CN112239434A - Epoxy chloropropane production device and process - Google Patents
Epoxy chloropropane production device and process Download PDFInfo
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- CN112239434A CN112239434A CN202011288662.5A CN202011288662A CN112239434A CN 112239434 A CN112239434 A CN 112239434A CN 202011288662 A CN202011288662 A CN 202011288662A CN 112239434 A CN112239434 A CN 112239434A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 209
- 239000007791 liquid phase Substances 0.000 claims abstract description 175
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 149
- 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 50
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 18
- 238000007670 refining Methods 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 115
- 239000012071 phase Substances 0.000 claims description 93
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 64
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 63
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 63
- 235000011187 glycerol Nutrition 0.000 claims description 51
- 238000003795 desorption Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 21
- 238000003860 storage 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 15
- 239000007788 liquid Substances 0.000 claims description 14
- 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 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims 5
- 230000005484 gravity Effects 0.000 claims 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000004458 analytical method Methods 0.000 description 6
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- 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
- 239000003225 biodiesel Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000126 substance Substances 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
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- 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
- 239000005416 organic matter Substances 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
- 238000000066 reactive distillation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FLTSEOGWHPJWRV-UHFFFAOYSA-N 1,2-dichloropropan-1-ol Chemical compound CC(Cl)C(O)Cl FLTSEOGWHPJWRV-UHFFFAOYSA-N 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 2,3-dichloropropan-1-ol Chemical compound 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
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 acetate propylene ester Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [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
- 239000003518 caustics Substances 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichlorine monoxide Inorganic materials ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 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
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 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
- 239000003960 organic solvent 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
- 238000004064 recycling Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
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Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 an analytical 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 analytical 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 epichlorohydrin production process using the epichlorohydrin production device. Compared with the prior art, the invention can effectively recover the light components of the rectifying tower to the reaction system while stabilizing the production, and reduce the energy consumption.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a production device and a production process of epichlorohydrin.
Background
Epichlorohydrin (synonym epichlorohydrin) with the chemical name of 1-chloro-2, 3-epoxypropane and the molecular formula of C3H5OCl, boiling point 115.2 deg.C, freezing point-57.2 deg.C, is a volatile, unstable, colorless liquid, slightly soluble in water, and miscible with various organic solvents.
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 surface active agent, plasticizer, stabilizer, adhesive and ion exchange resin. The method also has wide application in the industries of coatings, adhesives, reinforcing materials, casting materials, electronic laminated products and the like. In addition, the epichlorohydrin can also be used for synthesizing various products such as surfactants, medicines, pesticides, coatings, sizing materials, ion exchange resins and the like, and can also be used for producing chemical stabilizers, chemical dyes, water treatment agents and the like.
The prior production method of epichlorohydrin mainly comprises a propylene high-temperature chlorination method and an acetate propylene ester method, wherein the two methods both use propylene as a raw material and depend on the consumption of petroleum energy. With the further price rise and resource shortage of petroleum energy, the raw material source and price of propylene are greatly influenced by the market. Due to the international rise of biodiesel, a large amount of glycerol as a by-product causes a surplus in the glycerol market, and about 1 ton of glycerol as a by-product can be produced per 10 tons of biodiesel produced. The market of glycerin as a byproduct of biodiesel is more and more demanding, and the glycerin-method epichlorohydrin becomes a new epichlorohydrin production technology which is widely concerned recently. Dichloropropanol comprising 2, 3-dichloro-1-propanol and 1, 3-dichloro-2-propanolA seed isomer having a molecular formula of C3H6Cl2O, boiling point of 174 ℃, and colorless liquid has slight chloroform smell, and is an intermediate product for producing epoxy chloropropane. Dichloropropanol by reaction with Ca (OH)2After saponification reaction of NaOH, the dichloropropanol can be cyclized to generate the final product epichlorohydrin.
For example, patent application No. CN202010346652.6 (publication No. CN111499598A) discloses a process for preparing epichlorohydrin by a glycerol method, in which glycerol, a catalyst and hydrogen chloride are added into a reactor to react, monochloropropanediol and water are generated in the reactor, monochloropropanediol and hydrogen chloride continue to react in the reactor to generate dichloropropanol, the raw material in the reactor is reacted for a period of time, the obtained product enters a reactive distillation column, the raw material is reacted and separated in the reactive distillation column, dichloropropanol obtained by hydrochlorination is fed into a pre-reactor to perform cyclization reaction with alkali liquor, most of liquid alkali is added from the inlet of the pre-reactor, the other part of alkali liquor is added through feeding into the pre-reactor, the obtained product in the pre-reactor, the rest of 1, 2-dichloropropanol and alkali liquor enter the cyclization column, and fully reacting to generate epoxy chloropropane, sending a product obtained at the top of the cyclization tower into a second rectifying tower for further separation, and obtaining epoxy chloropropane at the top of the tower.
In the scheme, firstly, materials at the bottom of the first rectifying tower are directly fed into the reactor, so that on one hand, the mixing is not uniform, and on the other hand, heavy components in the materials return to the reaction system together, and the steam consumption is increased; secondly, dichlorohydrin and hydrogen chloride obtained from the top of the reaction rectifying tower and the first rectifying tower enter downstream, so that hydrogen chloride is wasted, 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 recover light components of a rectifying tower to a reaction system while stably producing and reduce energy consumption, aiming at the current situation of the prior art.
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 the glycerine chlorination unit that links to each other in proper order, the refined unit of dichloropropanol and dichloropropanol saponification unit, its characterized in that: the dichloropropanol refining unit comprises
The bottom of the desorption tower is provided with a first reboiler, the top of the desorption tower is provided with a first condenser, and a liquid phase inlet of the desorption tower is communicated with a material outlet of the glycerol chlorination unit;
the bottom of the rectifying tower is provided with a second reboiler, the top of the rectifying tower is provided with a second condenser, a liquid phase inlet of the rectifying tower is communicated with a liquid phase outlet of the desorption tower, the bottom of the rectifying tower is provided with a first liquid phase outlet for discharging heavy components, the side part of the rectifying tower is provided with a second liquid phase outlet for discharging light components, and the second liquid phase outlet is communicated with a material inlet of the dichloropropanol saponification unit;
a 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
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 glycerin catalyst solution;
a liquid phase inlet of the pre-reaction tower is communicated with a 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;
a liquid phase inlet of the first-stage reaction kettle is communicated with a liquid phase outlet of the pre-reaction tower, and a gas phase inlet of the first-stage reaction kettle is communicated with an external hydrogen chloride pipeline;
a liquid phase inlet of the second-stage reaction kettle is communicated with a liquid phase outlet of the pre-reaction tower and a liquid phase outlet of the first-stage reaction kettle, and a gas phase inlet of the second-stage reaction kettle is communicated with an externally-connected hydrogen chloride pipeline and a gas phase outlet of the first-stage reaction kettle; and
a liquid phase inlet of the three-section reaction kettle is communicated with a liquid phase outlet of the pre-reaction tower and a liquid phase outlet of the two-section reaction kettle, a gas phase inlet of the three-section reaction kettle is communicated with an externally-connected hydrogen chloride pipeline and a gas phase outlet of the two-section reaction kettle, and a gas phase outlet of the three-section reaction kettle is communicated with a gas phase inlet of the pre-reaction tower;
the liquid phase inlet of the desorption tower is communicated with the liquid phase outlet of the three-section reaction kettle;
and the second liquid phase outlet of the first layering tank is communicated with the 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 inlet of each reaction kettle, so that the materials of the pre-reaction tower can enter all the reaction kettles when the pre-reaction tower is started for the first time, and the start operation is convenient; in addition, the material of the upper-stage reaction kettle enters 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, a gas phase outlet of the desorption tower is communicated with a gas phase inlet of the pre-reaction tower. Since the gas phase outlet of the desorption column communicates with the gas phase inlet of the pre-reaction column, first, 200Nm is expected to be recovered3Hydrogen chloride per hour, reducing the consumption of lime milk by 1t per hour (15 wt% concentration); secondly, the load of a subsequent analysis tower and a saponification tower can be reduced; and thirdly, the content of monochloropropanediol in the saponification tower can be greatly reduced.
Furthermore, the refining unit of the dichloropropanol also comprises
A liquid phase inlet of the glycerol absorber is communicated with a material outlet of the raw material storage tank, a gas phase inlet of the glycerol absorber is communicated with a gas phase outlet of the rectifying tower, and a liquid phase outlet of the glycerol absorber is communicated with a 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 hydrogen chloride and the glycerol can be conveniently recovered as the liquid phase outlet of the glycerol absorber is communicated with the liquid phase inlet of the pre-reaction tower;
the organic matter cooled down by the first cooler is recycled to the first layering tank, and the dichloropropanol in the tail gas of the rectifying tower can be effectively recycled.
Still further, the refining unit of the dichloropropanol also comprises
An ejector, wherein a gas phase inlet of the ejector is communicated with a 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 non-condensable gas, so that the influence on the vacuum degree of the rectifying tower due to excessive non-condensable gas is prevented, and meanwhile, acidic non-condensable gas mixed in tail gas can corrode the first vacuum pump to influence the quality and the yield stability of the dichloropropanol;
the ejector pump can eject steam from the nozzle at a high speed to form low pressure in the vacuum chamber, so that gas at the top of the rectifying tower sequentially enters the vacuum chamber, the mixing chamber and the saponification tower, the ejected steam can be used for reaction of the saponification tower, and meanwhile, the ejector can reduce the load of a 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 guaranteed.
Further, the dichloropropanol saponification unit comprises
The lye tank is used for storing lye;
the saponification tower is provided with a material inlet arranged corresponding to the second tower plate and a hot water inlet arranged corresponding to the first tower plate, the material inlet of the saponification tower is communicated with the second liquid phase outlet of the rectification 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;
a gas phase inlet of the third condenser is communicated with a gas phase outlet of the saponification tower, and a gas phase outlet of the third condenser is connected with a second vacuum pump;
a liquid phase inlet of the second layering tank is communicated with a liquid phase outlet of the third condenser, the second layering tank 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 a reflux inlet of the saponification tower; and
and the material inlet of the crude epoxy chloropropane storage tank is communicated with the first liquid phase outlet of the crude epoxy chloropropane storage tank.
The feeding of the saponification tower is generally carried out by adopting a first tower plate, the feeding is carried out by adopting a second tower plate, and the first tower plate is washed by hot water, so that the method has the following advantages: firstly, the saponification tower is easy to scale, and the scale phenomenon can be avoided by adding a hot water flushing port; secondly, if the feed from the first tray causes the incoming material to be directly stripped by dichloropropanol steam, the dichloropropanol is polluted, if the feed from the third tray or even lower tray causes the influence on the reaction efficiency and yield, and the feed from the second tray can effectively avoid the problems; and thirdly, the first tower plate is washed by hot water, the second tower plate is fed, and the two inlets are not influenced by each other, so that the method has the advantage of higher starting efficiency compared with the original feeding mode of the first tower 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 column;
a liquid phase inlet of the second cooler is communicated with a liquid phase outlet of the flash tank, and a 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, a 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 large, the calcium chloride mother liquor is cooled by a cooler and is easy to block, and the calcium chloride mother liquor is cooled by vacuum flash evaporation at the position, so that the stable operation of the system is ensured.
The technical scheme adopted by the invention for solving the second technical problem is as follows: an epichlorohydrin production process applying the epichlorohydrin production device comprises the following steps:
step one, glycerol chlorination: the method comprises the following steps that a glycerin catalyst solution in a raw material storage tank is fed into a pre-reaction tower to pre-react with hydrogen chloride which is not reacted in each reaction kettle and hydrogen chloride which is analyzed out by an analysis tower, the reacted feed liquid is simultaneously fed into a first-stage reaction kettle, a second-stage reaction kettle and a third-stage reaction kettle, hydrogen chloride is fed into each reaction kettle by a hydrogen chloride pipeline, the feed liquid of the first-stage reaction kettle enters the second-stage reaction kettle, the feed liquid of the second-stage reaction kettle enters the third-stage reaction kettle, crude dichloropropanol which is reacted in the third-stage reaction kettle is fed into the analysis tower, the hydrogen chloride which is not reacted in the first-stage reaction kettle enters the second-stage reaction kettle, the hydrogen chloride which is not reacted in the second-stage reaction kettle enters the third;
secondly, refining dichloropropanol: the method comprises the following steps that (1) crude dichloropropanol is analyzed by an analyzing tower, analyzed gas phase is sent to a pre-reaction tower, the analyzed crude dichloropropanol is sent to a rectifying tower, heavy components from the rectifying tower enter a first layering tank, the layered heavy components in the first layering tank are sent to a dichloropropanol recovery tower to recover the dichloropropanol, the layered light components return to each reaction kettle to react again, and the refined dichloropropanol is discharged from the side line of the rectifying tower;
step three, dichloropropanol saponification: and (3) feeding the refined dichloropropanol conveyed from the rectifying tower into a dichloropropanol saponification unit for saponification to prepare the epichlorohydrin.
Preferably, the ratio of the hydrogen chloride fed into the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle from the hydrogen chloride pipeline is 8:1: 1-5: 5: 0.
The hydrogen chloride with proper ratio is respectively fed into the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle, so that the content of monochloropropanediol in the third-stage reaction kettle is ensured to be less than 1 percent, and the content of monochloropropanediol and COD in the calcium chloride mother liquor of the saponification tower is reduced.
Preferably, the operating pressure of the desorption tower is 0.15-0.30 MPa, the gas phase outlet of the desorption tower is communicated with the gas phase inlet of the pre-reaction tower through a self-flowing pipeline, the liquid phase outlet of the desorption tower is communicated with the liquid phase inlet of the rectification tower through a first pipeline, and the first pipeline is a self-flowing pipeline.
Hydrogen chloride in the ternary azeotrope in the desorption tower can be desorbed more by improving the operating pressure of the desorption tower, but the recovered monochloropropanediol is reduced due to overlarge operating pressure, so that the monochloropropanediol and the dichloropropanol enter the rectification tower together, and the operating pressure of the desorption tower needs to be reasonably controlled;
in addition, the operating pressure of the desorption tower is controlled to be 0.15-0.30 MPa, and the additional function is also achieved: on one hand, the hydrogen chloride analyzed by the analysis tower can be ensured to be automatically recycled to the pre-reaction tower, so that the energy consumption is reduced; on the other hand, because the desorption tower is in positive pressure and the rectifying tower is in negative pressure, the material in the desorption tower can automatically flow to the rectifying tower, and the energy consumption is reduced.
Compared with the prior art, the invention has the advantages that: firstly, materials in the rectifying tower directly return to the reaction kettle to be mixed unevenly, and the rectifying tower is provided with the first layering tank, so that the effect of stable production can be achieved, heavy components return to the reaction system can be reduced, the steam consumption is reduced, the catalyst content in the reaction kettle is uniform, and the reaction speed is more stable; secondly, the lower layer material can be discontinuously fed into a dichloropropanol recovery tower for recovery, continuous operation is not needed, and the steam consumption can be reduced.
Drawings
Fig. 1 is a schematic structural view of an embodiment of an epichlorohydrin production apparatus according to the present invention;
FIG. 2 is a schematic diagram of the structure of the glycerol chlorination unit of FIG. 1;
FIG. 3 is a schematic diagram of the structure of the dichloropropanol refining unit in FIG. 1;
FIG. 4 is a schematic diagram of the structure of the dichloropropanol saponification unit in FIG. 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
As shown in fig. 1 to 4, a preferred embodiment of the epichlorohydrin production apparatus of the present invention is shown.
As shown in fig. 1, the epichlorohydrin production apparatus includes a glycerin chlorination unit 1, a dichloropropanol refining unit 2, and a dichloropropanol saponification unit 3, which are connected in sequence.
As shown in fig. 2, the glycerol chlorination unit 1 includes 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 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; 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 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 rosettes as the filler, so that the corrosion of acid materials can be prevented, 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 primarily reacted with the desorption tower 21 and unreacted hydrogen chloride in each reaction kettle, then the mixture is sent into each reaction kettle to be further reacted with the hydrogen chloride, and finally the mixture is sent into the desorption tower 21 to remove the unreacted hydrogen chloride;
the top parts of the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 are provided with a liquid phase inlet and a gas phase outlet, and the bottom parts of the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 are 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 this embodiment, the number of the first section of reaction kettle 13 is at least two, and the first section of reaction kettle 13 is arranged in parallel, one is operated, and the other is reserved;
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 14 is communicated with an externally-connected hydrogen chloride pipeline 10 and a gas phase outlet of the first-stage reaction kettle 13;
the liquid phase inlet of the three-section reaction kettle 15 is communicated with the liquid phase outlet of the pre-reaction tower 12 and the liquid phase outlet of the two-section reaction kettle 14, the gas phase inlet of the three-section reaction kettle 15 is communicated with the external hydrogen chloride pipeline 10 and the gas phase outlet of the two-section reaction kettle 14, and the gas phase outlet of the three-section 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 inlet of each reaction kettle, so that the materials of the pre-reaction tower 12 can enter all the reaction kettles when the vehicle is started for the first time, and the start operation is convenient; in addition, the material of the upper-stage reaction kettle enters 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 comprises a desorption tower 21, a rectification tower 22, a glycerol 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 desorption tower 21, a first condenser 212 is installed at the top of the desorption tower 21, a liquid phase inlet of the desorption tower 21 is communicated with a liquid phase outlet of the three-stage reaction kettle 15, and a gas phase outlet at the top of the desorption tower 21 is communicated with a gas phase inlet of the pre-reaction tower 12 through a self-flow pipeline; in this embodiment, the analytical tower 21 uses PVDF taylor rosettes as a filler, so that the equipment can operate more stably;
in the existing scheme, the gas at the top of the desorption tower is usually condensed and then directly introduced into the saponification tower, the condensate mainly comprises an aqueous hydrogen chloride solution containing monochloropropanediol and dichloropropanol, the introduction of the condensate into the saponification tower increases the use amount of alkali liquor, the load of the saponification tower is increased, and the monochloropropanediol enters the aqueous calcium chloride solution, so that the quality of the saponified water is reduced, and further recycling is affected3Hydrogen chloride per hour, reducing the consumption of lime milk by 1t per hour (15 wt% concentration); secondly, the load of a subsequent analysis tower and a 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, a liquid phase inlet of the rectifying tower 22 is communicated with a liquid phase outlet at the bottom of the desorption tower 21, the bottom of the rectifying tower 22 is provided with a first liquid phase outlet for discharging heavy components, the side 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, a liquid phase outlet of the desorption tower 21 is communicated to a liquid phase inlet of the rectification tower 22 through a first pipeline 223 and a second pipeline 224 respectively, the first pipeline 223 is a self-flowing pipeline, and a first conveying pump 225 capable of conveying materials from the liquid phase outlet of the desorption tower 21 to the liquid phase inlet of the rectification tower 22 is installed on the second pipeline 224; 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 siphon self-circulation, during actual application, the circulation pump 228 is used for forced circulation in advance, and in the later stage, which circulation is selected according to actual conditions, so that energy is saved and consumption is reduced (90 KW can be saved per hour);
a liquid phase inlet of the glycerol absorber 23 is communicated with a material outlet of the raw material storage tank 11, a gas phase inlet of the glycerol absorber 23 is communicated with a gas phase outlet of the rectifying tower 22, and a liquid phase outlet of the glycerol absorber 23 is communicated with a 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 hydrogen chloride and the glycerol can be conveniently recovered as the liquid phase outlet of the glycerol absorber 23 is communicated with the liquid phase inlet of the pre-reaction tower 12;
the gas phase inlet of the first cooler 24 is communicated with the gas phase outlet of the glycerol absorber 23; the organic matter cooled down by the first cooler 24 is 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 is communicated with the gas phase outlet of the first cooler 24; the ejector 25 can eject steam from the nozzle at a high speed to 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 ejected steam can be used for reaction in the saponification tower 32, and meanwhile, the ejector 25 can reduce the load of a first vacuum pump 261 or partially replace the first vacuum pump 261 when the first vacuum pump 261 fails, so that stable operation of the rectifying tower 22 is guaranteed.
A gas phase inlet of the alkaline tower 26 is communicated with a gas phase outlet of the first cooler 24, and a gas phase outlet at the top of the alkaline tower 26 is connected with a first vacuum pump 261; the glycerol absorber 23, the first cooler 24 and the alkaline washing tower 26 can remove most of hydrogen chloride in the non-condensable gas, so that the influence on the vacuum degree of the rectifying tower 22 due to excessive non-condensable gas is prevented, and meanwhile, the acidic non-condensable gas in tail gas can corrode the first vacuum pump 261 to influence the quality and yield stability of the dichloropropanol;
a liquid phase inlet of the first layering tank 27 is communicated with a first liquid phase outlet of the rectifying tower 22 and a 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 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 rectification column 22 to the liquid phase inlet of the first stratified tank 27 is installed on the pipeline between the liquid phase inlet of the first stratified tank 27 and the first liquid phase outlet of the rectification column 22;
the compositions of the materials discharged from the first liquid phase outlet and the second liquid phase outlet of the first layering tank 27 are similar, but the proportions are different, wherein the contents of the catalyst and the dibasic acid ester in the materials discharged from the second liquid phase outlet are higher; the first stratified tank 27 mainly functions as follows: firstly, the materials in the rectifying tower 22 directly return to the reaction kettle and are unevenly mixed, and the first layering tank 27 is arranged, so that the effect of stable production can be achieved, heavy components return to the reaction system can be reduced, the steam consumption is reduced, the catalyst content in the reaction kettle is uniform, and the reaction speed is more stable; secondly, the lower layer material can be discontinuously fed into the dichloropropanol recovery tower 28 for recovery, continuous operation is not needed, and the steam consumption can be reduced;
a dichloropropanol recovery tower 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 by the dichloropropanol recovery tower in 28 years, and the benefit is obvious.
As shown in FIG. 4, the dichloropropanol saponification unit 3 comprises an alkali liquor tank 31, a saponification column 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 lye tank 31 is used for storing lye; in this example, the alkali solution 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 externally-connected hot water pipeline 30; specifically, a third transfer pump 321 capable of transferring the material from the second liquid phase outlet of the rectification column 22 to the material inlet of the saponification column 32 is installed on a pipeline between the material inlet of the saponification column 32 and the second liquid phase outlet of the rectification column 22;
the feeding of the saponification tower is generally carried out by adopting a first tower plate, the feeding is carried out by adopting a second tower plate, and the first tower plate is washed by hot water, so that the method has the following advantages: firstly, the saponification tower 32 is easy to scale, and the scale phenomenon can be avoided by adding a hot water flushing port; secondly, if the feed from the first tray causes the incoming material to be directly stripped by dichloropropanol steam, the dichloropropanol is polluted, if the feed from the third tray or even lower tray causes the influence on the reaction efficiency and yield, and the feed from the second tray can effectively avoid the problems; 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;
a liquid phase inlet of the second layering tank 34 is communicated with a 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 a reflux inlet of the saponification tower 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 pipeline between the reflux inlet of the saponification column 32 and the second liquid phase outlet of the second stratified tank 34;
a material inlet of the crude epichlorohydrin storage tank 35 is communicated with a first liquid phase outlet of the crude epichlorohydrin storage tank 35;
a liquid phase inlet of the flash tank 36 is communicated with a liquid phase outlet of the saponification tower 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 the pipeline 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 large, the calcium chloride mother liquor is cooled by a cooler and is easy to block, and the calcium chloride mother liquor is cooled by vacuum flash evaporation at the position, so that the stable operation of the system is ensured;
a liquid phase inlet of the second cooler 37 is communicated with a liquid phase outlet of the flash tank 36, and a liquid phase outlet of the second cooler 37 is connected to the calcium chloride pretreatment unit 371; and
a gas phase inlet of the fourth condenser 38 is communicated with a gas phase outlet of the flash tank 36, a gas phase outlet of the fourth condenser 38 is connected with a third vacuum pump 381, and a liquid phase outlet of the fourth condenser 38 is connected with a sewage treatment unit 382.
The invention also provides an epichlorohydrin production process using the epichlorohydrin production device.
Example 1:
step one, glycerol chlorination: controlling the operation pressure of a pre-reaction tower 12 to be 50kPa, feeding a glycerin catalyst solution in a raw material storage tank 11 into the pre-reaction tower 12 to pre-react with unreacted hydrogen chloride from each reaction kettle and hydrogen chloride resolved by a resolving tower 21, feeding the 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 the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 respectively by 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 pressure difference, feeding the feed liquid of the second-stage reaction kettle 14 into the third-stage reaction kettle 15 by using pressure difference, feeding crude dichloropropanol reacted in the third-stage reaction kettle 15 into the resolving tower 21, feeding the unreacted hydrogen chloride in the first-stage reaction kettle 13 into the second-stage reaction kettle 14, the unreacted hydrogen chloride in the three-section reaction kettle 15 is sent into a pre-reaction tower 12;
secondly, refining dichloropropanol: controlling the operating pressure of the desorption tower 21 to be 0.25MPa, desorbing the crude dichloropropanol by the desorption tower 21, feeding the desorbed gas phase into the pre-reaction tower 12, feeding the desorbed crude dichloropropanol into the rectifying tower 22, falling-film absorbing the non-condensable gas discharged from a gas phase outlet at the top of the rectifying tower 22 by a glycerol absorber 23, feeding the gas phase into a first cooler 24 for further condensation, and feeding 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 through the ejector 25, the other part is pumped out through the first vacuum pump 261 after entering the caustic 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 layered heavy components in 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 stream discharged from the rectifying tower 22 is refined dichloropropanol;
step three, dichloropropanol saponification: the refined dichloropropanol conveyed from the rectifying tower 22 is mixed with the alkali liquor from the alkali liquor tank 31 and then enters a second tower plate of the saponification tower 32, and the hot water of the hot water pipeline 30 enters a first tower plate of the saponification tower 32 for washing; the epichlorohydrin generated in the saponification tower 32 is steamed out along with steam stripping steam and then enters a third condenser 33, condensed non-condensable gas is pumped out by a second vacuum pump 331, and condensate enters a second layering tank 34; the condensate is separated in a second layering tank 34 in layers, the heavy component after layering is crude epichlorohydrin, the crude epichlorohydrin is sent to a crude epichlorohydrin storage tank 35 for further refining, the light component after layering is water, and the water is sent back to the saponification tower 32; the kettle liquid of the saponification tower 32 is sent into a flash tank 36, the liquid phase after flash evaporation is sent into a second cooler 37 to be cooled and then sent into a calcium chloride pretreatment unit 371, the gas phase after flash evaporation is sent into a fourth condenser 38, the condensed non-condensable gas is pumped out by a third vacuum pump 381, and the condensed liquid is sent into a sewage treatment unit 382;
and (4) detecting the materials at the liquid phase outlet of the three-section reaction kettle 15, and recording the contents of the monochloropropanediol and the dichloropropanol.
Example 2:
the difference from example 1 is that: in the first step, hydrogen chloride is fed into a first-stage reaction kettle 13, a second-stage reaction kettle 14 and a third-stage reaction kettle 15 respectively by a hydrogen chloride pipeline 10 in a ratio of 8:1: 1.
Example 3:
the difference from example 1 is that: in the first step, hydrogen chloride is fed into a first-stage reaction kettle 13, a second-stage reaction kettle 14 and a third-stage reaction kettle 15 respectively through a hydrogen chloride pipeline 10 in a ratio of 6:3: 1.
Example 4:
the difference from example 1 is that: in the first step, hydrogen chloride is fed into a first-stage reaction vessel 13, a second-stage reaction vessel 14 and a third-stage reaction vessel 15 by a hydrogen chloride line 10 at a ratio of 5:5:0, respectively.
Example 5:
the difference from example 1 is that: in the second step, the operating pressure of the desorption tower 21 is 0.15 MPa;
example 6:
the difference from example 1 is that: in the second step, the operating pressure of the desorption tower 21 is 0.30 MPa;
comparative example 1:
the difference from example 1 is that: in the first step, hydrogen chloride is fed into a first-stage reaction vessel 13, a second-stage reaction vessel 14 and a third-stage reaction vessel 15 by a hydrogen chloride line 10 at a ratio of 5:3:2, respectively.
Comparative example 2:
the difference from example 1 is that: in the second step, the operating pressure of the desorption tower 21 is 50 kPa;
comparative example 3:
the difference from example 1 is that: in the second step, the operating pressure of the desorption tower 21 is 0.35 MPa;
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 1-4 and comparative example 1, the appropriate ratio of hydrogen chloride is fed into the first-stage reaction kettle 13, the second-stage reaction kettle 14 and the third-stage reaction kettle 15 respectively, 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 example 1, example 5, example 6, comparative example 2 and comparative example 3, the hydrogen chloride in the ternary azeotrope in the desorption tower 21 can be desorbed more by increasing the operating pressure of the desorption tower 21, but the recovered monochloropropanediol is reduced due to the excessive operating pressure, so that the monochloropropanediol and dichloropropanol enter the rectification tower 22 together, and therefore, the operating pressure of the desorption tower 21 needs to be reasonably controlled;
in addition, the operation pressure of the desorption tower 21 is controlled to be 0.15-0.30 MPa, and the additional function is also realized: on one hand, the hydrogen chloride analyzed by the analysis tower can be ensured to be automatically recycled to the pre-reaction tower, so that the energy consumption is reduced; on the other hand, because the desorption tower is in positive pressure and the rectifying tower is in negative pressure, the material in the desorption tower can automatically flow to the rectifying tower, and the energy consumption is reduced.
Claims (10)
1. The utility model provides an epoxy chloropropane apparatus for producing, is including glycerine chlorination unit (1), the refined unit of dichloropropanol (2) and dichloropropanol saponification unit (3) that connect gradually, its characterized in that: the dichloropropanol refining unit (2) comprises
A desorption tower (21), wherein the bottom of the desorption tower is provided with a first reboiler (211), the top of the desorption tower is provided with a first condenser (212), and a liquid phase inlet of the desorption 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 the rectifying tower is communicated with a liquid phase outlet of the desorption 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 of the rectifying tower, and the second liquid phase outlet is communicated with a material inlet of the dichloropropanol saponification unit (3);
a first layering tank (27), a liquid phase inlet of which is communicated with a first liquid phase outlet of the rectifying tower (22), and is provided with a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, 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
and the dichloropropanol recovery tower (28) is communicated with the liquid phase inlet of the first layering tank (27) and the first liquid phase outlet thereof.
2. The epichlorohydrin production apparatus according to claim 1, characterized in that: 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 the top of the pre-reaction tower is provided with a gas phase outlet for discharging tail gas;
a liquid phase inlet of the first-stage reaction kettle (13) is communicated with a liquid phase outlet of the pre-reaction tower (12), and a gas phase inlet of the first-stage reaction kettle is communicated with an externally-connected hydrogen chloride pipeline (10);
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-section reaction kettle (15) is communicated with a liquid phase outlet of the pre-reaction tower (12) and a liquid phase outlet of the two-section reaction kettle (14), a gas phase inlet of the three-section reaction kettle is communicated with an externally-connected hydrogen chloride pipeline (10) and a gas phase outlet of the two-section reaction kettle (14), and a gas phase outlet of the three-section reaction kettle is communicated with a gas phase inlet of the pre-reaction tower (12);
a liquid phase inlet of the desorption tower (21) is communicated with a liquid phase outlet of the three-section reaction kettle (15);
and a second liquid phase outlet of the first layering tank (27) is communicated with liquid phase inlets of the first section of reaction kettle (13), the second section of reaction kettle (14) and the third section of reaction kettle (15).
3. The epichlorohydrin production apparatus according to claim 2, characterized in that: the gas phase outlet of the desorption tower (21) is communicated with the gas phase inlet of the pre-reaction tower (12).
4. The epichlorohydrin production apparatus according to claim 2, characterized in that: the dichloropropanol refining unit (2) also comprises
A glycerol absorber (23), the liquid phase inlet of which is communicated with the material outlet of the raw material storage tank (11), the gas phase inlet of which is communicated with the gas phase outlet of the rectifying tower (22), and the liquid phase outlet of which is communicated with the liquid phase inlet of the pre-reaction tower (12); and
a first cooler (24) having a gas phase inlet in communication with the gas phase outlet of the glycerol absorber (23) and a liquid phase outlet in communication with the liquid phase inlet of the first stratified tank (27).
5. The epichlorohydrin production apparatus according to claim 4, characterized in that: the dichloropropanol refining unit (2) also comprises
An ejector (25) having a gas phase inlet in communication with the 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 of the alkaline washing tower is connected with a first vacuum pump (261).
6. Epichlorohydrin production apparatus according to any one of claims 2 to 5, characterized in that: the dichloropropanol saponification unit (3) comprises
An alkali liquor tank (31) for storing alkali liquor;
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 rectification 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 an externally-connected hot water pipeline (30);
a third condenser (33) having a gas phase inlet communicated with the gas phase outlet of the saponification column (32), and having a gas phase outlet connected with a second vacuum pump (331);
a second stratified tank (34) having a liquid phase inlet connected to the liquid phase outlet of the third condenser (33), a first liquid phase outlet for discharging heavy components and a second liquid phase outlet for discharging light components, the second liquid phase outlet being connected to the reflux inlet of the saponification column (32); and
and the material inlet of the crude epoxy chloropropane storage tank (35) is communicated with the first liquid phase outlet of the crude epoxy chloropropane storage tank (35).
7. The epichlorohydrin production apparatus according to claim 6, 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) having a liquid phase inlet in communication with the liquid phase outlet of the flash tank (36) and a liquid phase outlet connected to a calcium chloride pre-treatment unit (371); and
and a fourth condenser (38) with a gas phase inlet communicated with the gas phase outlet of the flash tank (36), a gas phase outlet connected with a third vacuum pump (381), and a liquid phase outlet connected with a sewage treatment unit (382).
8. An epichlorohydrin production process using the epichlorohydrin production apparatus according to any one of claims 2 to 7, comprising the steps of:
step one, glycerol chlorination: the glycerin catalyst solution in the raw material storage tank (11) is sent into a pre-reaction tower (12) to pre-react with the unreacted hydrogen chloride from each reaction kettle and the hydrogen chloride resolved by a resolving tower (21), the reacted feed liquid is simultaneously sent into a first-stage reaction kettle (13), a second-stage reaction kettle (14) and a third-stage reaction kettle (15), hydrogen chloride is sent into each reaction kettle by a hydrogen chloride pipeline (10), feed liquid of a first-stage reaction kettle (13) enters a second-stage reaction kettle (14), feed liquid of the second-stage reaction kettle (14) enters a third-stage reaction kettle (15), crude dichloropropanol after reaction of the third-stage reaction kettle (15) is sent into a desorption tower (21), unreacted hydrogen chloride of the first-stage reaction kettle (13) enters the second-stage reaction kettle (14), unreacted hydrogen chloride of the second-stage reaction kettle (14) enters the third-stage reaction kettle (15), and unreacted hydrogen chloride of the third-stage reaction kettle (15) is sent into a pre-reaction tower (12);
secondly, refining dichloropropanol: the method comprises the following steps that (1) crude dichloropropanol is analyzed by an analyzing tower (21), analyzed gas phase is sent to a pre-reaction tower (12), analyzed crude dichloropropanol is sent to a rectifying tower (22), heavy components from the rectifying tower (22) enter a first layering tank (27), layered heavy parts of the first layering tank (27) are sent to a dichloropropanol recovery tower (28) to recover the dichloropropanol, layered light components are returned to each reaction kettle to react again, and the rectified dichloropropanol is discharged from the lateral line of the rectifying tower (22);
step three, dichloropropanol saponification: the refined dichloropropanol conveyed from the rectifying tower (22) enters a dichloropropanol saponification unit (3) for saponification to prepare the epichlorohydrin.
9. The epichlorohydrin production process according to claim 8, characterized in that: the ratio of hydrogen chloride fed 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) is 8:1: 1-5: 5: 0.
10. The epichlorohydrin production process according to claim 8, characterized in that: the operating pressure of the desorption tower (21) is 0.15-0.30 MPa, a gas phase outlet of the desorption tower (21) is communicated with a gas phase inlet of the pre-reaction tower (12) through a gravity flow pipeline, a liquid phase outlet of the desorption 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 gravity flow pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011288662.5A CN112239434B (en) | 2020-11-17 | 2020-11-17 | Epoxy chloropropane production device and technology |
Applications Claiming Priority (1)
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