CN112239434B - Epoxy chloropropane production device and technology - Google Patents
Epoxy chloropropane production device and technology Download PDFInfo
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- CN112239434B CN112239434B CN202011288662.5A CN202011288662A CN112239434B CN 112239434 B CN112239434 B CN 112239434B CN 202011288662 A CN202011288662 A CN 202011288662A CN 112239434 B CN112239434 B CN 112239434B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000005516 engineering process Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 218
- 239000007791 liquid phase Substances 0.000 claims abstract description 176
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 151
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000007127 saponification reaction Methods 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 58
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 19
- 238000007670 refining Methods 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 117
- 239000012071 phase Substances 0.000 claims description 94
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 66
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 66
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 66
- 235000011187 glycerol Nutrition 0.000 claims description 52
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 40
- 238000003860 storage Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 239000006096 absorbing agent Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 15
- 239000012452 mother liquor Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013072 incoming material Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FLTSEOGWHPJWRV-UHFFFAOYSA-N 1,2-dichloropropan-1-ol Chemical compound CC(Cl)C(O)Cl FLTSEOGWHPJWRV-UHFFFAOYSA-N 0.000 description 1
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical class ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 2,3-dichloropropan-1-ol Chemical class OCC(Cl)CCl ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
Abstract
The invention discloses an epoxy chloropropane production device, which comprises a glycerol chlorination unit, a dichloropropanol refining unit and a dichloropropanol saponification unit which are sequentially connected, and is characterized in that: the dichloropropanol refining unit comprises a resolving tower (21) with a liquid phase inlet communicated with a material outlet of the glycerol chlorination unit (1), a rectifying tower (22) with a liquid phase inlet communicated with a liquid phase outlet of the resolving tower (21), a first layering tank (27) with a liquid phase inlet communicated with a first liquid phase outlet of the rectifying tower (22) and a dichloropropanol recovery tower (28) with a liquid phase inlet communicated with a first liquid phase outlet of the first layering tank (27). The invention also discloses an epoxy chloropropane production process using the epoxy chloropropane production device. Compared with the prior art, the invention can effectively recycle the light components of the rectifying tower to the reaction system while stabilizing production and reduce energy consumption.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to an epoxy chloropropane production device and an epoxy chloropropane production process.
Background
Epichlorohydrin (also known as epichlorohydrin) is 1-chloro-2, 3-epoxypropane of formula C 3 H 5 OCl, boiling point 115.2 ℃, solidifying point-57.2 ℃, is a colorless liquid which is easy to volatilize and unstable, is slightly soluble in water, and can be mixed with various organic solvents.
The epichlorohydrin is an important organic chemical raw material and a fine chemical product, is a large variety of products in propylene derivatives, is mainly used for synthesizing glycerol, epoxy resin, chlorohydrin rubber, nitroglycerin explosive and the like, and can also be used as a solvent for cellulose ester, resin and cellulose ether; is also the main raw material for producing surfactants, plasticizers, stabilizers, adhesives and ion exchange resins. It is also widely used in the industries of paint, adhesive, reinforcing material, casting material, electronic laminated product, etc. In addition, the epichlorohydrin can be used for synthesizing various products such as surfactants, medicines, pesticides, coatings, sizing materials, ion exchange resins and the like, and can be used for producing chemical stabilizers, chemical dyes, water treatment agents and the like.
The existing production methods of epichlorohydrin mainly comprise a propylene high-temperature chlorination method and a propylene acetate method, and the two methods both use propylene as a raw material and depend on consumption of petroleum energy. With further price rising and resource shortage of petroleum energy sources, the raw material source and price of propylene are greatly influenced by markets. Because of the international rise of biodiesel, a large amount of by-product glycerol is a surplus in the glycerol market, and about 1 ton of by-product glycerol can be produced per 10 tons of biodiesel produced. The glycerol market of biodiesel byproducts is more in demand, and glycerol epichlorohydrin is an emerging epichlorohydrin production technology, and recently, the glycerol epichlorohydrin production technology is widely focused. Dichloropropanol containing two isomers of 2, 3-dichloro-1-propanol and 1, 3-dichloro-2-propanol and having molecular formula of C 3 H 6 Cl 2 O, the boiling point of which is 174 ℃, and the colorless liquid has little chloroform smell and is an intermediate product for producing epichlorohydrin. Dichloropropanol is treated with Ca (OH) 2 After the saponification of NaOH, dichloropropanol can be cyclized to generate the final product epichlorohydrin.
According to the invention patent application No. CN202010346652.6 (publication No. CN 111499598A), a process for producing epichlorohydrin by a glycerin method is disclosed, glycerin, a catalyst and hydrogen chloride are added into a reactor for reaction, so that monochloropropanediol and water are generated in the reactor, the monochloropropanediol continuously reacts with the hydrogen chloride in the reactor to generate dichloropropanol, raw materials in the reactor react for a period of time, the obtained product enters the reaction rectifying tower, the raw materials react and are separated in the reaction rectifying tower, dichloropropanol obtained by hydrochlorination is sent into a pre-reactor for cyclization reaction with alkali liquor, most of alkali liquor is added from an inlet of the pre-reactor, the obtained product in the pre-reactor, the rest 1, 2-dichloropropanol and the alkali liquor enter the cyclization tower for full reaction to generate epichlorohydrin, and the obtained product at the top of the cyclization tower is sent into a second rectifying tower for further separation, so that epichlorohydrin is obtained.
In the scheme, firstly, the materials at the bottom of the first rectifying tower are directly fed into the reactor, so that on one hand, uneven mixing can be caused, and on the other hand, heavy components in the materials can be returned to a reaction system together, so that steam consumption is increased; secondly, dichloropropanol obtained from the tops of the reactive rectifying tower and the first rectifying tower enter downstream together with hydrogen chloride, so that the waste of the hydrogen chloride is caused, and the consumption of alkali liquor in the saponification unit is increased.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide an epichlorohydrin production device which can effectively recycle the light components of the rectifying tower to the reaction system while stabilizing production and reduce energy consumption.
The second technical problem to be solved by the invention is to provide an epichlorohydrin production process using the epichlorohydrin production device.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the utility model provides an epoxy chloropropane apparatus for producing, is including glycerin chlorination unit, dichloropropanol refining element and dichloropropanol saponification unit that connects in proper order, its characterized in that: the dichloropropanol refining unit comprises
The bottom of the analytic tower is provided with a first reboiler, the top of the analytic tower is provided with a first condenser, and a liquid phase inlet of the analytic tower is communicated with a material outlet of the glycerol chlorination unit;
the rectifying tower is provided with a second reboiler at the bottom, a second condenser at the top, a liquid phase inlet of the second condenser is communicated with a liquid phase outlet of the resolving tower, a first liquid phase outlet for discharging heavy components is arranged at the bottom, a second liquid phase outlet for discharging light components is arranged at the side, and the second liquid phase outlet is communicated with a material inlet of the dichloropropanol saponification unit;
the liquid phase inlet of the first layering tank is communicated with a first liquid phase outlet of the rectifying tower, and is provided with a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, and the second liquid phase outlet of the first layering tank is communicated with a material inlet of the glycerol chlorination unit; and
and the liquid phase inlet of the dichloropropanol recovery tower is communicated with the first liquid phase outlet of the first layering tank.
Preferably, the glycerol chlorination unit comprises
A raw material storage tank for storing a glycerol catalyst solution;
the liquid phase inlet of the pre-reaction tower is communicated with the material outlet of the raw material storage tank, and the top of the pre-reaction tower is provided with a gas phase outlet for discharging tail gas;
the liquid phase inlet of the first-stage reaction kettle is communicated with the liquid phase outlet of the pre-reaction tower, and the gas phase inlet of the first-stage reaction kettle is communicated with an external hydrogen chloride pipeline;
the liquid phase inlet of the second-stage reaction kettle is communicated with the liquid phase outlet of the pre-reaction tower and the liquid phase outlet of the first-stage reaction kettle, and the gas phase inlet of the second-stage reaction kettle is communicated with an externally connected hydrogen chloride pipeline and the gas phase outlet of the first-stage reaction kettle; and
the liquid phase inlet of the three-stage reaction kettle is communicated with the liquid phase outlet of the pre-reaction tower and the liquid phase outlet of the two-stage reaction kettle, the gas phase inlet of the three-stage reaction kettle is communicated with an externally connected hydrogen chloride pipeline and the gas phase outlet of the two-stage reaction kettle, and the gas phase outlet of the three-stage reaction kettle is communicated with the gas phase inlet of the pre-reaction tower;
the liquid phase inlet of the resolving tower is communicated with the liquid phase outlet of the three-section reaction kettle;
and a second liquid phase outlet of the first layering tank is communicated with liquid phase inlets of the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle.
In the glycerol chlorination unit, the liquid phase outlet of the pre-reaction tower is communicated with the liquid phase inlets of all the reaction kettles, so that materials for starting the pre-reaction tower for the first time can enter all the reaction kettles, and the starting operation is convenient; in addition, the materials of the upper-stage reaction kettle enter the lower stage, so that the reaction efficiency between the glycerol and the hydrogen chloride in the lower-stage reaction kettle can be effectively improved.
Further, the gas phase outlet of the resolving tower is communicated with the gas phase inlet of the pre-reaction tower. Since the gas phase outlet of the analytical column communicates with the gas phase inlet of the pre-reaction column, first, it is expected that 200Nm can be recovered 3 Hydrogen chloride per hour, reducing 1t/h lime milk consumption (15 wt% concentration); secondly, the load of the subsequent analytic tower and saponification tower can be reduced; third, the content of monochloropropanediol in the saponification column can be greatly reduced.
Further, the dichloropropanol refining unit also comprises
The liquid phase inlet of the glycerol absorber is communicated with the material outlet of the raw material storage tank, the gas phase inlet of the glycerol absorber is communicated with the gas phase outlet of the rectifying tower, and the liquid phase outlet of the glycerol absorber is communicated with the liquid phase inlet of the pre-reaction tower; and
and the gas phase inlet of the first cooler is communicated with the gas phase outlet of the glycerol absorber, and the liquid phase outlet of the first cooler is communicated with the liquid phase inlet of the first layering tank.
The glycerol absorber can absorb part of organic matters and hydrogen chloride in the tail gas of the rectifying tower, and the liquid phase outlet of the glycerol absorber is communicated with the liquid phase inlet of the pre-reaction tower, so that the hydrogen chloride and the glycerol can be conveniently recovered;
the organic matters cooled down by the first cooler are recycled to the first layering tank, so that dichloropropanol in the tail gas of the rectifying tower can be effectively recycled.
Still further, the dichloropropanol refining unit also comprises
An ejector, the gas phase inlet of which is communicated with the gas phase outlet of the first cooler; and
and a gas phase inlet of the alkaline washing tower is communicated with a gas phase outlet of the first cooler, and a gas phase outlet at the top of the alkaline washing tower is connected with a first vacuum pump.
The glycerol absorber, the first cooler and the alkaline washing tower can remove most of hydrogen chloride in the noncondensable gas, so that the influence on the vacuum degree of the rectifying tower caused by excessive noncondensable gas is prevented, and meanwhile, the acid noncondensable gas mixed in tail gas can corrode the first vacuum pump, so that the quality and the yield stability of dichloropropanol are influenced;
the jet pump can jet the steam from the nozzle at a very high speed, and low pressure is formed in the vacuum chamber, so that the gas at the top of the rectifying tower sequentially enters the vacuum chamber, the mixing chamber and the saponification tower, the jetted steam can be used for the saponification tower to react, and meanwhile, the jet pump can reduce the load of the first vacuum pump or partially replace the first vacuum pump when the first vacuum pump fails, so that the stable operation of the rectifying tower is ensured.
Further, the dichloropropanol saponification unit comprises
The alkali liquor tank is used for storing alkali liquor;
the saponification tower is provided with a material inlet corresponding to the second tower plate and a hot water inlet corresponding to the first tower plate, the material inlet of the saponification tower is communicated with the second liquid phase outlet of the rectifying tower and the material outlet of the alkali liquor tank, and the hot water inlet of the saponification tower is communicated with an external hot water pipeline;
the gas phase inlet of the third condenser is communicated with the gas phase outlet of the saponification tower, and the gas phase outlet of the third condenser is connected with a second vacuum pump;
the liquid phase inlet of the second layering tank is communicated with the liquid phase outlet of the third condenser, and is provided with a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, and the second liquid phase outlet is communicated with the reflux inlet of the saponification tower; and
and the material inlet of the crude epichlorohydrin storage tank is communicated with the first liquid phase outlet of the crude epichlorohydrin storage tank.
The general saponification column feed adopts first piece column plate feeding, adopts the feeding of second piece column plate here, and first piece column plate is hot water washing, has following advantage: the first saponification tower is easy to scale, and the scaling phenomenon can be avoided by adding a hot water flushing port; secondly, if the material is fed from the first tray, the incoming material is directly stripped by dichloropropanol steam, so that dichloropropanol is polluted, if the material is fed from the third tray and even lower tray, the reaction efficiency and the yield are influenced, and the problem can be effectively avoided when the material is fed from the second tray; thirdly, the first column plate is washed with hot water, the second column plate is fed, and the two inlets are not mutually influenced, so that the method has the advantage of higher starting efficiency compared with the original feeding mode of the first column plate.
Still further, the dichloropropanol saponification unit also comprises
A flash tank, wherein a liquid phase inlet of the flash tank is communicated with a liquid phase outlet of the saponification tower;
the liquid phase inlet of the second cooler is communicated with the liquid phase outlet of the flash tank, and the liquid phase outlet of the second cooler is connected to the calcium chloride pretreatment unit; and
and a gas phase inlet of the fourth condenser is communicated with a gas phase outlet of the flash tank, the gas phase outlet of the fourth condenser is connected with a third vacuum pump, and a liquid phase outlet of the fourth condenser is connected to the sewage treatment unit.
The solid content of the calcium chloride mother liquor discharged from the liquid phase outlet of the saponification tower is high, the calcium chloride mother liquor is easy to block when cooled by a cooler, and the calcium chloride mother liquor is cooled by vacuum flash evaporation, so that the stable operation of the system is ensured.
The invention solves the second technical problem by adopting the technical proposal that: the epichlorohydrin production process using the epichlorohydrin production device comprises the following steps:
first, glycerol chlorination: the glycerin catalyst solution in the raw material storage tank is sent into a pre-reaction tower to be pre-reacted with unreacted hydrogen chloride from each reaction kettle and hydrogen chloride resolved by a resolving tower, the reacted feed liquid is simultaneously sent into a first-stage reaction kettle, a second-stage reaction kettle and a third-stage reaction kettle, the hydrogen chloride pipeline is used for sending the hydrogen chloride into each reaction kettle, the feed liquid of the first-stage reaction kettle is sent into the second-stage reaction kettle, the feed liquid of the second-stage reaction kettle is sent into the third-stage reaction kettle, the crude dichloropropanol after the reaction of the third-stage reaction kettle is sent into the resolving tower, the unreacted hydrogen chloride of the first-stage reaction kettle is sent into the second-stage reaction kettle, the unreacted hydrogen chloride of the second-stage reaction kettle is sent into the third-stage reaction kettle, and the unreacted hydrogen chloride of the third-stage reaction kettle is sent into the pre-reaction tower;
second, refining dichloropropanol: the method comprises the steps that the crude dichloropropanol is resolved by the resolving tower, the resolved gas phase is sent to the pre-reaction tower, the resolved crude dichloropropanol is sent to the rectifying tower, heavy components from the rectifying tower enter the first layering tank, the heavy components layered by the first layering tank are sent to the dichloropropanol recovery tower to recover the dichloropropanol therein, the layered light components return to each reaction kettle to react again, and the lateral line of the rectifying tower is discharged to obtain refined dichloropropanol;
thirdly, saponification of dichloropropanol: and (3) allowing refined dichloropropanol conveyed from the rectifying tower to enter a dichloropropanol saponification unit for saponification to obtain epichlorohydrin.
Preferably, the ratio of hydrogen chloride fed from the hydrogen chloride pipeline into the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle is 8:1:1-5:5:0.
The hydrogen chloride with proper ratio is respectively sent into the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle, so that the content of the monochloropropanediol in the third-stage reaction kettle is ensured to be less than 1%, and the content of the monochloropropanediol and COD in the calcium chloride mother liquor of the saponification tower is reduced.
Preferably, the operation pressure of the resolving tower is 0.15-0.30 MPa, the gas phase outlet of the resolving tower is communicated with the gas phase inlet of the pre-reaction tower through a self-flowing pipeline, and the liquid phase outlet of the resolving tower is communicated with the liquid phase inlet of the rectifying tower through a first pipeline, wherein the first pipeline is a self-flowing pipeline.
The operation pressure of the analysis tower is increased to enable more hydrogen chloride in the ternary azeotrope in the analysis tower to be analyzed, but the operation pressure is too high to cause less recovered monochloropropanediol, so that the monochloropropanediol and dichloropropanol enter the rectification tower together, and therefore, the operation pressure of the analysis tower needs to be reasonably controlled;
in addition, the operation pressure of the analysis tower is controlled to be 0.15-0.30 MPa, and the additional function is also realized: on one hand, the hydrogen chloride resolved by the resolving tower can be guaranteed to automatically flow and be recycled to the pre-reaction tower, so that the energy consumption is reduced; on the other hand, because the analytic tower is positive in pressure and the rectifying tower is negative in pressure, the materials in the analytic tower can automatically flow to the rectifying tower, so that the energy consumption is reduced.
Compared with the prior art, the invention has the advantages that: firstly, the rectifying tower materials are directly returned to the reaction kettle to be mixed unevenly, and the first layering tank is arranged, so that the effect of stable production can be achieved, meanwhile, the heavy component return to the reaction system is reduced, the steam consumption is reduced, the catalyst content in the reaction kettle is relatively uniform, and the reaction speed is relatively stable; secondly, the lower material can be intermittently recycled in the dichloropropanol recycling tower, continuous operation is not needed, and steam consumption can be reduced.
Drawings
FIG. 1 is a schematic structural view showing an example of an epichlorohydrin production apparatus of the invention;
FIG. 2 is a schematic diagram of the glycerol chlorination unit of FIG. 1;
FIG. 3 is a schematic structural view of the dichloropropanol refining unit of FIG. 1;
FIG. 4 is a schematic diagram of the structure of the dichloropropanol saponification unit of FIG. 1.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
As shown in fig. 1 to 4, a preferred embodiment of the epichlorohydrin production apparatus of the invention is shown.
As shown in figure 1, the epichlorohydrin production device comprises a glycerol chlorination unit 1, a dichloropropanol refining unit 2 and a dichloropropanol saponification unit 3 which are sequentially connected.
As shown in fig. 2, the glycerol chlorination unit 1 comprises a raw material storage tank 11, a pre-reaction tower 12, a first-stage reaction kettle 13, a second-stage reaction kettle 14 and a third-stage reaction kettle 15.
Specifically, the raw material storage tank 11 is used for storing a glycerin catalyst solution;
the top of the pre-reaction tower 12 is provided with a liquid phase inlet and a gas phase outlet, and the bottom is provided with a gas phase inlet and a liquid phase outlet; the liquid phase inlet of the pre-reaction tower 12 is communicated with the material outlet of the raw material storage tank 11, and the gas phase outlet of the pre-reaction tower 12 is connected to the tail gas absorption unit 121; in the embodiment, the pre-reaction tower 12 adopts PVDF taylor rings as the filler, so that the corrosion of acid materials can be resisted, the reaction contact area is increased, and the stable operation of equipment is ensured; in the pre-reaction tower 12, the mixed glycerol and catalyst in the raw material storage tank 11 are subjected to preliminary reaction with the unreacted hydrogen chloride in the analysis tower 21 and each reaction kettle, then are sent into each reaction kettle to further react with the hydrogen chloride, and finally the materials are sent into the analysis tower 21 to remove the unreacted hydrogen chloride;
the tops of the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 are respectively provided with a liquid phase inlet and a gas phase outlet, and the bottoms are respectively provided with a gas phase inlet and a liquid phase outlet;
the liquid phase inlet of the first-stage reaction kettle 13 is communicated with the liquid phase outlet of the pre-reaction tower 12, and the gas phase inlet of the first-stage reaction kettle 13 is communicated with the externally connected hydrogen chloride pipeline 10; in the embodiment, the number of the first-stage reaction kettles 13 is at least two, and the first-stage reaction kettles 13 are mutually connected in parallel, one is operated, and the other is reserved;
the liquid phase inlet of the second-stage reaction kettle 14 is communicated with the liquid phase outlet of the pre-reaction tower 12 and the liquid phase outlet of the first-stage reaction kettle 13, and the gas phase inlet of the second-stage reaction kettle 14 is communicated with the externally connected hydrogen chloride pipeline 10 and the gas phase outlet of the first-stage reaction kettle 13;
the liquid phase inlet of the three-stage reaction kettle 15 is communicated with the liquid phase outlet of the pre-reaction tower 12 and the liquid phase outlet of the two-stage reaction kettle 14, the gas phase inlet of the three-stage reaction kettle 15 is communicated with the external hydrogen chloride pipeline 10 and the gas phase outlet of the two-stage reaction kettle 14, and the gas phase outlet of the three-stage reaction kettle 15 is communicated with the gas phase inlet of the pre-reaction tower 12.
In the glycerol chlorination unit 1, the liquid phase outlet of the pre-reaction tower 12 is communicated with the liquid phase inlets of all the reaction kettles, so that materials of the pre-reaction tower 12 can enter all the reaction kettles for the first time, and the operation of starting is convenient; in addition, the materials of the upper-stage reaction kettle enter the lower stage, so that the reaction efficiency between the glycerol and the hydrogen chloride in the lower-stage reaction kettle can be effectively improved.
As shown in fig. 3, the dichloropropanol refining unit 2 includes a desorption tower 21, a rectifying tower 22, a glycerin absorber 23, a first cooler 24, an ejector 25, an alkaline washing tower 26, a first layering tank 27, and a dichloropropanol recovery tower 28.
Specifically, a first reboiler 211 is installed at the bottom of the analysis tower 21, a first condenser 212 is installed at the top of the analysis tower 21, a liquid phase inlet of the analysis tower 21 is communicated with a liquid phase outlet of the three-section reaction kettle 15, and a gas phase outlet at the top of the analysis tower 21 is communicated with a gas phase inlet of the pre-reaction tower 12 through a self-flowing pipeline; in the embodiment, the analysis tower 21 adopts PVDF taylor rings as the packing, so that the equipment can be operated more stably;
in the prior art, the gas at the top of the resolving tower is condensed and then directly introduced into the saponification tower, the main component of the condensate is hydrogen chloride aqueous solution containing monochloropropanediol and dichloropropanol, the introduction of the condensate into the saponification tower increases the alkali liquor consumption, the load of the saponification tower is improved, and the monochloropropanediol enters into the calcium chloride aqueous solution, so that the quality of the saponified water is reduced, and the further recycling is affected, in this embodiment, since the gas phase outlet of the resolving tower 21 is communicated with the gas phase inlet of the pre-reaction tower 12, firstly, 200Nm of the condensate is expected to be recycled 3 Hydrogen chloride per hour, reducing 1t/h lime milk consumption (15 wt% concentration); secondly, the load of the subsequent analytic tower and saponification tower can be reduced; thirdly, the content of monochloropropanediol in the saponification tower can be greatly reduced;
the bottom of the rectifying tower 22 is provided with a second reboiler 221, the top of the rectifying tower 22 is provided with a second condenser 222, the liquid phase inlet of the rectifying tower 22 is communicated with the liquid phase outlet at the bottom of the resolving tower 21, the bottom of the rectifying tower 22 is provided with a first liquid phase outlet for discharging heavy components, the side part of the rectifying tower 22 is provided with a second liquid phase outlet for discharging light components, and the top of the rectifying tower 22 is provided with a gas phase outlet for discharging tail gas; specifically, the liquid phase outlet of the resolution column 21 is respectively connected to the liquid phase inlet of the rectifying column 22 through a first pipeline 223 and a second pipeline 224, the first pipeline 223 is a self-flow pipeline, and the second pipeline 224 is provided with a first conveying pump 225 capable of conveying materials from the liquid phase outlet of the resolution column 21 to the liquid phase inlet of the rectifying column 22; the second reboiler 221 is connected to the bottom of the rectifying tower 22 through a first circulation pipeline 226 and a second circulation pipeline 227, the first circulation pipeline 226 adopts a siphon self-circulation pipeline, and the second circulation pipeline 227 is provided with a circulation pump 228 capable of conveying materials from an inlet of the second circulation pipeline 227 to an outlet of the second circulation pipeline 227, so that the second reboiler 221 of the rectifying tower 22 can reduce energy consumption by means of the siphon self-circulation, and in actual application, the circulation pump 228 is used for forced circulation in advance, and the later stage can select which circulation according to actual conditions, thereby saving energy and reducing consumption (90 KW can be saved per hour);
the liquid phase inlet of the glycerol absorber 23 is communicated with the material outlet of the raw material storage tank 11, the gas phase inlet of the glycerol absorber 23 is communicated with the gas phase outlet of the rectifying tower 22, and the liquid phase outlet of the glycerol absorber 23 is communicated with the liquid phase inlet of the pre-reaction tower 12; the glycerol absorber 23 can absorb part of organic matters and hydrogen chloride in the tail gas of the rectifying tower 22, and the liquid phase outlet of the glycerol absorber 23 is communicated with the liquid phase inlet of the pre-reaction tower 12, so that the hydrogen chloride and the glycerol can be conveniently recovered;
the gas phase inlet of the first cooler 24 is communicated with the gas phase outlet of the glycerin absorber 23; the organic matters cooled by the first cooler 24 are recycled to the first layering tank 27, so that dichloropropanol in the tail gas of the rectifying tower 22 can be effectively recycled;
the gas phase inlet of the ejector 25 communicates with the gas phase outlet of the first cooler 24; the jet pump 25 can jet the steam from the nozzle at a high speed, and form a low pressure in the vacuum chamber, so that the gas at the top of the rectifying tower 22 sequentially enters the vacuum chamber, the mixing chamber and the saponification tower, the jetted steam can be used for the saponification tower 32 to react, and meanwhile, the jet pump 25 can reduce the load of the first vacuum pump 261 or partially replace the first vacuum pump 261 when the first vacuum pump 261 fails, so that the stable operation of the rectifying tower 22 is ensured.
The gas phase inlet of the alkaline washing tower 26 is communicated with the gas phase outlet of the first cooler 24, and the gas phase outlet at the top of the alkaline washing tower 26 is connected with a first vacuum pump 261; the glycerin absorber 23, the first cooler 24 and the alkaline washing tower 26 can remove most of hydrogen chloride in the noncondensable gas, so that the influence on the vacuum degree of the rectifying tower 22 caused by excessive noncondensable gas is prevented, and meanwhile, the acid noncondensable gas mixed in tail gas can corrode the first vacuum pump 261, so that the quality and the yield stability of dichloropropanol are influenced;
the liquid phase inlet of the first layering tank 27 is communicated with the first liquid phase outlet of the rectifying tower 22 and the liquid phase outlet of the first cooler 24, the first layering tank 27 is provided with a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, and the second liquid phase outlet of the first layering tank 27 is communicated with the liquid phase inlets of the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15; specifically, a second transfer pump 271 capable of transferring the material from the first liquid phase outlet of the rectifying column 22 to the liquid phase inlet of the first layering tank 27 is installed on a pipe between the liquid phase inlet of the first layering tank 27 and the first liquid phase outlet of the rectifying column 22;
the materials discharged from the first liquid phase outlet and the second liquid phase outlet of the first layering tank 27 have similar compositions but different proportions, wherein the content of the catalyst and the dibasic acid ester in the materials discharged from the second liquid phase outlet is higher; the first stratified tank 27 functions principally as follows: firstly, the materials in the rectifying tower 22 are directly returned to the reaction kettle to be mixed unevenly, and the first layering tank 27 is provided, so that the stable production effect can be achieved, meanwhile, the heavy component return to the reaction system is reduced, the steam consumption is reduced, the catalyst content in the reaction kettle is relatively uniform, and the reaction speed is more stable; secondly, the lower material can be intermittently recycled in the dichloropropanol recycling tower 28, so that the steam consumption can be reduced without continuous operation;
a dichloropropanol recovery column 28, the liquid phase inlet of which is communicated with the first liquid phase outlet of the first layering tank 27; in the embodiment, 760 tons of DCH can be recovered in the dichloropropanol recovery tower for 28 years, and the benefit is obvious.
As shown in fig. 4, the dichloropropanol saponification unit 3 comprises an alkali solution tank 31, a saponification tower 32, a third condenser 33, a second layering tank 34, a crude epichlorohydrin storage tank 35, a flash tank 36, a second cooler 37 and a fourth condenser 38.
The alkali solution tank 31 is used for storing alkali solution; in this example, the lye is calcium hydroxide;
the saponification tower 32 is provided with a material inlet corresponding to the second tower plate and a hot water inlet corresponding to the first tower plate, the material inlet of the saponification tower 32 is communicated with the second liquid phase outlet of the rectifying tower 22 and the material outlet of the alkali liquor tank 31, and the hot water inlet of the saponification tower 32 is communicated with the external hot water pipeline 30; specifically, a third transfer pump 321 capable of transferring the material from the second liquid phase outlet of the rectifying column 22 to the material inlet of the saponification column 32 is installed on a pipe between the material inlet of the saponification column 32 and the second liquid phase outlet of the rectifying column 22;
the general saponification column feed adopts first piece column plate feeding, adopts the feeding of second piece column plate here, and first piece column plate is hot water washing, has following advantage: the first saponification tower 32 is easy to scale, and the scaling phenomenon can be avoided by adding a hot water flushing port; secondly, if the material is fed from the first tray, the incoming material is directly stripped by dichloropropanol steam, so that dichloropropanol is polluted, if the material is fed from the third tray and even lower tray, the reaction efficiency and the yield are influenced, and the problem can be effectively avoided when the material is fed from the second tray; thirdly, the first tower plate is washed by hot water, the second tower plate is fed, and the two inlets are not mutually influenced, so that the method has the advantage of higher starting efficiency compared with the original feeding mode of the first tower plate;
the gas phase inlet of the third condenser 33 is communicated with the gas phase outlet at the top of the saponification tower 32, and the gas phase outlet of the third condenser 33 is connected with a second vacuum pump 331;
the liquid phase inlet of the second layering tank 34 is communicated with the liquid phase outlet of the third condenser 33, the second layering tank 34 is provided with a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, and the second liquid phase outlet is communicated with the reflux inlet of the saponification column 32; specifically, a fourth transfer pump 322 capable of transferring the material from the second liquid phase outlet of the second stratified tank 34 to the reflux inlet of the saponification column 32 is installed on a line between the reflux inlet of the saponification column 32 and the second liquid phase outlet of the second stratified tank 34;
the material inlet of the crude epichlorohydrin storage tank 35 is communicated with the first liquid phase outlet of the crude epichlorohydrin storage tank 35;
the liquid phase inlet of flash tank 36 communicates with the liquid phase outlet of saponification column 32; specifically, a fifth transfer pump 361 capable of transferring the material from the liquid phase outlet of the saponification column 32 to the liquid phase inlet of the flash tank 36 is installed on a line between the liquid phase inlet of the flash tank 36 and the liquid phase outlet of the saponification column 32; the solid content of the calcium chloride mother liquor discharged from the liquid phase outlet of the saponification tower 32 is high, the calcium chloride mother liquor is easy to block when cooled by a cooler, and the calcium chloride mother liquor is cooled by vacuum flash evaporation, so that the stable operation of the system is ensured;
the liquid phase inlet of the second cooler 37 is communicated with the liquid phase outlet of the flash tank 36, and the liquid phase outlet of the second cooler 37 is connected to the calcium chloride pretreatment unit 371; and
the gas phase inlet of the fourth condenser 38 is communicated with the gas phase outlet of the flash tank 36, the gas phase outlet of the fourth condenser 38 is connected with a third vacuum pump 381, and the liquid phase outlet of the fourth condenser 38 is connected to a sewage treatment unit 382.
The invention also provides an epoxy chloropropane production process using the epoxy chloropropane production device.
Example 1:
first, glycerol chlorination: controlling the operation pressure of the pre-reaction tower 12 to be 50kPa, feeding glycerin catalyst solution in a raw material storage tank 11 into the pre-reaction tower 12 to perform pre-reaction with unreacted hydrogen chloride from each reaction kettle and hydrogen chloride resolved by a resolving tower 21, feeding reacted feed liquid into a first-stage reaction kettle 13, a second-stage reaction kettle 14 and a third-stage reaction kettle 15 at the same time, feeding hydrogen chloride into the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 respectively through a hydrogen chloride pipeline 10 according to the ratio of 6:4:0, feeding the feed liquid of the first-stage reaction kettle 13 into the second-stage reaction kettle 14 by using the pressure difference, feeding the feed liquid of the second-stage reaction kettle 14 into the third-stage reaction kettle 15 by using the pressure difference, feeding crude dichloropropanol after the reaction of the third-stage reaction kettle 15 into the resolving tower 21, feeding unreacted hydrogen chloride of the first-stage reaction kettle 13 into the second-stage reaction kettle 14, feeding unreacted hydrogen chloride of the second-stage reaction kettle 14 into the third-stage reaction kettle 15, and feeding unreacted hydrogen chloride of the third-stage reaction kettle 15 into the pre-reaction tower 12;
second, refining dichloropropanol: controlling the operation pressure of the analysis tower 21 to be 0.25MPa, analyzing the crude dichloropropanol by the analysis tower 21, conveying the analyzed gas phase into the pre-reaction tower 12, conveying the analyzed crude dichloropropanol into the rectifying tower 22, conveying the non-condensable gas discharged from a gas phase outlet at the top of the rectifying tower 22 to a first cooler 24 for further condensation after the non-condensable gas is absorbed by a falling film of a glycerol absorber 23, and conveying the liquid phase into the pre-reaction tower 12; the gas phase condensed by the first cooler 24 is divided into two parts, one part is pumped out by the ejector 25, the other part is pumped out by the first vacuum pump 261 after entering the alkaline washing tower 26, and the liquid phase flow after condensation enters the first layering tank 27; the heavy components from the rectifying tower 22 also enter a first layering tank 27, the heavy components layered by the first layering tank 27 are sent to a dichloropropanol recovery tower 28 to recover dichloropropanol therein, and the layered light components are returned to each reaction kettle for re-reaction; the side discharge of the rectifying tower 22 is refined dichloropropanol;
thirdly, saponification of dichloropropanol: the refined dichloropropanol conveyed from the rectifying tower 22 and the alkali liquor from the alkali liquor tank 31 are mixed and then enter a second column plate of the saponification tower 32, and hot water in the hot water pipeline 30 enters a first column plate of the saponification tower 32 for flushing; the epichlorohydrin generated in the saponification tower 32 is distilled out along with stripping steam and then enters a third condenser 33, the condensed noncondensable gas is pumped out by a second vacuum pump 331, and the condensate enters a second layering tank 34; the condensate is separated in a second layering tank 34 in a layering way, the layered heavy component is coarse epichlorohydrin, the coarse epichlorohydrin is sent to a coarse epichlorohydrin storage tank 35 to wait for further refining, the layered light component is water, and the water is sent back to the saponification tower 32; the kettle liquid of the saponification tower 32 is sent to a flash tank 36, the liquid phase after flash evaporation is sent to a second cooler 37 for cooling and then sent to a calcium chloride pretreatment unit 371, the gas phase after flash evaporation is sent to a fourth condenser 38, the condensed non-condensable gas is pumped out by a third vacuum pump 381, and the condensate is sent to a sewage treatment unit 382;
and detecting the liquid phase outlet materials of the three-stage reaction kettle 15, and recording the contents of monochloropropanediol and dichloropropanol.
Example 2:
the difference from example 1 is that: in the first step, the hydrogen chloride pipeline 10 feeds hydrogen chloride into the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 in a ratio of 8:1:1 respectively.
Example 3:
the difference from example 1 is that: in the first step, the hydrogen chloride pipeline 10 feeds hydrogen chloride into the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 in a ratio of 6:3:1 respectively.
Example 4:
the difference from example 1 is that: in the first step, the hydrogen chloride pipeline 10 feeds hydrogen chloride into the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 in a ratio of 5:5:0 respectively.
Example 5:
the difference from example 1 is that: in the second step, the operation pressure of the analyzing column 21 was 0.15MPa;
example 6:
the difference from example 1 is that: in the second step, the operation pressure of the analyzing column 21 was 0.30MPa;
comparative example 1:
the difference from example 1 is that: in the first step, the hydrogen chloride pipeline 10 feeds hydrogen chloride into a first-stage reaction kettle 13, a second-stage reaction kettle 14 and a third-stage reaction kettle 15 in a ratio of 5:3:2 respectively.
Comparative example 2:
the difference from example 1 is that: in the second step, the operation pressure of the analysis column 21 was 50kPa;
comparative example 3:
the difference from example 1 is that: in the second step, the operation pressure of the analyzing column 21 was 0.35MPa;
the results of the performance tests of all the above examples and comparative examples are shown in table 1.
As can be seen from table 1:
(1) As can be seen from examples 1 to 4 and comparative example 1, the hydrogen chloride with a proper ratio is respectively fed into the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15, so that the content of monochloropropanediol in the third-stage reaction kettle 15 is ensured to be less than 1%, and the content of monochloropropanediol and COD in the calcium chloride mother liquor of the saponification tower is reduced;
(2) As can be seen from examples 1, 5, 6, 2 and 3, the operation pressure of the resolving tower 21 can be increased to resolve more hydrogen chloride in the ternary azeotrope in the resolving tower 21, but too high an operation pressure can result in less monochloropropanediol being recovered, so that monochloropropanediol can enter the rectifying tower 22 together with dichloropropanol, thus the operation pressure of the resolving tower 21 needs to be reasonably controlled;
in addition, the operation pressure of the analysis column 21 is controlled to be 0.15 to 0.30MPa, and the additional function is also achieved: on one hand, the hydrogen chloride resolved by the resolving tower can be guaranteed to automatically flow and be recycled to the pre-reaction tower, so that the energy consumption is reduced; on the other hand, because the analytic tower is positive in pressure and the rectifying tower is negative in pressure, the materials in the analytic tower can automatically flow to the rectifying tower, so that the energy consumption is reduced.
Claims (5)
1. The utility model provides an epoxy chloropropane apparatus for producing, is including glycerin chlorination unit (1), dichloropropanol refining element (2) and dichloropropanol saponification unit (3) that are connected in proper order, its characterized in that: the dichloropropanol refining unit (2) comprises
The bottom of the analysis tower (21) is provided with a first reboiler (211), the top of the analysis tower is provided with a first condenser (212), and a liquid phase inlet of the analysis tower is communicated with a material outlet of the glycerol chlorination unit (1);
the rectifying tower (22) is provided with a second reboiler (221) at the bottom, a second condenser (222) at the top, a liquid phase inlet of which is communicated with a liquid phase outlet of the resolving tower (21), a first liquid phase outlet for discharging heavy components is arranged at the bottom, a second liquid phase outlet for discharging light components is arranged at the side part, and the second liquid phase outlet is communicated with a material inlet of the dichloropropanol saponification unit (3);
a first layering tank (27), wherein a liquid phase inlet of the first layering tank is communicated with a first liquid phase outlet of the rectifying tower (22), a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components are formed, and a second liquid phase outlet of the first layering tank (27) is communicated with a material inlet of the glycerol chlorination unit (1); and
a dichloropropanol recovery column (28) with a liquid phase inlet communicated with a first liquid phase outlet of the first layering tank (27);
the glycerol chlorination unit (1) comprises
A raw material storage tank (11) for storing a glycerin catalyst solution;
a liquid phase inlet of the pre-reaction tower (12) is communicated with a material outlet of the raw material storage tank (11), and a gas phase outlet for discharging tail gas is arranged at the top of the pre-reaction tower;
the liquid phase inlet of the first-stage reaction kettle (13) is communicated with the liquid phase outlet of the pre-reaction tower (12), the gas phase inlet of the first-stage reaction kettle is communicated with an external hydrogen chloride pipeline (10), the number of the first-stage reaction kettle (13) is at least two, and the first-stage reaction kettles (13) are mutually connected in parallel;
a liquid phase inlet of the second-stage reaction kettle (14) is communicated with a liquid phase outlet of the pre-reaction tower (12) and a liquid phase outlet of the first-stage reaction kettle (13), and a gas phase inlet of the second-stage reaction kettle is communicated with an externally connected hydrogen chloride pipeline (10) and a gas phase outlet of the first-stage reaction kettle (13); and
a liquid phase inlet of the three-stage reaction kettle (15) is communicated with a liquid phase outlet of the pre-reaction tower (12) and a liquid phase outlet of the two-stage reaction kettle (14), a gas phase inlet of the three-stage reaction kettle is communicated with an externally connected hydrogen chloride pipeline (10) and a gas phase outlet of the two-stage reaction kettle (14), and a gas phase outlet of the three-stage reaction kettle is communicated with a gas phase inlet of the pre-reaction tower (12);
the dichloropropanol saponification unit (3) comprises
An alkali solution tank (31) for storing alkali solution;
a saponification column (32) provided with a material inlet corresponding to the second column plate and a hot water inlet corresponding to the first column plate, wherein the material inlet of the saponification column (32) is communicated with a second liquid phase outlet of the rectifying column (22) and a material outlet of the alkali liquor tank (31), and the hot water inlet of the saponification column (32) is communicated with an external hot water pipeline (30);
a third condenser (33) with a gas phase inlet communicated with a gas phase outlet of the saponification tower (32), and a second vacuum pump (331) connected with the gas phase outlet;
a second stratified tank (34) whose liquid phase inlet communicates with the liquid phase outlet of the third condenser (33) and has a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, said second liquid phase outlet communicating with the reflux inlet of the saponification column (32); and
a crude epichlorohydrin storage tank (35), wherein the material inlet of the crude epichlorohydrin storage tank (35) is communicated with the first liquid phase outlet of the crude epichlorohydrin storage tank;
the liquid phase inlet of the resolving tower (21) is communicated with the liquid phase outlet of the three-section reaction kettle (15);
the gas phase outlet of the analysis tower (21) is communicated with the gas phase inlet of the pre-reaction tower (12);
the second liquid phase outlet of the first layering tank (27) is communicated with the liquid phase inlets of the first-stage reaction kettle (13), the second-stage reaction kettle (14) and the third-stage reaction kettle (15).
2. The epichlorohydrin production apparatus according to claim 1, characterized in that: the dichloropropanol refining unit (2) also comprises
A glycerol absorber (23) with a liquid phase inlet communicated with a material outlet of the raw material storage tank (11), a gas phase inlet communicated with a gas phase outlet of the rectifying tower (22), and a liquid phase outlet communicated with a liquid phase inlet of the pre-reaction tower (12); and
-a first cooler (24) with its gas phase inlet communicating with the gas phase outlet of the glycerol absorber (23) and its liquid phase outlet communicating with the liquid phase inlet of the first stratified tank (27).
3. The epichlorohydrin production apparatus according to claim 2, characterized in that: the dichloropropanol refining unit (2) also comprises
-an ejector (25) with a gas phase inlet communicating with a gas phase outlet of the first cooler (24); and
and a gas phase inlet of the alkaline washing tower (26) is communicated with a gas phase outlet of the first cooler (24), and a gas phase outlet at the top is connected with a first vacuum pump (261).
4. The epichlorohydrin production apparatus according to claim 1, characterized in that: the dichloropropanol saponification unit (3) also comprises
A flash tank (36) having a liquid phase inlet in communication with a liquid phase outlet of the saponification column (32);
a second cooler (37) whose liquid phase inlet communicates with the liquid phase outlet of the flash tank (36), and whose liquid phase outlet is connected to the calcium chloride pretreatment unit (371); and
and a fourth condenser (38) with a gas phase inlet communicated with a gas phase outlet of the flash tank (36), a third vacuum pump (381) connected to the gas phase outlet, and a liquid phase outlet connected to a sewage treatment unit (382).
5. A epichlorohydrin production process using the epichlorohydrin production apparatus as claimed in any one of claims 1 to 4, comprising the steps of:
first, glycerol chlorination: feeding a glycerol catalyst solution in a raw material storage tank (11) into a pre-reaction tower (12) to perform pre-reaction with unreacted hydrogen chloride from each reaction kettle and hydrogen chloride resolved by a resolving tower (21), feeding reacted feed liquid into a first-stage reaction kettle (13), a second-stage reaction kettle (14) and a third-stage reaction kettle (15) at the same time, feeding the hydrogen chloride into each reaction kettle through a hydrogen chloride pipeline (10), feeding feed liquid of the first-stage reaction kettle (13) into the second-stage reaction kettle (14), feeding feed liquid of the second-stage reaction kettle (14) into the third-stage reaction kettle (15), feeding crude dichloropropanol after the reaction of the third-stage reaction kettle (15) into the resolving tower (21), feeding unreacted hydrogen chloride of the first-stage reaction kettle (13) into the second-stage reaction kettle (14), feeding unreacted hydrogen chloride of the second-stage reaction kettle (14) into the third-stage reaction kettle (15), and feeding unreacted hydrogen chloride of the third-stage reaction kettle (15) into the pre-reaction tower (12);
second, refining dichloropropanol: the method comprises the steps that crude dichloropropanol is resolved by a resolving tower (21), a resolved gas phase is sent to a pre-reaction tower (12), resolved crude dichloropropanol is sent to a rectifying tower (22), heavy components from the rectifying tower (22) enter a first layering tank (27), a heavy component from the first layering tank (27) is sent to a dichloropropanol recovery tower (28) to recover the dichloropropanol, the layered light components are returned to each reaction kettle to react again, and a side line of the rectifying tower (22) is discharged to obtain refined dichloropropanol;
thirdly, saponification of dichloropropanol: refined dichloropropanol conveyed from a rectifying tower (22) enters a dichloropropanol saponification unit (3) for saponification to prepare epoxy chloropropane;
the hydrogen chloride is sent into the first-stage reaction kettle (13), the second-stage reaction kettle (14) and the third-stage reaction kettle (15) from the hydrogen chloride pipeline (10) in a ratio of 8:1:1-5:5:0;
the operation pressure of the analysis tower (21) is 0.15-0.30 MPa, a gas phase outlet of the analysis tower (21) is communicated with a gas phase inlet of the pre-reaction tower (12) through a self-flowing pipeline, a liquid phase outlet of the analysis tower (21) is communicated with a liquid phase inlet of the rectifying tower (22) through a first pipeline (223), and the first pipeline (223) is a self-flowing pipeline.
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| CN115745920A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Method for recovering effective components in waste liquid in epoxy chloropropane production |
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