanol steam as light component, rationally utilize heat, instead of the use of low pressure or middle pressure steam, completely without the raw steam of consumption during device normal operation, process energy consumption is greatly reduced, has been achieved the purpose that energy-saving；It is pressurizeed using compressor to light component, improve the condensation temperature of light component so that the discharging of the tower top of pre-rectifying tower and light component treating column can be cooled down using cooling water, avoid the higher chilled brine of use cost, production cost is reduced, improves the economy of technique；And this method is stronger to the separating capacity of each component, and methanol and the rate of recovery of by-product dimethoxym ethane and chloromethanes are high, purity is high, quality is good, can industrially apply.
Description
Technical field
The invention belongs to chemical fields, are related to the method for glyphosate solvent and by-product recovery.
Background technology
Glyphosate be it is a kind of efficiently, the good herbicide of low toxicity, low-residual, broad spectrum activity, being compatible with the environment property, because its performance is excellent
More and as most popular herbicide kind in current world wide.There are many production methods of glyphosate, domestic at present
The main alkyl esterification method used using glycine and dimethylphosphite as primary raw material produces.This method is molten as reaction using methanol
Agent, in the presence of catalyst of triethylamine, glycine reacts to form N with polyformaldehyde first, N- dihydroxymethyl glycine, then with Asia
After dimethyl phosphate reaction plus hydrochloric acid hydrolysis generates glyphosate and by-product dimethoxym ethane and chloromethanes.It is generated in hydrolytic process big
Steam is measured, main component is methanol, dimethoxym ethane, chloromethanes, water and a small amount of hydrogen chloride gas.Traditional recovery process is to hydrolysis
Steam is condensed, and the relatively high methanol of mid-boiling point, dimethoxym ethane, water and the condensation of a small amount of hydrogen chloride gas become liquid phase, claim
For dilute methanol；Chloromethanes is gas phase, methyl chloride gas is obtained after washing, alkali cleaning, sulfuric acid drying reach purification purpose, through pressure
Chloromethanes product is obtained after contracting, condensation.It condenses obtained dilute methanol and adds alkali neutralization, be separately recovered by two rectifying columns therein
Methanol and dimethoxym ethane, methanol is as solvent reclaiming to glyphosate synthesis link, and dimethoxym ethane is as byproduct.
Hydrolysis and two processes of solvent recovery are most important steam consumption process, wherein solvent in glyphosate generating process
The steam consumption of recovery process accounts for the 50% of entire glyphosate production process steam consumption.In existing process, a large amount of methanol, first
The materials such as acetal, water are first condensed into liquid, and need to consume a large amount of steam is heated into steam state again after rectifying column is entered, and not only wastes
The heat of hydrolysis steam also additionally consumes a large amount of raw steam, causes great heat waste.
In the prior art, the patent of invention of Publication No. CN106748637A discloses a kind of glyphosate hydrolyzing tail gas recycling
Method, hydrolysis tail gas enter rectifying column with gas form, and are first by water decomposition gas condensation separation by way of B-grade condensation
The mixing lime set of the mixing lime set and dimethoxym ethane and chloromethanes of alcohol and dimethoxym ethane, and respectively carry out rectification and purification obtain methanol,
Dimethoxym ethane, chloromethanes product.This method energy consumption decreases compared with traditional handicraft, but stills need to consume a certain amount of raw steam conduct
The heat source of rectifying tower reboiler.Since the boiling point of chloromethanes is relatively low, can not be condensed using cooling water, therefore in B-grade condensation
It needs to be cooled down using a large amount of chilled brines in device.And compared with cooling water, prepare the chilled brine that identical cold is provided
More energy, cost also higher are consumed, therefore, the use of chilled brine considerably increases production cost, also weakens vapour
The effect of process energy consumption is reduced caused by mutually feeding.
The patent of invention of Publication No. CN101225030B discloses a kind of side of heat energy utilization during glyphosate continuously synthesizes
Method, the steam that generation is hydrolyzed in glyphosate production process is preheated into tower, in tower in and/or the outer gas phase of tower neutralize, through dehydration,
Tower top distillates steam and is preheating to superheat state again, is sent into Second distillation column separation, obtains dimethoxym ethane and methanol product.Although effectively profit
With the thermal energy of hydrolysis steam, but when heating rectifying tower reboiler still need to consume a certain amount of raw steam.In addition, in the second essence
It evaporates column overhead to distillate dimethoxym ethane and isolate on-condensible gas chloromethanes, tower reactor discharge refined methanol product.Tower top partial condensation, due to
The presence of chloromethanes causes the reduction of Second distillation column overhead condensation temperature, can not reach condensation purpose using cooling water, therefore must
It must be cooled down using a large amount of chilled brines, similarly weaken the effect that process energy consumption is reduced caused by vapour phase charging, greatly
Add production cost greatly.
Therefore, there is an urgent need for a kind of methods of glyphosate solvent and by-product recovery with good energy conservation and consumption reduction effects.
The content of the invention
In view of this, it is an object of the invention to provide a kind of method for being used for glyphosate solvent and by-product recovery, tools
There are good energy conservation and consumption reduction effects, glyphosate solvent and by-product recovery rate are high, and product quality is high, and application prospect is wide.
In order to achieve the above objectives, the present invention provides following technical solution：
For glyphosate solvent and the method for by-product recovery, which is characterized in that include the following steps：By glyphosate production
The steam for hydrolyzing generation in the process is passed through vapour phase neutralizing tower, is neutralized using lye, and the vapour phase neutralized is pre-rectifying tower
It is passed through after reboiler heat supply in pre-rectifying tower, the liquid phase part neutralized is recycled back to vapour phase neutralizing tower, and a part is passed through pre-
Rectifying column；
For the liquid and vapor capacity being passed through in pre-rectifying tower rectifying, tower top obtains the light component containing dimethoxym ethane and chloromethanes, tower
Bottom obtains the mixture containing methanol, water and heavy constituent, and the obtained light component containing dimethoxym ethane and chloromethanes is pressed through compressor I
Pre-rectifying tower condenser is passed through after contracting and carries out partial condensation, the vapour phase that partial condensation obtains is passed through light group after the compression of compressor II
Divide cooler, be passed through light component cooler after the pressurized pump pressurization of the liquid phase that partial condensation obtains, then led to by light component cooler
Enter light component treating column；The light component containing dimethoxym ethane and chloromethanes of light component treating column will be passed through by rectification process, tower
Top obtains chloromethanes product, and bottom of towe obtains dimethoxym ethane product；
Mixture containing methanol, water and heavy constituent is passed through intermediate buffer tank buffering, is passed through after intermediate heater heats
Refining methanol tower rectification process, bottom of towe obtains the water containing heavy constituent after processing, and tower top obtains refined methanol steam, and obtained methanol steams
Vapour is used as the heat that light component refines tower reboiler and refining methanol tower reboiler after methanol compressor pressurizes and improves energy grade
Source collects to obtain refined methanol product after heat exchange condensation with methanol lime set collecting tank.
As preferred embodiments of the present invention, the refined methanol steam that refining methanol column overhead is obtained is through methanol compressor compresses
The heat source that energy grade rear portion is used as refining methanol tower reboiler is improved, another part is after secondary methanol compressor compresses
The heat source of tower reboiler is refined as light component.As preferred embodiments of the present invention, the smart first that refining methanol column overhead is obtained
Alcohol steam improves heat source of the energy grade rear portion as intermediate reboiler through methanol compressor compresses, and another part enters two
Grade methanol compressor, compressed rear portion of upgrading are used as the heat source of refining methanol tower reboiler, and another part is through three-level
It is used as the heat source that light component refines tower reboiler after methanol compressor compresses.It is furthermore preferred that described in the intermediate heater use
Refining methanol tower bottom of towe discharges waste water as heat source.
It is furthermore preferred that the steam of generation is hydrolyzed in the glyphosate production process includes following component：Mass fraction is
20%~60% methanol, mass fraction is 5%~30% chloromethanes, dimethoxym ethane and the matter that mass fraction is 1%~20%
Measure the water that fraction is 20%~45%；Further include necessary impurity, such as a small amount of hydrogen chloride, air, dimethyl ether.
It is furthermore preferred that the lye is the aqueous solution or methanol solution of alkali metal hydroxide, after lye dosage is to neutralize
Tower top discharging pH reaches subject to 7.0.
It is furthermore preferred that the lye in temperature is 40~90 DEG C, carries out under condition of normal pressure and.
It is furthermore preferred that the pre-rectifying tower is 0.07~0.1MPa in pressure, overhead reflux ratio is smart under the conditions of being 0.3~2
It evaporates.
It is furthermore preferred that the light component treating column pressure be 0.75~1.1MPa, overhead reflux ratio is 0.8~3 condition
Lower rectifying.
It is furthermore preferred that the refining methanol tower, in normal pressure, overhead reflux ratio is rectifying under the conditions of 0.5~2.5.
The beneficial effects of the present invention are：
(1) refining methanol tower employs heat pump distillation, and the low grade heat energy of tower top is converted into high-grade thermal energy, is methanol
The reboiler heat supply for the treatment of column and light component treating column, rationally using heat, instead of the use of low pressure or middle pressure steam, and in advance
For rectifying tower reboiler using the vapour phase that vapour phase neutralizing tower neutralizes as heat source, intermediate heater uses discharging waste water as heat
Source, therefore greatly reduce process energy consumption completely without the raw steam of consumption during device normal operation, reached energy-saving
Purpose；
(2) pressurizeed using compressor to light component, improve the condensation temperature of light component so that pre-rectifying tower and light
The tower top discharging of component treating column can be cooled down using cooling water, avoided the higher chilled brine of use cost, reduced
Production cost improves the economy of technique；
(3) glyphosate solvent and by-product recovery method of the invention are stronger to the separating capacity of each component, solvent methanol
And the rate of recovery of by-product dimethoxym ethane and chloromethanes is high, purity is high, quality is good；
(4) vapour phase neutralizing tower, pre-rectifying tower, refining methanol tower operate under normal pressure or condition of negative pressure, avoid raw material
In the corrosion of the non-volatile impurity to equipment such as saline and alkaline, the corrosion-resistant requirement to equipment material is reduced, so as to save equipment throwing
Money.
Description of the drawings
In order to make the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides drawings described below and carries out
Explanation：
Fig. 1 is glyphosate solvent and by-product recovery process flow diagram.
Fig. 2 is glyphosate solvent and by-product recovery selection process flow schematic diagram.
Fig. 3 is glyphosate solvent and by-product recovery most preferred process flow diagram.
1- vapour phase neutralizing towers；2- pre-rectifying towers；3- light component treating columns；4- refining methanol towers；5- pre-rectifying tower reboilers；
6- compressors I；7- pre-rectifying tower condensers；8- compressors II；9- force (forcing) pumps；10- light component coolers；11- light components refine
Tower condenser；12- light components refine tower reboiler；13- intermediate buffer tanks；14- intermediate heaters；15- methanol compressors；16-
Refining methanol tower reboiler；17- methanol lime set collecting tanks；18- secondary methanol compressors；19- three-level methanol compressors；In 20-
Between reboiler.
Specific embodiment
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
Embodiment 1
The present invention provides a kind of methods for being used for glyphosate solvent and by-product recovery, have good energy-saving effect
Fruit, glyphosate solvent and by-product recovery rate are high, and product quality is high, and application prospect is wide, and concrete technology route is as shown in Figure 1, tool
Body method is as follows：
The steam that generation is hydrolyzed in glyphosate production process is passed through vapour phase neutralizing tower 1, is neutralized using lye, is neutralized
Obtained vapour phase is is passed through in pre-rectifying tower 2 after 5 heat supply of pre-rectifying tower reboiler, the liquid phase part cycle back-steam neutralized
Phase neutralizing tower 1, a part are passed through pre-rectifying tower 2；
The liquid and vapor capacity being passed through obtains the light component containing dimethoxym ethane and chloromethanes in 2 tower top of pre-rectifying tower, and bottom of towe obtains
To the mixture containing methanol, water and heavy constituent, the obtained light component containing dimethoxym ethane and chloromethanes is compressed through compressor I 6
After be passed through pre-rectifying tower condenser 7 carry out partial condensation, the vapour phase that partial condensation obtains through compressor II 8 be passed through light component cool down
Device 10 is passed through light component cooler 10 after pressurized 9 pressurization of pump of liquid phase that partial condensation obtains, then is led to by light component cooler 10
Enter light component treating column 3；The light component containing dimethoxym ethane and chloromethanes for being passed through light component treating column 3 is passed through into rectification process,
Tower top obtains chloromethanes product, and bottom of towe obtains dimethoxym ethane product；II 8 pairs of light component steam of compressor I 6 and compressor are used in the process
It pressurizes, the purpose is to improve its condensation temperature, light component is enable to be cooled with circulating water, avoids use cost higher cold
Freeze brine；
Mixture containing methanol, water and heavy constituent is passed through refining methanol tower 4, to avoid vapour phase Feedstock fluctuation to methanol essence
The stable operation of 4 heat pump system of tower processed impacts, and an intermediate buffer tank 13 is set before refining methanol tower 4.Intermediate buffering
Material in tank 13 is passed through refining methanol tower 4 again after being heated by intermediate heater 14, after rectification process, bottom of towe is obtained containing restructuring
The water divided, tower top obtain refined methanol steam, and obtained methanol steam is used as after methanol compressor 15 pressurizes and improves energy grade
Light component refines the heat source of tower reboiler 12 and refining methanol tower reboiler 16, is received after heat exchange condensation with methanol lime set collecting tank 17
Collection obtains refined methanol product.To make full use of stream stock heat, using discharging waste water as the heat source of intermediate heater 14, using adding
Supplemental heat source of the methanol as intermediate heater 14 after pressure.
The steam each component content that generation is hydrolyzed in the present invention, in glyphosate production process is as follows：Mass content is 20%
~60% methanol, 5%~30% chloromethanes, 1%~20% dimethoxym ethane, 20%~45% water and a small amount of chlorination
The impurity such as hydrogen, air, dimethyl ether.
Vapour phase neutralizing tower 1 is atmospheric operation, and operation temperature is 40~90 DEG C.
2 operating pressure of pre-rectifying tower is 0.07~0.1MPa (absolute pressure), and overhead reflux is 0.3~2 than range of choice.
3 operating pressure of light component treating column is 0.75~1.1MPa (absolute pressure), and overhead reflux is 0.8~3 than range of choice.
Refining methanol tower 4 is atmospheric operation, and overhead reflux is 0.5~2.5 than range of choice.
Power needed for compressor can be provided by variable-frequency motor, can also be provided by back pressure turbine, the back of the body of steam turbine discharge
Pressure steam can be used as the supplemental heat source of each rectifying tower reboiler, also can make technological process as the heating medium of intermediate heater
It is more energy efficient.
Reach more than 85% using chloromethanes mass content in this method chloromethanes product, remaining ingredient is mainly nitrogen, oxygen
Deng；Dimethoxym ethane mass content reaches more than 85% in dimethoxym ethane product, remaining ingredient is mainly methanol, reaches commercial goods content
It is required that；Methanol quality content reaches more than 99.7% in methanol product；The mass content of water is big in the discharging of refining methanol tower bottom of towe
In 98.5%, remaining ingredient is mainly the neutralized reaction product salt i.e. chloride of alkali metal, and content of organics is less than 0.1%；Entirely
Glyphosate solvent and by-product recovery technique, the refined methanol rate of recovery >=96.9%, total Methanol Recovery rate >=99.9%, dimethoxym ethane return
Yield >=99.9%, the rate of recovery >=99.9% of chloromethanes.
Embodiment 2
Embodiment 2 is the preferred embodiment of embodiment 1, and methanol compressor uses two-stage compression scheme, can further reduce work
Artistic skill consumes, and for concrete technology as shown in Fig. 2, its technique is same as Example 1, difference is the overhead vapours of refining methanol tower 4 through first
15 one stage of compression of alcohol compressor improves the heat source that energy grade rear portion is used as refining methanol tower reboiler 16, another part warp
Secondary methanol compressor 18 is used as the heat source that light component refines tower reboiler 12 after compressing.Due to the tower reactor of light component treating column 3
Temperature is higher than the bottom temperature of refining methanol tower 4, therefore in the one stage of compression scheme of embodiment 1, it need to be by all refining methanols
The pressurization of 4 tower top methanol steam of tower is upgrade to can be degree that light component refines 12 heat supply of tower reboiler.And the present embodiment
Due to using methanol two-stage compression scheme, need not pressurize raising product for this some vapor of 16 heat supply of refining methanol tower reboiler
Position extremely can be the degree that light component refines 12 heat supply of tower reboiler, and methanol compressor 15 can set relatively low outlet pressure,
Compared with the scheme of embodiment 1, reduce and compress the electric energy that this some vapor needs consumes, reach the mesh for reducing process energy consumption
's.
In the present embodiment, feedstock flow is 15000kg/hr, and composition is shown in Table 1, and lye is that mass fraction is
30% sodium hydrate aqueous solution, flow 70kg/hr.The operating parameter of each rectifying column is shown in Table 2, and methanol compressor is driven using electricity
Dynamic, two-stage compression scheme, obtains product form and is shown in Table 3, table 4, table 5.
Table 1, raw material composition (mass fraction, %)
| Methanol | Water | Dimethoxym ethane | Chloromethanes | Hydrogen chloride | Oxygen | Nitrogen | Dimethyl ether |
| 0.425 | 0.368 | 0.0911 | 0.0993 | 0.00127 | 0.00301 | 0.00997 | 0.00235 |
Table 2, each rectifying column operating parameter
Table 3, methanol product composition (mass fraction, %)
| Methanol | Water | Dimethoxym ethane | Chloromethanes | Dimethyl ether |
| ≥0.999 | 77ppm | 7ppm | Trace | Trace |
Table 4, dimethoxym ethane product form (mass fraction, %)
| Dimethoxym ethane | Methanol | Water | Chloromethanes | Dimethyl ether |
| ≥0.850 | 0.149 | 0.000127 | Trace | Trace |
Table 5, chloromethanes product form (mass fraction, %)
| Chloromethanes | Oxygen | Nitrogen | Dimethyl ether | Methanol | Water | Dimethoxym ethane |
| 0.869 | 0.0257 | 0.0851 | 0.0201 | 67ppm | 20ppm | 13ppm |
The energy consumption data of the present embodiment is compared with existing process, including the heating steam consumption, cooling water consume, chilled water
Consumption, power consumption of compressor and the energy unit consumption that is thus calculated convert into mark coal, and the results are shown in Table 6.
Table 6, energy consumption comparison
As shown in Table 6, the technique of the present embodiment can save energy more than 61.2% compared with the prior art.
Embodiment 3
Embodiment 3 be embodiment 1 preferred embodiment, can further reduce process energy consumption, concrete technology as shown in figure 3, its
Technique is same as Example 1, and difference lies in an intermediate reboiler 20 is increased for refining methanol tower 4, methanol compressor uses three
Grade compression scheme, specially：The overhead vapours of refining methanol tower 4 is latter through 15 one stage of compression of methanol compressor raising energy grade
Part is used as the heat source of intermediate reboiler 20, and another part enters secondary methanol compressor 18, the compressed latter portion that upgrades
Divide the heat source as refining methanol tower reboiler 16, another part refines after the compression of three-level methanol compressor 19 as light component
The heat source of tower reboiler 12.Since the Temperature Distribution of refining methanol tower 4 is continuously decreased from bottom of towe to tower top, and bottom of towe and tower
The temperature difference on top is larger, sets intermediate reboiler 20, can share the thermic load of part refining methanol tower reboiler 16, and centre is boiled again
Device 20 can use more low-grade heat source to heat, therefore can accordingly reduce the outlet pressure of methanol compressor 15, reduce methanol compression
The power consumption of machine 15.And the purpose of compression of secondary methanol compressor 18 is for refining methanol tower reboiler heat supply, therefore equally also may be used
The corresponding outlet pressure for reducing secondary methanol compressor 18 reduces the power consumption of secondary methanol compressor 18.Final only a fraction
Methanol steam need to pressurize and upgrade to can be degree that light component refines 12 heat supply of tower reboiler.Therefore the present embodiment
Scheme on the basis of 2 scheme of embodiment, further reduce process energy consumption, reached more preferably energy conservation and consumption reduction effects.
In the present embodiment, feedstock flow is 8000kg/hr, and composition is shown in Table 7, and the sodium hydroxide that lye is 32% is water-soluble
Liquid, flow 69kg/hr；The operating parameter of each rectifying column is shown in Table 8, and methanol compressor is obtained using electric drive, three stage compression scheme
9, table 10, table 11 are shown in Table to product form.
Table 7, raw material composition (mass fraction, %)
| Methanol | Water | Dimethoxym ethane | Chloromethanes | Hydrogen chloride | Oxygen | Nitrogen | Dimethyl ether |
| 0.408 | 0.382 | 0.103 | 0.0882 | 0.00250 | 0.00315 | 0.0105 | 0.00265 |
Table 8, each rectifying column operating parameter
| Rectifying column title | Tower top pressure/kPa | Tower pressure drop/kPa | Reflux ratio |
| Pre-rectifying tower | 85 | 10 | 0.5 |
| Light component treating column | 1100 | 20 | 1.7 |
| Refining methanol tower | 102 | 10 | 1.0 |
Table 9, methanol product composition (mass fraction, %)
| Methanol | Water | Dimethoxym ethane | Chloromethanes | Dimethyl ether |
| ≥0.998 | 0.00170 | 5ppm | Trace | Trace |
Table 10, dimethoxym ethane product form (mass fraction, %)
| Dimethoxym ethane | Methanol | Water | Chloromethanes | Dimethyl ether |
| 0.852 | 0.147 | 0.000956 | 19ppm | 25ppm |
Table 11, chloromethanes product form (mass fraction, %)
| Chloromethanes | Oxygen | Nitrogen | Dimethyl ether | Methanol | Water | Dimethoxym ethane |
| 0.862 | 0.0270 | 0.0886 | 0.0223 | 55ppm | 9ppm | 36ppm |
The energy consumption data of the present embodiment is compared with existing process, including the heating steam consumption, cooling water consume, chilled water
Consumption, power consumption of compressor and the energy unit consumption that is thus calculated convert into mark coal, as a result as shown in table 12.
Table 12, energy consumption comparison
As shown in Table 12, the technique of the present embodiment can save energy more than 68.0% compared with the prior art.
In conclusion using the method recycling glyphosate solvent and by-product of the present invention, there is good energy-saving effect, because
This can be used for the recycling of solvent and by-product in industrialized production glyphosate.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. for glyphosate solvent and the method for by-product recovery, which is characterized in that include the following steps：By glyphosate production mistake
The steam that generation is hydrolyzed in journey is passed through vapour phase neutralizing tower, is neutralized using lye, the vapour phase neutralized for pre-rectifying tower again
It is passed through after boiling device heat supply in pre-rectifying tower, the liquid phase part neutralized is recycled back to vapour phase neutralizing tower, and a part is passed through pre- essence
Evaporate tower；
For the liquid and vapor capacity being passed through in pre-rectifying tower rectifying, tower top obtains the light component containing dimethoxym ethane and chloromethanes, and bottom of towe obtains
To the mixture containing methanol, water and heavy constituent, the obtained light component containing dimethoxym ethane and chloromethanes is after the compression of compressor I
It is passed through pre-rectifying tower condenser and carries out partial condensation, it is cold that the vapour phase that partial condensation obtains is passed through light component after the compression of compressor II
But device is passed through light component cooler after the pressurized pump pressurization of liquid phase that partial condensation obtains, then is passed through gently by light component cooler
Component treating column；The light component containing dimethoxym ethane and chloromethanes for being passed through light component treating column is passed through into rectification process, tower top obtains
To chloromethanes product, bottom of towe obtains dimethoxym ethane product；
Mixture containing methanol, water and heavy constituent is passed through intermediate buffer tank buffering, and methanol is passed through after intermediate heater heats
Treating column rectification process, bottom of towe obtains the water containing heavy constituent after processing, and tower top obtains refined methanol steam, obtained methanol steam warp
The pressurization of methanol compressor is used as the heat source that light component refines tower reboiler and refining methanol tower reboiler after improving energy grade, changes
It collects to obtain refined methanol product with methanol lime set collecting tank after heat condensation.
2. according to the method described in claim 1, it is characterized in that：The refined methanol steam that refining methanol column overhead is obtained is through first
Alcohol compressor compresses improve the heat source that energy grade rear portion is used as refining methanol tower reboiler, and another part is through secondary methanol
It is used as the heat source that light component refines tower reboiler after compressor compresses.
3. according to the method described in claim 1, it is characterized in that：The refined methanol steam that refining methanol column overhead is obtained is through first
Alcohol compressor compresses improve the heat source that energy grade rear portion is used as intermediate reboiler, and another part enters secondary methanol compression
Machine, compressed rear portion of upgrading are used as the heat source of refining methanol tower reboiler, and another part is through three-level methanol compressor
It is used as the heat source that light component refines tower reboiler after compression.
4. according to the method described in claim 1, it is characterized in that：The steamdrum of generation is hydrolyzed in the glyphosate production process
Include following component：Mass fraction is 20%~60% methanol, and mass fraction is 5%~30% chloromethanes, and mass fraction is
1%~20% dimethoxym ethane, mass fraction are 20%~45% water and other impurity.
5. according to the method described in claim 1, it is characterized in that：The lye is the aqueous solution or first of alkali metal hydroxide
Alcoholic solution, lye dosage is subject to neutralize after tower top discharging pH reach 7.0.
6. according to the method described in claim 1, it is characterized in that：The lye is 40~90 DEG C, under condition of normal pressure in temperature
It is neutralized.
7. according to the method described in claim 1, it is characterized in that：The pre-rectifying tower is 0.07~0.1MPa (A) in pressure,
Overhead reflux ratio is rectifying under the conditions of 0.3~2.
8. according to the method described in claim 1, it is characterized in that：The light component treating column is 0.75~1.1MPa in pressure
(A), overhead reflux ratio is rectifying under the conditions of 0.8~3.
9. according to the method described in claim 1, it is characterized in that：For the refining methanol tower in normal pressure, overhead reflux ratio is 0.5
Rectifying under the conditions of~2.5.
10. according to the method described in claim 1, it is characterized in that：Power needed for the compressor by variable-frequency motor provide or
It is provided by back pressure turbine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711466028.4A CN108083984B (en) | 2017-12-28 | 2017-12-28 | Method for recovering glyphosate solvent and byproducts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711466028.4A CN108083984B (en) | 2017-12-28 | 2017-12-28 | Method for recovering glyphosate solvent and byproducts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108083984A true CN108083984A (en) | 2018-05-29 |
| CN108083984B CN108083984B (en) | 2021-02-26 |
Family
ID=62180473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711466028.4A Active CN108083984B (en) | 2017-12-28 | 2017-12-28 | Method for recovering glyphosate solvent and byproducts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108083984B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041164A (en) * | 2019-05-08 | 2019-07-23 | 江西金龙化工有限公司 | A method of recycling chloromethanes |
| CN111203090A (en) * | 2020-03-16 | 2020-05-29 | 浙江新安化工集团股份有限公司 | System and process for treating hydrolysis tail gas of glyphosate and phosphonated synthetic liquid |
| CN111995499A (en) * | 2020-08-26 | 2020-11-27 | 吴嘉 | Methanol heat pump rectification method and device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457873A (en) * | 1983-03-24 | 1984-07-03 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| US4568432A (en) * | 1984-12-28 | 1986-02-04 | Monsanto Company | Process for preparing glyphosate and glyphosate derivatives |
| CN101225030A (en) * | 2007-01-15 | 2008-07-23 | 浙江新安化工集团股份有限公司 | Method for utilizing thermal energy during continuous synthesis of glyphosate |
| CN104353339A (en) * | 2014-10-30 | 2015-02-18 | 江西金龙化工有限公司 | Method for continuously recovering by-products from tail gas obtained by hydrolyzing glyphosate |
-
2017
- 2017-12-28 CN CN201711466028.4A patent/CN108083984B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457873A (en) * | 1983-03-24 | 1984-07-03 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| US4568432A (en) * | 1984-12-28 | 1986-02-04 | Monsanto Company | Process for preparing glyphosate and glyphosate derivatives |
| CN101225030A (en) * | 2007-01-15 | 2008-07-23 | 浙江新安化工集团股份有限公司 | Method for utilizing thermal energy during continuous synthesis of glyphosate |
| CN104353339A (en) * | 2014-10-30 | 2015-02-18 | 江西金龙化工有限公司 | Method for continuously recovering by-products from tail gas obtained by hydrolyzing glyphosate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041164A (en) * | 2019-05-08 | 2019-07-23 | 江西金龙化工有限公司 | A method of recycling chloromethanes |
| CN110041164B (en) * | 2019-05-08 | 2021-11-09 | 浙江金帆达生化股份有限公司 | Method for recovering methyl chloride |
| CN111203090A (en) * | 2020-03-16 | 2020-05-29 | 浙江新安化工集团股份有限公司 | System and process for treating hydrolysis tail gas of glyphosate and phosphonated synthetic liquid |
| CN111995499A (en) * | 2020-08-26 | 2020-11-27 | 吴嘉 | Methanol heat pump rectification method and device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108083984B (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104788289B (en) | A kind of pump coupled heat technique of ethylene glycol rectifying | |
| CN104311383B (en) | A kind of method of the hydrogen chloride production monochloro methane that utilizes by-product in tetrachloro-ethylene production process | |
| CN102936198B (en) | Produce the method for vinyl acetate | |
| CN108083984A (en) | For glyphosate solvent and the method for by-product recovery | |
| CN104817481A (en) | Technological method for recovering DMSO from DMSO aqueous solution | |
| CN111592446A (en) | Rectification system and process for preparing ethylene glycol by dimethyl oxalate hydrogenation | |
| CN103788026A (en) | Method of purifying propylene epoxide | |
| CN105315132A (en) | System and method used for energy utilization between ethylene glycol device dehydrating tower and refining tower | |
| CN111233690A (en) | DMAc thermal coupling refining and recycling system and method | |
| CN111635293A (en) | Sodium methoxide production device and method | |
| CN111333484A (en) | Ultrahigh-purity methane chloride production system and process | |
| CN217264857U (en) | Concentration and reuse device for chlorine gas drying waste acid | |
| CN109232166A (en) | A kind of carbonated hydrogen chloride gas produces monochloro methane Processes and apparatus | |
| CN102452925B (en) | Method for separating acetic acid from water | |
| CN102442893B (en) | Separation method of aldehyde condensation products | |
| CN211753893U (en) | System for recovering hydrolysis tail gas of glyphosate-phosphonated synthetic liquid | |
| CN107473294A (en) | A kind of handling process and processing system of acrylonitrile recovery tower tower bottoms | |
| CN113121314A (en) | Device and method for recycling tertiary butanol by using dividing wall rectifying tower and combining heat pump technology | |
| CN206843352U (en) | A kind of 1,4 butynediols purification systems | |
| CN212425916U (en) | Ultra-high-purity methane chloride production system | |
| CN209836040U (en) | Potassium tert-butoxide indirect compression self-backheating rectification system | |
| CN219595861U (en) | Device for recycling ethanol from waste liquid of preparing glycol from natural gas | |
| CN217511198U (en) | Four-tower heat pump thermal coupling methanol rectification device | |
| CN217367194U (en) | Energy-conserving BDO rectifier unit | |
| CN215310246U (en) | Sodium hyaluronate cryoconcentration extraction system |
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 |