CN114621057B - Production method of dichloropropanol - Google Patents
Production method of dichloropropanol Download PDFInfo
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- CN114621057B CN114621057B CN202210454221.0A CN202210454221A CN114621057B CN 114621057 B CN114621057 B CN 114621057B CN 202210454221 A CN202210454221 A CN 202210454221A CN 114621057 B CN114621057 B CN 114621057B
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- allyl alcohol
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- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 210
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 118
- 230000007062 hydrolysis Effects 0.000 claims abstract description 82
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 73
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 62
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 61
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 61
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000011552 falling film Substances 0.000 claims description 38
- 238000010521 absorption reaction Methods 0.000 claims description 35
- 238000003795 desorption Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 39
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 28
- 235000011187 glycerol Nutrition 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 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 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 241000906682 Hemsleya Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method of dichloropropanol, which comprises a chloropropene hydrolysis step and an allyl alcohol chlorination step. The dichloropropanol production method overcomes the technical defects of long process flow, short catalyst service life, high investment cost and the like in the prior art, and produces the dichloropropanol product with the purity of more than 98 percent.
Description
[ Field of technology ]
The invention belongs to the technical field of chemical industry, and particularly relates to a production method of dichloropropanol.
[ Background Art ]
Dichloropropanol is an important organic synthesis intermediate and is an important raw material for producing epoxy chloropropane. The industrial method for producing dichloropropanol mainly comprises a propylene high-temperature chlorination method, a propylene acetate method and a glycerol chlorination method.
The high-temperature chlorination method of propylene mainly comprises the preparation of chloropropene by high-temperature chlorination of propylene and the synthesis of dichloropropanol by hypochlorous acid of chloropropene, and is a classical method for producing epoxy chloropropane in the traditional industry. However, the method has the advantages of high concentration difficulty, high energy consumption and large amount of wastewater generated by directly cyclizing and preparing the epichlorohydrin because the dichloropropanol concentration is low by about 4 percent, belongs to the technology of 'two heights', and gradually tends to be eliminated.
The technological process of the propylene acetate method mainly comprises the steps of synthesizing propylene acetate by propylene, oxygen and acetic acid under the catalysis of noble metal, hydrolyzing the propylene acetate and synthesizing dichloropropanol by chlorination of allyl alcohol. The method has the defects of long process flow, short catalyst life and high investment cost.
The glycerol chlorination method is a main production method of epoxy chloropropane at present, and the glycerol and hydrogen chloride gas react to generate dichloropropanol under the action of a catalyst. However, the current glycerol method for producing epichlorohydrin has 90% of the domestic epichlorohydrin market, and the result is that the raw material glycerol is supplied in tension. Raw material crude glycerine for producing epoxy chloropropane by glycerol method comes from international market, since domestic glycerol method production device is on the rise, foreign merchants can live in the market, price is increased, in the near future, the market of domestic epoxy chloropropane will be limited by the supply of crude glycerine in western countries, and the glycerol method epoxy chloropropane process will not be sustainable.
Therefore, in order to solve the defects existing in the prior art, it is very necessary to develop a new way for producing dichloropropanol. The present inventors have completed the present invention through a great deal of experiments and studies.
[ Invention ]
[ Problem to be solved ]
The invention aims to provide a production method of dichloropropanol.
Technical scheme
The invention is realized by the following technical scheme.
The invention relates to a production method of dichloropropanol.
The production method comprises the following steps:
A. Chloropropene hydrolysis
The chloropropene from outside the world enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 through a pipeline, meanwhile, water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, and when the water and the chloropropene pass through the hydrolysis reactor 1 filled with the hydrolysis catalyst from bottom to top, the water and the chloropropene undergo hydrolysis reaction to obtain hydrolysis reaction liquid;
The hydrolysis reaction liquid is conveyed to the middle part of a phase separator 2 from the top of a hydrolysis reactor 1 through a pipeline for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reactor 1 for reuse, the low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2 and conveyed to an allyl alcohol tower 3 through a pipeline for rectification to obtain water and high-concentration allyl alcohol solution, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. Allyl alcohol chlorination
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top of the falling film absorption tower through a pipeline, meanwhile, hydrogen chloride gas from outside the boundary enters the falling film absorption tower 4 from the lower part of the falling film absorption tower through a pipeline, and the high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4; the solution is sent to the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, and the chlorine is subjected to chlorination reaction in the chlorination reactor 5 to generate allyl alcohol chlorinated product, the product is sent to the tower from the middle part of a hydrogen chloride desorption tower 6 through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to the falling film absorption tower 4 for recycling, the bottom product is dichloropropanol and water mixed solution, and the mixed solution is purified to obtain a high-purity dichloropropanol product.
According to a preferred embodiment of the present invention, in step a, the chloropropene content is 99.3% or more by weight; the weight ratio of the chloropropene to the water is 1:1 to 5.
According to another preferred embodiment of the invention, in step a, the hydrolysis catalyst is selected from the group consisting of styrenic or acrylic acid resins.
According to another preferred embodiment of the present invention, in step A, the hydrolysis reaction is carried out at a temperature of 60 to 150℃and a pressure of 0.1 to 1.5MPa and a chloropropene volume space velocity of 0.25 to 1.0h -1.
According to another preferred embodiment of the present invention, in step a, the low concentration allyl alcohol solution is rectified in the allyl alcohol column 3 under conditions of a column bottom temperature of 103 to 105 ℃, a column top temperature of 90.9 to 91.2 ℃ and normal pressure to obtain a high concentration allyl alcohol solution having an allyl alcohol concentration of 68 to 72% by weight.
According to another preferred embodiment of the invention, in step a, the hydrolysis reactor 1 is a reactor having a support plate and a distribution tray at the bottom and a filter plate structure at the top; the phase separator 2 is a phase separator having a hollow structure; the allyl alcohol column 3 is a column having a tray structure.
According to another preferred embodiment of the present invention, in step B, the hydrogen chloride content of the high concentration allyl alcohol solution containing high concentration hydrogen chloride is 15 to 25% by weight.
According to another preferred embodiment of the present invention, in the step B, the high concentration allyl alcohol solution containing high concentration hydrogen chloride and hydrogen chloride are subjected to chlorination reaction at a temperature of 0 to 10 ℃ and a pressure of 0.1 to 0.3MPa for 0.5 to 2.0 hours in the chlorination reactor 5.
According to another preferred embodiment of the invention, in step B, the dichloropropanol product has a purity of more than 98% by weight.
According to another preferred embodiment of the present invention, in step B, the falling film absorption column 4 is a column having a round block structure; the chlorination reactor 5 is a reactor having a stirring structure; the hydrogen chloride stripping column 6 is a column having a packing structure.
The present invention will be described in more detail below.
The invention relates to a production method of dichloropropanol. The specific steps of the production method are shown in fig. 1 and fig. 2.
The production method comprises the following steps:
A. Chloropropene hydrolysis
The chloropropene from outside the world enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 through a pipeline, meanwhile, water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, and when the water and the chloropropene pass through the hydrolysis reactor 1 filled with the hydrolysis catalyst from bottom to top, the water and the chloropropene undergo hydrolysis reaction to obtain hydrolysis reaction liquid;
The content of chloropropene used in the invention is more than 99.3 percent by weight; the chloropropene is a product currently sold on the market, for example, a product sold under the trade name 3-chloropropene by Shandong Ji chemical Co., ltd or a product sold under the trade name chloropropene by Pingming chemical Co., ltd.
In this step, the weight ratio of chloropropene to water is 1:1 to 5. If the weight ratio of chloropropene to water is greater than 1:1, hydrolysis is not easy to carry out; if the weight ratio of chloropropene to water is less than 1: and 5, the influence of the increased water amount on the reaction conversion rate is small, and the energy consumption is increased, so that the method is uneconomical. Thus, the weight ratio of chloropropene to water is controlled to be 1:1 to 5 are suitable, preferably 1:2 to 4, more preferably 1:2.5 to 3.5.
The hydrolysis catalyst used in the present invention is selected from a styrene-based or acrylic acid-based acid resin, which is a product currently commercially available, for example, a product sold under the trade name D001 strongly acidic cation exchange resin by the company of the division of the resin technology of the division of the Tianjin, or a product sold under the trade name YKCHWD-1 catalytic resin; acrylic acid resins are currently commercially available products such as those sold under the trade name D113 resin by Tianjin Bao Hongjinshi resin technologies Co.
According to the invention, the hydrolysis reaction is carried out under the conditions of the temperature of 60-150 ℃, the pressure of 0.1-1.5 MPa and the volume space velocity of chloropropene of 0.25-1.0 h -1.
In the present invention, when the hydrolysis reaction pressure and the volume space velocity of chloropropene are within the ranges, if the hydrolysis reaction temperature is lower than 60 ℃, the hydrolysis reaction is difficult to be thoroughly carried out; if the hydrolysis reaction temperature is higher than 150 ℃, chloropropene is easy to volatilize, which is unfavorable for the hydrolysis reaction. Accordingly, the hydrolysis reaction temperature is suitably 60 to 150 ℃, preferably 80 to 140 ℃, more preferably 90 to 120 ℃.
When the hydrolysis reaction temperature and the volume space velocity of the chloropropene are in the ranges, if the hydrolysis reaction pressure is lower than 0.1MPa, the chloropropene is easy to volatilize; if the hydrolysis reaction pressure is higher than 1.5MPa, the influence on the reaction result is not great, but the equipment investment is increased, so that the method is uneconomical. Therefore, the hydrolysis reaction pressure is suitably 0.1 to 1.5MPa, preferably 0.2 to 1.2MPa, more preferably 0.4 to 1.0MPa.
When the hydrolysis reaction temperature and the hydrolysis reaction pressure are in the ranges, if the volume space velocity of chloropropene is smaller than 0.25h -1, the side reaction is increased, and the product yield is low; if the chloropropene volume space velocity is greater than 1.0h -1, the reaction time is insufficient, resulting in low conversion of the raw material. Thus, the chloropropene volume space velocity is in the range of 0.25 to 1.0h -1, preferably 0.30 to 0.80h -1, more preferably 0.40 to 0.60h -1.
The hydrolysis reaction liquid is conveyed to the middle part of a phase separator 2 from the top of a hydrolysis reactor 1 through a pipeline for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reactor 1 for reuse, the low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2 and conveyed to an allyl alcohol tower 3 through a pipeline for rectification to obtain water and high-concentration allyl alcohol solution, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
According to the present invention, the low concentration allyl alcohol solution is rectified in the allyl alcohol tower 3 under the conditions of the bottom temperature of 103 to 105 ℃, the top temperature of 90.9 to 91.2 ℃ and normal pressure, and the high concentration allyl alcohol solution with the allyl alcohol concentration of 68 to 72% by weight is obtained. The allyl alcohol concentration was analyzed according to the gas chromatography internal standard method.
In this step, the hydrolysis reactor 1 is a reactor having a support plate and a distribution plate at the bottom and a filter plate structure at the top. The support plate is used for bearing the hydrolysis reaction catalyst, the distribution plate is used for uniformly distributing materials, the distribution plate can be a spray head type, a plate type, a tubular type, a groove type or a groove plate type distribution plate, the filter plate structure is used for filtering and removing the catalyst to prevent the catalyst from losing, and the filter plate is a plate provided with a filter medium with the aperture of 0.5-1.0 mm;
the phase separator 2 is a phase separator with a hollow structure, and realizes phase separation by using the principle of incompatibility of substances; the allyl alcohol column 3 is a column having a tray structure, which is a float plate or bubble cap plate.
The hydrolysis reactor 1, the phase separator 2 and the allyl alcohol tower 3 used in the present invention are all products currently sold in the market, for example, the hydrolysis reactor 1 sold under the trade name of a packed bed reactor by the company of the chemical holding equipment, inc. in Shandong, the phase separator 2 sold under the trade name of a separator by the company of the machinery, hemsleya, inc., and the allyl alcohol tower 3 sold under the trade name of a rectifying tower by the company of the petrochemical equipment, centario, inc.;
B. Allyl alcohol chlorination
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top of the falling film absorption tower through a pipeline, meanwhile, hydrogen chloride gas from outside the boundary enters the falling film absorption tower 4 from the lower part of the falling film absorption tower through a pipeline, and the high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4; the solution is sent to the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, and the chlorine is subjected to chlorination reaction in the chlorination reactor 5 to generate allyl alcohol chlorinated product, the product is sent to the tower from the middle part of a hydrogen chloride desorption tower 6 through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to the falling film absorption tower 4 for recycling, the bottom product is dichloropropanol and water mixed solution, and the mixed solution is purified to obtain a high-purity dichloropropanol product.
According to the present invention, the hydrogen chloride content of the high concentration allyl alcohol solution containing high concentration hydrogen chloride is 15 to 25% by weight. If the hydrogen chloride content of the high-concentration allyl alcohol solution is lower than 15%, the allyl alcohol has more chlorination side reactions; if the hydrogen chloride content of the high-concentration allyl alcohol solution is higher than 25%, the effect of the content improvement on the reaction result is not great; thus, a high concentration allyl alcohol solution having a hydrogen chloride content of 15 to 25%, preferably 18 to 22%, is appropriate;
According to the present invention, in the chlorination reactor 5, the high concentration allyl alcohol solution containing high concentration hydrogen chloride and hydrogen chloride are subjected to chlorination reaction at a temperature of 0to 10 ℃ and a pressure of 0.1 to 0.3MPa for 0.5 to 2.0 hours.
When the chlorination reaction pressure and the chlorination reaction time are within the ranges, if the chlorination reaction temperature is lower than 0 ℃, the chlorination reaction is difficult to proceed; if the chlorination reaction temperature is higher than 10 ℃, there are too many side reaction products. Therefore, a chlorination reaction temperature of 0 to 10℃is suitable, preferably 1 to 8℃and more preferably 2 to 6 ℃.
When the chlorination reaction temperature and the chlorination reaction time are within the ranges, if the chlorination reaction pressure is lower than 0.1MPa, the chlorination reaction is not easy to be carried out; if the chlorination reaction pressure is higher than 0.3MPa, the influence on the reaction result is not great, but the equipment investment is increased, and the method is uneconomical. Therefore, it is reasonable that the chlorination reaction pressure is 0.1 to 0.3MPa, preferably 0.15 to 0.25MPa, more preferably 0.18 to 0.23MPa.
When the chlorination reaction temperature and the chlorination reaction pressure are within the ranges, if the chlorination reaction time is shorter than 0.5h, the chlorination reaction is insufficient, and the conversion rate of raw materials is low; if the chlorination reaction time is longer than 2.0 hours, the number of side reaction products is too large, affecting the product yield. Thus, the chlorination reaction time is suitably from 0.5 to 2.0 hours, preferably from 0.8 to 1.8 hours, more preferably from 1.0 to 1.5 hours.
The bottom product discharged from the bottom of the hydrogen chloride desorption column 6 is a mixed liquid of dichloropropanol, water and a small amount of hydrogen chloride. The mixed solution is subjected to extraction, rectification and purification to obtain a high-purity dichloropropanol product, and the purity of the dichloropropanol product is more than 98% by weight according to analysis of gas chromatography normalization.
The falling film absorber 4 used in the present invention is a tower having a round block structure, such as a falling film absorber sold under the trade name of a round block hole type graphite falling film absorber by the company limited of anti-corrosion equipment of eastern Xinbo; the chlorination reactor 5 is a reactor having a stirring structure, such as a reactor sold under the trade name of a chlorination reactor by the company of chemical equipment, inc. of Shandong Cheng Ming; the hydrogen chloride stripping column 6 is a column having a packed structure, such as a column sold under the trade name of graphite packed column by the company of the anti-corrosion equipment limited of eastern, bosch.
[ Advantageous effects ]
The beneficial effects of the invention are as follows: the dichloropropanol production method overcomes the technical defects of long process flow, short catalyst service life, high investment cost and the like in the prior art, and produces the dichloropropanol product with the purity of more than 98 percent.
[ Description of the drawings ]
FIG. 1 is a flow chart of the hydrolysis process of the dichloropropanol manufacturing process of the invention;
FIG. 2 is a flow chart of the chlorination process of the dichloropropanol manufacturing process of the invention;
In the figure:
1-a hydrolysis reactor; a 2-phase separator; a 3-allyl alcohol column; 4-falling film absorption tower; a 5-chlorination reactor; 6-hydrogen chloride desorber.
[ Detailed description ] of the invention
The invention will be better understood by the following examples.
Example 1: the invention relates to a dichloropropanol production method
The implementation steps of this embodiment are as follows:
A. Chloropropene hydrolysis
Chloropropene with the content of 99.3% from the outside of the boundary enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold under the trade name of a packed bed reactor by the chemical filling equipment limited company in Shandong through a pipeline, meanwhile water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, and the weight ratio of the chloropropene to the water is 1:3, a step of; when water and chloropropene pass through a hydrolysis reactor 1 filled with a styrene acid resin hydrolysis catalyst sold by Tianjin let-off resin technology Co., ltd under the trade name of D001 strong acid cation exchange resin, they are subjected to hydrolysis reaction under the conditions of a temperature of 120 ℃, a pressure of 1.0MPa and a volume space velocity of chloropropene of 1.0h -1 to obtain a hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle part of a phase separator 2 sold by Shandong Hengke mechanical limited company under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reactor 1 for reuse, a low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Jia petrochemical equipment limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the bottom temperature of 103-105 ℃ and the top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and a high-concentration allyl alcohol solution, wherein the allyl alcohol concentration of the solution is 71% by weight, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. Allyl alcohol chlorination
The high concentration allyl alcohol solution obtained in the step A enters the tower from the top of the falling film absorption tower 4 through a pipeline, meanwhile, hydrogen chloride gas from outside enters the tower from the lower part of the falling film absorption tower 4 through a pipeline, and a high concentration allyl alcohol solution containing high concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the hydrogen chloride content is 22% by weight according to the analysis of the method described in the specification of the application; the solution is sent to the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, and the chlorine is subjected to chlorination reaction for 2.0h in the chlorination reactor 5 under the conditions of the temperature of 8 ℃ and the pressure of 0.2MPa, so that allyl alcohol chlorinated product is generated, the product is sent to the tower from the middle part of the hydrogen chloride desorption tower 6 through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to the falling film absorption tower 4 for recycling, the tower bottom product is dichloropropanol and water mixed solution, the mixed solution is subjected to conventional extraction and rectification purification, and the analysis is carried out according to the method described in the specification, so that the purity of the dichloropropanol product is 98.1% by weight.
Example 2: the invention relates to a dichloropropanol production method
The implementation steps of this embodiment are as follows:
A. Chloropropene hydrolysis
Chloropropene with the content of 99.6% from the outside of the boundary enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold under the trade name of a packed bed reactor by the chemical holding equipment limited company in Shandong through a pipeline, meanwhile water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, and the weight ratio of the chloropropene to the water is 1:1, a step of; when water and chloropropene pass through a hydrolysis reactor 1 filled with an acrylic acid resin hydrolysis catalyst sold by Tianjin Baohong resin technology Co., ltd under the trade name D113 resin, they are subjected to hydrolysis reaction under the conditions of a temperature of 60 ℃, a pressure of 0.1MPa and a chloropropene volume space velocity of 0.50h -1 to obtain a hydrolysis reaction liquid;
The hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle part of a phase separator 2 sold by Shandong Hengke mechanical limited company under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reactor 1 for reuse, a low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Jia petrochemical equipment limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the bottom temperature of 103-105 ℃ and the top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and a high-concentration allyl alcohol solution, wherein the allyl alcohol concentration of the solution is 68% by weight, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. Allyl alcohol chlorination
The high-concentration allyl alcohol solution obtained in the step A enters the tower from the top of the falling film absorption tower 4 through a pipeline, meanwhile, hydrogen chloride gas from outside enters the tower from the lower part of the falling film absorption tower 4 through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the hydrogen chloride content is 15% by weight according to the analysis of the method described in the specification of the application; the solution is sent to the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, and the chlorine is subjected to chlorination reaction for 1.0h in the chlorination reactor 5 under the conditions of the temperature of 0 ℃ and the pressure of 0.1MPa, so that allyl alcohol chlorinated product is generated, the product is sent to the tower from the middle part of the hydrogen chloride desorption tower 6 through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to the falling film absorption tower 4 for recycling, the bottom product is dichloropropanol and water mixed solution, and the mixed solution is extracted, rectified and purified, and analyzed according to the method described in the specification of the application, so that the purity of the dichloropropanol product is 99.2% by weight.
Example 3: the invention relates to a dichloropropanol production method
The implementation steps of this embodiment are as follows:
A. Chloropropene hydrolysis
Chloropropene with the content of 99.4% from the outside of the boundary enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold under the trade name of a packed bed reactor by the company of the chemical holding equipment, east and middle, through a pipeline, and water enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, wherein the weight ratio of the chloropropene to the water is 1:5, a step of; when water and chloropropene pass through a hydrolysis reactor 1 filled with an acrylic acid resin hydrolysis catalyst sold by Tianjin Baohong resin technology Co., ltd under the trade name D113 resin, they are subjected to hydrolysis reaction under the conditions of a temperature of 150 ℃ and a pressure of 1.5MPa and a chloropropene volume space velocity of 0.25h -1 to obtain a hydrolysis reaction liquid;
The hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle part of a phase separator 2 sold by Shandong Hengke mechanical limited company under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reactor 1 for reuse, a low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Jia petrochemical equipment limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the bottom temperature of 103-105 ℃ and the top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and a high-concentration allyl alcohol solution, wherein the allyl alcohol concentration of the solution is 68% by weight, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. Allyl alcohol chlorination
The high-concentration allyl alcohol solution obtained in the step A enters the tower from the top of the falling film absorption tower 4 through a pipeline, meanwhile, hydrogen chloride gas from outside enters the tower from the lower part of the falling film absorption tower 4 through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the hydrogen chloride content is 18% by weight according to the analysis of the method described in the specification of the application; the solution is sent to the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, and the chlorine is subjected to chlorination reaction for 1.5 hours in the chlorination reactor 5 under the conditions of the temperature of 10 ℃ and the pressure of 0.3MPa, so that allyl alcohol chlorinated product is generated, the product is sent to the tower from the middle part of the hydrogen chloride desorption tower 6 through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to the falling film absorption tower 4 for recycling, the bottom product is dichloropropanol and water mixed solution, and the mixed solution is extracted, rectified and purified, and analyzed according to the method described in the specification of the application, so that the purity of the dichloropropanol product is 98.5% by weight.
Example 4: the invention relates to a dichloropropanol production method
The implementation steps of this embodiment are as follows:
A. Chloropropene hydrolysis
Chloropropene with the content of 99.5% from the outside of the boundary enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold under the trade name of a packed bed reactor by the company of the chemical holding equipment, east and middle, through a pipeline, and water enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, wherein the weight ratio of the chloropropene to the water is 1:4, a step of; when water and chloropropene pass through a hydrolysis reactor 1 provided with a styrene acid resin hydrolysis catalyst sold by Tianjin let-down resin technologies and technologies under the trade name YKCHWD-1, they are subjected to hydrolysis reaction under the conditions of temperature 90 ℃, pressure 0.5MPa and chloropropene volume space velocity 0.75h -1 to obtain a hydrolysis reaction liquid;
The hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle part of a phase separator 2 sold by Shandong Hengke mechanical limited company under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reactor 1 for reuse, a low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Jia petrochemical equipment limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the bottom temperature of 103-105 ℃ and the top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and a high-concentration allyl alcohol solution, wherein the allyl alcohol concentration of the solution is 72% by weight, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. Allyl alcohol chlorination
The high-concentration allyl alcohol solution obtained in the step A enters the tower from the top of the falling film absorption tower 4 through a pipeline, meanwhile, hydrogen chloride gas from outside enters the tower from the lower part of the falling film absorption tower 4 through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the hydrogen chloride content is 25% by weight according to the analysis and determination of the method described in the specification of the application; the solution is sent to the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, and the chlorine is subjected to chlorination reaction for 0.5h in the chlorination reactor 5 under the conditions of temperature 5 ℃ and pressure of 0.2MPa, so that allyl alcohol chlorinated product is generated, the product is sent to the tower from the middle part of the hydrogen chloride desorption tower 6 through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to the falling film absorption tower 4 for recycling, the bottom product is dichloropropanol and water mixed solution, and the mixed solution is extracted, rectified and purified, and analyzed according to the method described in the specification of the application, so that the purity of the dichloropropanol product is 98.8% by weight.
Claims (8)
1. The production method of dichloropropanol is characterized by comprising the following steps of:
A. Chloropropene hydrolysis
The chloropropene from outside the boundary enters the hydrolysis reactor (1) from the bottom of the hydrolysis reactor (1) through a pipeline, meanwhile, water also enters the hydrolysis reactor (1) from the lower part of the hydrolysis reactor (1), and when the water and the chloropropene pass through the hydrolysis reactor (1) filled with the hydrolysis catalyst from bottom to top, the hydrolysis reaction is carried out under the conditions of the temperature of 60-150 ℃ and the pressure of 0.1-1.5 MPa and the volume airspeed of the chloropropene of 0.25-1.0 h < -1 >, so as to obtain hydrolysis reaction liquid; the hydrolysis catalyst is selected from styrene-based or acrylic acid-based resins;
The hydrolysis reaction liquid is conveyed to the middle part of a phase separator (2) from the top of a hydrolysis reactor (1) through a pipeline for separation, unreacted chloropropene is discharged from the top of the phase separator (2) and returned to the hydrolysis reactor (1) for recycling, the low-concentration allyl alcohol solution is discharged from the bottom of the phase separator (2), the low-concentration allyl alcohol solution is conveyed to an allyl alcohol tower (3) through a pipeline for rectification to obtain water and high-concentration allyl alcohol solution, the water is discharged from the bottom of the allyl alcohol tower (3) and returned to the hydrolysis reactor (1) for recycling, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower (3);
B. Allyl alcohol chlorination
The high-concentration allyl alcohol solution obtained in the step A enters the tower from the top of the falling film absorption tower (4) through a pipeline, meanwhile, hydrogen chloride gas from outside the boundary enters the tower from the lower part of the falling film absorption tower (4) through a pipeline, and the high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower (4); the solution is sent to the chlorination reactor (5) from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor (5) through a pipeline, the chlorine is subjected to chlorination reaction in the chlorination reactor (5) to generate allyl alcohol chlorinated product, the product is sent to the tower from the middle part of a hydrogen chloride desorption tower (6) through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower (6) and returned to a falling film absorption tower (4) for recycling, the bottom product is dichloropropanol and water mixed solution, and the mixed solution is purified to obtain the high-purity dichloropropanol product.
2. The production method according to claim 1, characterized in that in step a, the chloropropene content is 99.3% by weight or more; the weight ratio of the chloropropene to the water is 1:1 to 5.
3. The production method according to claim 1, wherein in step a, the low concentration allyl alcohol solution is rectified in the allyl alcohol column (3) under conditions of a column bottom temperature of 103 to 105 ℃, a column top temperature of 90.9 to 91.2 ℃ and normal pressure to obtain a high concentration allyl alcohol solution having an allyl alcohol concentration of 68 to 72% by weight.
4. The production method according to claim 1, characterized in that in step a, the hydrolysis reactor (1) is a reactor having a support plate and a distribution tray at the bottom and a filter plate structure at the top; the phase separator (2) is a phase separator with a hollow structure; the allyl alcohol column (3) is a column having a tray structure.
5. The production method according to claim 1, wherein in step B, the hydrogen chloride content of the high concentration allyl alcohol solution containing high concentration hydrogen chloride is 15 to 25% by weight.
6. The production method according to claim 1, wherein in the step B, the high concentration allyl alcohol solution containing high concentration hydrogen chloride and hydrogen chloride are subjected to chlorination reaction at a temperature of 0 to 10 ℃ and a pressure of 0.1 to 0.3MPa in the chlorination reactor (5) for 0.5 to 2.0 hours.
7. The process according to claim 1, characterized in that in step B the dichloropropanol product has a purity of more than 98% by weight.
8. The production method according to claim 1, characterized in that in step B, the falling film absorption column (4) is a column having a round block structure; the chlorination reactor (5) is a reactor with a stirring structure; the hydrogen chloride desorption column (6) is a column with a packing structure.
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| CN103333047A (en) * | 2013-07-09 | 2013-10-02 | 南京奥凯化工科技有限公司 | Preparation method of dichloropropanol |
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
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| CN103333047A (en) * | 2013-07-09 | 2013-10-02 | 南京奥凯化工科技有限公司 | Preparation method of dichloropropanol |
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
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| 氯丙烯及其衍生物的制备和应用;梅群波等;精细化工中间体;第34卷(第04期);1-7 * |
| 环氧氯丙烷的生产、消费和发展前景;蔡建利;中国氯碱(第11期);6-9 * |
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