CN101007751A - Preparation method of dichloro propanol from glycerin - Google Patents
Preparation method of dichloro propanol from glycerin Download PDFInfo
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- CN101007751A CN101007751A CN 200710019466 CN200710019466A CN101007751A CN 101007751 A CN101007751 A CN 101007751A CN 200710019466 CN200710019466 CN 200710019466 CN 200710019466 A CN200710019466 A CN 200710019466A CN 101007751 A CN101007751 A CN 101007751A
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- glycerol
- dichloropropanol
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 142
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 title claims description 53
- 235000011187 glycerol Nutrition 0.000 title description 38
- 238000002360 preparation method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000005587 bubbling Effects 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 44
- 229960000583 acetic acid Drugs 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 2,3-dichloropropan-1-ol Chemical compound OCC(Cl)CCl ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparing method of dichlorohydrin from glycerol, which comprises the following steps: adding glycerol and HCl and carboxyl acid activator into mixer; charging into tubular reactor continually to proceed chlorination reaction; reacting through chlorination reaction; transforming glycerol swiftly; entering into HCl bubbling still to react continually; evaporating azeotropic material comprised by water through reaction, dichlorohydrin, HCl and part of activator from the top of bubbling still; recycling product through condensation; separating liquid of bubbling still in the fractionating tower; getting dichlorohydrin from the top of fractionating tower; delivering liquid of fractionating tower to proceed circular response.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to a preparation method of a propylene oxide intermediate. More specifically a process for the preparation of dichloropropanol from glycerol.
Background
Dichloropropanol is a key intermediate in the production process of epoxy chloropropane, and the annual yield of the dichloropropanol is close to 200 ten thousand tons. The main worldwide production method of dichloropropanol is based on the high-temperature chlorination method of propylene developed by the American shell company in 1948, and the preparation process comprises the following steps:
CH2＝CHCH3+Cl2→CH2＝CHCH2Cl
CH2＝CHCH2Cl+Cl2+H2O→CH2ClCH(OH)CH2Cl+CH2(OH)CHClCH2Cl
the process has mature process, sufficient propylene source as a raw material and can meet huge market demands, but the process route also has the serious defects of high-temperature chlorination of ①, high energy consumption and more side reactions, easy coke generation in the ② reaction process and frequent shutdown and coke cleaning of equipment, wherein the utilization rate of chlorine in the ③ reaction process is only about 38 percent, and the concentration of the dichloropropanol product is generally controlled to be 4 percent, so a great amount of chlorine-containing wastewater is generated in the production process, however, the dichloropropanol is produced by the method in about 90 percent of epoxy chloropropane industrial devices at present.
Another less frequently used method for the industrial production of dichloropropanol is the propylene acetate process, the reaction process comprising:
CH2＝CHCH2OH+Cl2→CH2ClCHClCH2OH
compared with the traditional propylene high-temperature chlorination method, the method for preparing the propylene acetate has the advantages of stable operation, less chlorine consumption and relatively less side reaction. However, the process has long route, large investment, short service life of the palladium catalyst and high production cost.
In general, both industrial processes consume a large amount of non-renewable petroleum resources and also consume a large amount of chlorine gas, resulting in serious environmental pollution.
Thus, in recent years, new processes for producing dichloropropanol are being sought worldwide, and glycerol processes derived from renewable resources are being emphasized. The basic reaction principle of the method isas follows:
the research method of German patent No. 197308, 1906 is to react HCl gas with glycerin for 20-40 h at about 100 ℃ by using acetic acid or propionic acid as a catalyst to obtain dichloropropanol with the yield of 75%. The water produced inhibits the reaction from proceeding.
In U.S. Pat. No. 2144612, a solvent such as n-butyl ether, dichloroethane or chlorobenzene is added to the reaction system, and the azeotropic distillation method is used to continuously remove water produced during the reaction to promote the reaction and suppress the production of high boiling substances. Acetic acid accounting for 5% of the glycerol is used as a catalyst, HCl gas reacts with the glycerol for 35 hours at the temperature of about 100 ℃, the molar yield of dichloropropanol is more than 87%, and no condensation compound is generated. However, such a process is difficult to be applied industrially because the amount of solvent used is large, the utilization rate of equipment is reduced, the energy consumption for refluxing a large amount of solvent is large, the loss of HCl gas is large, and the residual solvent also affects the purity of the product, increasing the burden on the separation device.
Czech chemical metallurgy combination discloses in its patent CN1845888A (or WO2005021476) a continuous cyclic reaction process. Reacting HCl gas and glycerol in a bubble reactor under the catalysis of acetic acid, then feeding reactants into a rectifying tower, evaporating water and dichloropropanol generated from the top of the tower, and pumping tower bottom liquid into the reactor so as to carry out a circulating reaction. Under the condition of not using an external solvent, dichloropropanol and water in reactants are continuously removed by a rectifying tower embedded in the middle of the reaction circulation, so that the reaction is smoothly carried out. The disadvantages caused by using a large amount of solvent are avoided. However, such a process has low reaction efficiency because reactants continuously enter a rectifying tower for rectification, usually vacuum distillation, so that HCl is distilled out of the reaction system first to form waste acid, resulting in a very low HCl concentration in the reaction system and thus a low reaction rate. In addition, continuous reduced pressure distillation can ensure that most of the catalyst acetic acid is distilled out, thus causing large catalyst dosage.
In addition, Solvay corporation in its patent WO2005054167 (or Fr2862644) discloses a process similar to the aforementioned czech chemical metallurgy combination. The reaction is carried out in a single or a plurality of bubbling reaction kettles, reactants continuously enter a rectifying tower, generated dichloropropanol and water are removed by azeotropic distillation, the reaction is carried out smoothly, and tower bottom liquid is circulated for reaction. This Solvay patent differs from the Czech chemical metallurgy combination patent by the trend of the materials. The Solvay corporation patents show that the HCl gas flows counter-currently to the liquid reactants, so the HCl utilization is increased. In addition, the preferred catalyst in this patent is adipic acid, which is not volatile, so there is little loss of catalyst in the feed recycle reaction. However, the process still has high energy consumption and low equipment utilization rate.
In general, the prior art carries out the reaction in a bubbling kettle (tower) or a stirring kettle, and the HCl concentration in the reaction system is low and the reaction rate is low. The reactor form determines low reaction efficiency and high energy consumption. In addition, the reaction is inefficient, and high boiling point substances are easily generated, so that the selectivity of the reaction is reduced.
Disclosure of Invention
To overcome these drawbacks of the prior art, the present invention proposes a process for preparing dichloropropanol from glycerol.
The reaction of glycerol with HCl to produce dichloropropanol is carried out in two steps, and the reaction formula is as follows:
it is known from the general knowledge of reaction kinetics that, in the initial stage of the reaction and at low conversion, the reaction is not thermodynamically limited, i.e., the presence of water has little effect on the reaction, and in the latter stage of the reaction, i.e., at high conversion, the reaction is thermodynamically limited and the presence of water in the reaction system inhibits the progress of the reaction.
The technical scheme of the invention is as follows:
firstly, glycerol, HCl and a carboxylic acid catalyst are added into a mixer together, and are continuously pressed into a tubular reactor for chlorination reaction, and the glycerol is quickly converted through the reaction of the tubular reactor. The reaction mass was then fed to an HCl bubble column to continue the reaction. The water generated in the reaction, dichloropropanol, HCl and part of catalyst form an azeotrope which is evaporated from the upper part of the bubbling kettle, the product is recovered by condensation, the kettle liquid of the bubbling kettle continuously enters a rectifying tower for separation, the dichloropropanol product is obtained from the top of the rectifying tower, and the kettle liquid of the rectifying tower is sentto a circulating reaction.
The molar ratio of the glycerol to the HCl entering the tubular reactor is 1: 0.5-1: 3, preferably 1: 1.0-1: 2.0, and the concentration of the available glycerol is 85-100%. The HCl can be gas or hydrochloric acid with the concentration ranging from 25% to 38%, and HCl gas is preferred.
The catalyst is C1～C12The carboxylic acid is preferably butyric acid or valeric acid. The amount of the catalyst accounts for 0.5 to 5 percent of the amount of the glycerol,preferably 1 to 3%.
The tubular reactor has packing or suitable internals inside to ensure good mixing of the reactants during the flow. The packing used in a conventional packed column or the internals used in a static mixer can be used.
The reaction temperature in the tubular reactor is 80-140 ℃, preferably 95-105 ℃. Too high a reaction temperature may lead to the formation of coke.
The reaction time in the tubular reactor is from 2 to 12 hours, preferably from 4 to 6 hours.
And continuously feeding the material reacted in the tubular reactor into a bubbling reactor for continuous reaction, and continuously discharging the generated water, dichloropropanol and HCl from the upper part of the reactor. The bubble reactor may be of a stirring type, a column type, a packed column type or a jet type. Preference is given to a column bubble reactor. Stirring paddles or internals may be provided in the reactor to enhance the gas-liquid mass transfer effect and thus the reaction rate.
The gas is blown from below into the bubble reactor by means of a gas distributor, and may be blown in by any dispersion method, such as porous nozzles, porous ceramic plates, etc. The gas sparged may be pure HCl in a molar ratio to glycerol of 0.5: 1 to 3:1, preferably 1: 1.0 to 2.0: 1. It may also be a mixture of HCl and other gases in a certain ratio. The other gas mentioned here is generally a gas inert to the reaction system, such as nitrogen, air, carbon dioxide, argon, helium, etc., and preferably nitrogen or carbon dioxide. The volume ratio of the inert gas to the HCl is 0-1: 1, and preferably 0-0.5: 1. Use of inert gas to produce H2O can be removed from the reaction system in time, thereby promoting the reaction.
The operating temperature of the bubbling reactor is 90-140 ℃, preferably 105-115 ℃, and the residence time of reactants in the bubbling reactor is 6-16 h, preferably 8-10 h.
The reactor combination method provided by the invention is designed according to the characteristics of different stages of the reaction, so that the reaction rate is improved, the equipment utilization rate is improved, the glycerol is completely converted within 12-16 h, and the yield of the dichloropropanol can be more than 90%. Because the reflux reaction does not need a long time like the prior art, the utilization rate of HCl is improved to more than 70 percent, and the energy consumption is greatly reduced.
Drawings
FIG. 1 is a schematic view of the structure of the present invention
1. Mixer 2, charging pump 3, tubular reactor 4, 11, sampling valve 5, 12, flow control valve 6, bubbling reactor 7, gas distributor 8, 15, condenser 9, 16, discharge valve 10, tail gas condensate tank 13, rectifying tower 14, tower top product tank 17, tank liquor circulating pump
The tubular reactor (3) is a teflon coil filled with ceramic rings, the effective volume of the reactor is about 400ml, the reactor is placed in an oil bath, and a flow control valve (5) is arranged at the outlet of the reactor to control the pressure in the reactor.
The bubble-tank reactor in the figure is a glass reactor, i.e. a bubble column reactor (6), with an effective reaction volume of about 900ml, and HCl gas is introduced from the bottom through a gas distributor (7). The lower outlet of the bubble column is provided with a flow regulating valve (12) for regulating the residence time of reactants. CaCO for reaction solution3After neutralization, vacuum distillation is carried out, and products of dichloropropanol and a small amount of H are collected from the top of the tower2An azeotrope of O with dichloropropanol.
Detailed Description
Example 1 Glycerol (95% of technical product) was mixed with HCl (from PCl) at 0.6mol/h (containing 2% of acetic acid as catalyst)3And H2O is produced in a 1: 3.5 reaction) at 0.6 mol/h. Pumping the mixture into a reaction system shown in figure 1 by a pump for premixing, wherein the oil bath temperature of the tubular reactor is 105 ℃, and the residence time of the materials in the tubular reactor is 6h by adjusting through an outlet flow adjusting valve 5. Gas chromatography analysis of the sample by the sampling valve 4 revealed that the conversion of glycerin was 93.6%, the yield of monochloropropanediol was 84.4%, and the yield of dichloropropanol was 8.9%. The acid concentration of the reaction solution is calibrated by NaOH and is 0.49 mol/L.
The reaction liquid flowing out of the tubular reactor directly enters an HCl bubble column reactor, the reaction temperature is controlled to be 108 ℃, the introduction amount of HCl is 1.2mol/H, the retention time of the materials in the bubble column reactor is controlled to be 10H through the flow regulation of anoutlet valve 12 (the excessive HCl is discharged from the reactor along with an azeotrope, the azeotrope comprises the components of 19.6 percent of dichloropropanol, 30.4 percent of HCl and 48 percent of H2O, 2% acetic acid). Sampling is performed through a sampling valve 11, and CaCO is used as a reaction liquid sample3After sufficient neutralization, gas chromatography was performed: monochloropropanediol 21.6%, 1, 3-dichloroisopropanol 77.1%, 2, 3-dichloro-n-propanol 0.6% (1, 3-dichloroisopropanol and 2, 3-dichloro-n-propanol for the formation of epoxy chloridePropane was not different and so it is not differentiated hereinafter and is collectively referred to as dichloropropanol, the remainder (including the condensate) being 0.7%. The acid concentration of the reaction solution was titrated with NaOH to 0.45 mol/L.
After 10h of continuous feeding, the reaction system entered steady state operation. Within 5h of steady state operation 295g (3mol) of glycerol (95%) and 9mol of HCl were fed and glycerol was completely converted. 187.6g of condensate (containing 37.6g of dichloropropanol, 56.3g of HCl, 89.7g of water and 4g of acetic acid) is condensed from the tail gas of the bubbling reactor. Collecting 30-32 ℃/15mmHg dichloropropanol and water azeotrope and 70-72 ℃/15mmHg dichloropropanol from the top of the vacuum rectification tower to obtain 352.6g, wherein the water content is 33g, and the dichloropropanol content is 319.6 g. Dichloropropanol yield 92.3% (based on glycerol).
Example 2. the residence time of the material in the bubble reactor was varied. Industrial glycerol (95%) was premixed with HCl (2% acetic acid) at 0.6mol/h and HCl at 0.6mol/h, and pumped into the reaction system shown in FIG. 1, the oil bath temperature in the tubular reactor was 100 ℃ and the residence time of the material in the tubular reactor was 6h, as regulated by the outlet pressure and flow rate.
Controlling the temperature of the bubbling reactor at 110 ℃, adjusting the flow of an outlet, ensuring that the retention time of the materials in the bubbling reactor is 7 hours, the introduction amount of HCl is 0.8mol/h, and collecting the generated azeotrope after condensation along with tail gas through gas-liquid separation.
Within 5h of steady state operation, 295g (3mol) of glycerol were fed, 9mol of HCl were fed and glycerol was completely converted. 198g of condensate (containing 39.1g of dichloropropanol, 62g of HCl, 91.8g of water and 5.2g of acetic acid) was condensed from the bubbling reactor off-gas. 30-32 ℃/15mmHg of dichloropropanol and water azeotrope and 70-72 ℃/15mmHg of dichloropropanol are collected from the top of the rectification tower, 338g of dichloropropanol is obtained, wherein the water content is 26.3g, the yield of the dichloropropanol is 311.7g, and the yield of the dichloropropanol is 90.6%.
Example 3 the residence time of the material in the tubular reactor was varied. Industrial glycerin (95%) was fed at 1.0mol/h (containing 2% acetic acid) and HCl1.0mol/h, the tubular reactor temperature was controlled at 105 ℃, the residence time of the material in the tubular reactor was about 3.5h, the tubular reactor outlet glycerin conversion rate was 81.6, the monochloropropanediol formation rate was 79.2, and the dichloropropanol formation rate was 2.0%. The acid value of NaOH is 1.4 mol/L.
And (3) allowing the reaction liquid in the tubular reactor to enter an HCl bubbling reactor for continuous reaction, wherein the introduction amount of HCl is 2mol/h, the temperature of the bubbling reactor is controlled at 110 ℃, and the retention time is 10 h.
Within 5h of steady state operation, glycerol was fed at 5mol, HCl was fed at 15mol, and glycerol was completely converted. 257.2g of condensate containing 50.8g of dichloropropanol and H is condensed from the tail gas of the bubbling reactor2O122g, HCl77.6g and acetic acid 6.8 g. Collecting 30-32 ℃/15mmHg dichloropropanol and water azeotrope and 70-72 ℃/15mmHg dichloropropanol from the top of the rectification tower to obtain 514.8g, wherein the dichloropropanol comprises 469.8g dichloropropanol and HO25g of the total weight. The dichloropropanol yield was 80.7%.
Example 4 the reaction temperature in the tubular reactor was controlled to 95 deg.C, and the same operation as in example 1 was carried out, and the reaction results are shown in Table 1.
Example 5 bubble reactor with 0.8mol HCl/h +0.6mol N2The mixed gas/h was bubbled, the same operation as in example 1 was repeated, and the reaction results are shown in Table 1.
Example 6 bubbling reactor with 0.8mol HCl/h +0.6mol CO2The mixed gas/h was bubbled, the same operation as in example 1 was repeated, and the reaction results are shown in Table 1.
Example 7 the bubble reactor temperature was controlled at 115 c as in example 1 and the results are given in table 1.
Example 8. feed glycerol containing 2% valeric acid as catalyst and the rest of example 1, the results are given in Table 1.
Example 9 feed glycerol 95% technical glycerol was replaced with 99% analytical grade glycerol reagent and the results are given in Table 1, as in example 1.
Example 10 the bubble column reactor of FIG. 1 was replaced by a 1000ml glass flask with mechanical stirring and the reaction results are given in Table 1, except that the flask was siphoned off from the bottom.
Example 11 tubular reactor feed proportioning was varied. Industrial glycerol (95%) was premixed with HCl at 0.3mol/h and 0.6mol/h (2% acetic acid as catalyst) and the material had a residence time of 7.5h in the tube reactor. The reaction results are shown in Table 1, as in example 1.
Example 12 tubular reactor feed ratios were varied. Industrial glycerol (95%) was premixed with HCl at 1.2mol/h and 0.6mol/h (2% acetic acid as catalyst) and the material had a residence time of 5.5h in the tube reactor. The reaction results are shown in Table 1, as in example 1.
Example 13 tubular reactor feed HCl gas was replaced by hydrochloric acid with a concentration of 36%. Industrial glycerol (95%) was premixed with 0.6mol/h (2% acetic acid in the catalyst) and 36% hydrochloric acid at 0.6mol/h, and the residence time of the material in the tube reactor was about 3.7 h. The reaction results are shown in Table 1, as in example 1.
Comparative example: according to the method of Solvay WO2005054167 (or Fr2862644), 453g of glycerol (4.92mol) and 29.5g of glacial acetic acid (0.49mol) were charged into a 1000ml four-neck flask with mechanical stirring, tail gas condenser and gas conduit, heated to 110 ℃ and reacted by passing HCl gas through the flask, first 2h, then 3.8 min and finally 380min, respectively. In total 25.0mol of HCl are passed. The total reaction time was 10 h. The glycerol conversion was complete and the results for the off-gas condensate and the distillate product are given in table 1.
TABLE 1 Change of operating conditions Experimental results (Mass Unit: g)
| Examples of the invention | The amount and composition of the tail gas condensate of the bubbling reactor, | fraction and composition at top of rectifying tower | Dichloropropanol (DCP) Yield and content of | ||||||
| Total amount of | DCP | H2O | HCl | Catalyst and process for preparing same | Total amount of | DCP | H2O | ||
| Example 4 | 180.2 | 35.8 | 84.3 | 55.6 | 4.5 | 306.3 | 285.1 | 21.2 | 82.9 |
| Example 5 | 226.7 | 45.8 | 108.1 | 67.9 | 4.9 | 308.8 | 300.2 | 8.6 | 89.4 |
| Example 6 | 230.3 | 46.2 | 110.6 | 68.8 | 4.7 | 310.7 | 302.9 | 7.8 | 90.2 |
| Example 7 | 183.5 | 37.1 | 87.5 | 53.8 | 5.1 | 350.4 | 316.6 | 33.8 | 91.4 |
| Example 8 | 185.6 | 37.5 | 89.8 | 56.2 | 2.1 | 354.4 | 323.2 | 31.2 | 93.2 |
| Example 9 | 181.6 | 35.7 | 85.9 | 55.1 | 4.9 | 358.0 | 323.4 | 34.6 | 92.8 |
| Example 10 | 222.2 | 43.5 | 106.5 | 67.5 | 4.7 | 329.2 | 311.0 | 18.2 | 91.6 |
| Example 11 | 165.8 | 31.5 | 79.6 | 51.4 | 3.3 | 293.4 | 273.1 | 20.3 | 78.7 |
| Example 12 | 195.3 | 37.2 | 94.1 | 59.8 | 4.2 | 352.4 | 328.9 | 23.5 | 94.6 |
| Example 13 | 571.7 | 107.3 | 285.5 | 170.2 | 8.7 | 144.9 | 131.5 | 13.4 | 61.7 |
| Comparative example | 298.9 | 56.2 | 138.6 | 85.9 | 18.2 | 394.5 | 384.3 | 10.2 | 69.4 |
Claims (4)
1. A method for preparing dichloropropanol from glycerol is characterized by adding glycerol, HCl and a carboxylic acid catalyst into a mixer, continuously pressing the mixture into a tubular reactor for chlorination reaction, reacting in the tubular reactor, allowing reactants to enter an HCl bubble reactor for continuous reaction, allowing water generated by the reaction, dichloropropanol, HCl and part of the catalyst to form an azeotrope to be evaporated from the upper part of the bubble reactor, condensing and recovering a product, continuously allowing reaction liquid of the bubble reactor to enter a rectifying tower for separation, obtaining a dichloropropanol product from the top of the rectifying tower, and allowing the residue liquid of the rectifying tower to be sent to a circulating reaction;
the molar ratio of the glycerol to the HCl entering the tubular reactor is 1: 0.5-1: 3, preferably 1: 1.0-1: 2.0, and the concentration of the glycerol is 85-100%. HCl is gas or hydrochloric acid with the concentration range of 25-38%, and HCl gas is preferred;
the catalyst is C1～C6The carboxylic acid is preferably butyric acid or valeric acid, and the amount of the catalyst accounts for 0.5-5%, preferably 1-3% of the amount of the glycerol;
the reaction temperature in the tubular reactor is 80-140 ℃, and preferably 95-105 ℃; the reaction time in the tubular reactor is 2 to 12 hours, preferably 4 to 6 hours;
the gas blown into the bubbling reactor is pure HCl or a mixture of HCl and other gases, the other gases are nitrogen, air, carbon dioxide, argon and helium, preferably nitrogen or carbon dioxide, and the molar ratio of the gas blown into the bubbling reactor to glycerol is 0.5: 1-3: 1, preferably 1: 1.0-2.0: 1; the volume ratio of the inert gas to the HCl is 0-1: 1, preferably 0-0.5: 1;
the operating temperature of the bubbling reactor is 90-140 ℃, preferably 105-115 ℃, and the residence time of reactants in the bubbling reactor is 6-16 h, preferably 8-10 h.
2. The process according to claim 1, wherein the bubble reactor is a stirred, column, packed column or jet reactor, preferably a column bubble reactor.
3. The process for preparing dichloropropanol from glycerol according to claim 2, wherein stirring paddles, internals or packing are arranged in the reactor.
4. The process for preparing dichloropropanol from glycerol according to claim 1, wherein the gas is blown into the bubbling reactor from the bottom by a gas distributor.
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