CN112479811A - Method and system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol - Google Patents
Method and system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol Download PDFInfo
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 47
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 86
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 66
- 230000018044 dehydration Effects 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 45
- UOORRWUZONOOLO-OWOJBTEDSA-N (E)-1,3-dichloropropene Chemical compound ClC\C=C\Cl UOORRWUZONOOLO-OWOJBTEDSA-N 0.000 claims abstract description 38
- UOORRWUZONOOLO-UHFFFAOYSA-N telone II Natural products ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 claims abstract description 38
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 28
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 28
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
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- 239000002245 particle Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 210000003278 egg shell Anatomy 0.000 claims description 7
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- VRTNIWBNFSHDEB-UHFFFAOYSA-N 3,3-dichloroprop-1-ene Chemical compound ClC(Cl)C=C VRTNIWBNFSHDEB-UHFFFAOYSA-N 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 25
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000013064 chemical raw material Substances 0.000 abstract description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 32
- 238000003860 storage Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 11
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000413 hydrolysate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000036983 biotransformation Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018979 CoPt Inorganic materials 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910007162 SnPd Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000008103 glucose Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- WQWLQWVLHSPEAR-UHFFFAOYSA-N propane-1,3-diol;terephthalic acid Chemical compound OCCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 WQWLQWVLHSPEAR-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- 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
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol. The method comprises the following steps: continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst for dehydration reaction to prepare 1, 3-dichloropropene; continuously inputting the 1, 3-dichloropropene and hydrogen into a reaction device provided with a hydrogenation catalyst for hydrogenation reaction to prepare 1, 3-dichloropropane; and carrying out hydrolysis reaction on the mixed reaction system containing the 1, 3-dichloropropane, a hydrolysis agent and a solvent to prepare the 1, 3-propanediol. The invention takes the intermediate product 1, 3-dichloropropanol of the epichlorohydrin preparation by the cheap glycerol chlorination method as the raw material, prepares the important chemical raw material 1, 3-propanediol by 3 steps of dehydration, hydrogenation and hydrolysis, provides a new way for preparing the 1, 3-propanediol by the glycerol, and has the advantages of mild condition, low cost, environmental protection, economy and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method and a system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol.
Background
1, 3-propanediol (1, 3-propanediol, 1,3-PDO for short, chemical formula: CH)2OHCH2CH2OH) is an important organic chemical raw material, is mainly applied to the industries of printing ink, coating, cosmetics, pharmacy, antifreeze and the like, and has the most important application of producing the main raw material of the poly (1, 3-propylene glycol terephthalate) fiber (PTT for short). The prepared PTT fiber not only has the performance of polyethylene terephthalate (PET), but also has good rebound resilience and pollution resistance of nylon, is widely applied in the fields of carpets, engineering plastics, garment materials and the like, and becomes a hotspot for the international development of synthetic fibers at present. However, the higher price and insufficient productivity of 1, 3-propanediol become the key to limit the production cost of PTT fiber.
At present, the preparation method of 1,3-PDO mainly adopts a chemical synthesis method taking petrochemical products as raw materials and a biological conversion method taking biomass glycerol as a raw material. The chemical synthesis method is mainly represented by an ethylene oxide method of shell company and an acrolein route of Degussa company of Germany, is in a technical monopoly state, and has the defects of more byproducts, harsh conditions, non-renewable raw materials, higher production cost and the like in the technology. The biotransformation method is represented by DuPont in the United states, and adopts renewable resources such as corn starch and the like as raw materials for microbial fermentation production. Although the biological fermentation method has mild conditions and simple operation, the method has the defects of complex product components, low yield of 1,3-PDO and difficult subsequent separation.
The units such as Qinghua university, university of great graduate and Chinese agriculture university in China also develop research and development work of the technology for producing 1,3-PDO by using the glycerol biotransformation method, and have obtained stage results. The 1,3-PDO is produced by a fermentation method of a national fifteen-science and technology project of the university of Qinghua, which is born by the chemical industry system, glucose or crude starch (such as cassava powder) is used as a raw material, and a two-strain two-step fermentation production process is adopted, but the process has the problems of high strain cultivation difficulty, low industrial yield and the like.
In conclusion, 1, 3-propanediol is mostly produced in the research and development stage in China at the present stage, and the large-scale production process technology of the chemical method is still in a blank state. In recent years, although the technology for producing 1, 3-propylene glycol by adopting a biological method in China has made great progress, and some research results are in industrial demonstration production, the requirement of the high-end polyester industry in China on the 1, 3-propylene glycol cannot be met. Therefore, China still has great demands on the industrial technology for producing the 1, 3-propylene glycol in a large scale.
Disclosure of Invention
The invention mainly aims to provide a method and a system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for producing 1, 3-propylene glycol from 1, 3-dichloropropanol, which comprises the following steps:
continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst, and keeping the temperature at 200--1Carrying out dehydration reaction under the condition of (1) to prepare 1, 3-dichloropropene;
continuously feeding the 1, 3-dichloropropene into a reaction device provided with a hydrogenation catalyst, wherein the hydrogen pressure is 1-10MPa, the temperature is 20-100 ℃, and the space velocity is 0.1-5.0h-1Carrying out hydrogenation reaction under the condition of (1) to obtain 1, 3-dichloropropane;
and carrying out hydrolysis reaction on the mixed reaction system containing the 1, 3-dichloropropane, the hydrolysis agent and the solvent at the temperature of 50-150 ℃ for 2-10h to prepare the 1, 3-propylene glycol.
Further, the raw material 1, 3-dichloropropanol in the invention is prepared by a cheap glycerol chlorination method.
The embodiment of the invention also provides a system for producing 1, 3-propylene glycol, which is applied to the method and comprises the following steps:
a dehydration reaction unit capable of performing a dehydration reaction of at least 1, 3-dichloropropanol and a dehydration catalyst to produce 1, 3-dichloropropene;
a hydrogenation reaction unit which can perform hydrogenation reaction on at least 1, 3-dichloropropene, hydrogen and a hydrogenation catalyst to prepare 1, 3-dichloropropane;
a hydrolysis reaction unit capable of performing a hydrolysis reaction of at least 1, 3-dichloropropane and a hydrolysis agent to produce 1, 3-propanediol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes the intermediate product 1, 3-dichloropropanol of the epichlorohydrin prepared by a cheap glycerol chlorination method as a raw material, obtains the important chemical raw material 1, 3-propanediol through dehydration, hydrogenation and hydrolysis reactions, and the single-pass conversion rate in the whole process is more than 75 percent, thereby widening the application range of the 1, 3-dichloropropanol, providing a new way for preparing the 1, 3-propanediol by the glycerol and being suitable for industrial production;
(2) the method provided by the invention adopts the steps of dehydration, hydrogenation, hydrolysis reaction and the like, and has the advantages of mild reaction conditions, low cost, environmental friendliness, economy and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic representation of the production of 1, 3-propanediol from 1, 3-dichloropropanol according to an exemplary embodiment of the invention.
Description of the drawings: 1-protective gas, 2-1, 3-dichloropropanol, 3-transfer pump, 4-preheating furnace, 5-dehydration reactor, 6-condenser, 7-dehydration product storage tank, 8-transfer pump, 9-hydrogen, 10-hydrogenation reactor, 11-carbonate aqueous solution, 12-hydrolysis reaction device, 13-condenser and 14-hydrolysis product storage tank.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for producing 1, 3-propanediol from 1, 3-dichloropropanol, comprising:
continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst, and keeping the temperature at 200--1Carrying out dehydration reaction under the condition of (1) to prepare 1, 3-dichloropropene;
continuously feeding the 1, 3-dichloropropene into a reaction device provided with a hydrogenation catalyst, wherein the hydrogen pressure is 1-10MPa, the temperature is 20-100 ℃, and the space velocity is 0.1-5.0h-1Carrying out hydrogenation reaction under the condition of (1) to obtain 1, 3-dichloropropane;
and carrying out hydrolysis reaction on the mixed reaction system containing the 1, 3-dichloropropane, the hydrolysis agent and the solvent at the temperature of 50-150 ℃ for 2-10h to prepare the 1, 3-propylene glycol.
Further, the product of the dehydration reaction also comprises unreacted 1, 3-dichloropropanol, water and other organic matters. In some more specific embodiments, the method comprises: continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst at the temperature of 300-450 ℃ and the space velocity of 0.5-2.0h-1The dehydration reaction is carried out under the conditions of (1).
Further, the method further comprises: preheating and gasifying the 1, 3-dichloropropanol, mixing the 1, 3-dichloropropanol with protective gas, continuously inputting the mixture into a reaction device provided with a dehydration catalyst, and performing dehydration reaction.
In a further pair, the method further comprises: after the dehydration reaction is completed, the obtained mixture is subjected to condensation treatment to obtain the 1, 3-dichloropropene.
Further, the protective gas includes nitrogen and/or an inert gas, and is not limited thereto.
In some more specific embodiments, the dehydration catalyst comprises a zeolitic molecular sieve catalyst and/or a solid acid catalyst.
Further, the zeolite molecular sieve catalyst includes, but is not limited to, a Beta molecular sieve.
Further, the solid acid catalyst comprises a carrier and a solid acid loaded on the carrier.
Further, the solid acid includes any one or a combination of two or more of heteropolyacid, solid phosphoric acid, solid sulfuric acid, metal oxide, metal chloride, and metal fluoride, and is not limited thereto.
In some more specific embodiments, the hydrogenation catalyst comprises a raney nickel catalyst and/or a supported noble metal catalyst.
Further, the raney nickel catalyst is composed of fine nickel-aluminum alloy grains having a porous structure.
Further, the supported noble metal catalyst is a supported noble metal eggshell type catalyst.
In some more specific embodiments, the supported noble metal catalyst comprises a support and a noble metal and a promoter supported on the support.
Further, the noble metal includes any one or a combination of two or more of platinum, palladium, ruthenium, and rhodium, and is not limited thereto.
Further, the auxiliary agent includes any one or a combination of two or more of nickel, iron, cobalt, tin, and zinc, and is not limited thereto.
Further, the carrier includes any one or a combination of two or more of alumina, silica, and zirconia, and is not limited thereto, and particularly, γ -alumina is preferable.
Further, the content of the noble metal in the supported noble metal catalyst is 1-20 wt%.
Furthermore, the content of the auxiliary agent in the supported noble metal catalyst is 5-30 wt%.
In some more specific embodiments, the reaction device provided with the hydrogenation catalyst comprises a kettle type reaction device and/or a fixed bed type reaction device
Further, when the reaction device is a fixed bed type reaction device, the hydrogenation catalyst is the supported noble metal catalyst.
Further, when the reaction device is a kettle type reaction device, the raney nickel catalyst and/or a supported noble metal catalyst are/is selected as the hydrogenation catalyst.
In some more specific embodiments, the hydrolyzing agent comprises a carbonate and/or bicarbonate salt.
Further, the hydrolyzing agent includes any one or a combination of two or more of carbonates and/or bicarbonates of Li, Na, K, Ru, Cs, ammonium, and is not limited thereto.
Further, the solvent includes water, and is not limited thereto.
In some more specific embodiments, the molar ratio of the hydrolyzing agent to 1, 3-dichloropropane is 0.5-3: 1.
Furthermore, the molar ratio of the solvent to the 1, 3-dichloropropane is 10-100: 1.
Another aspect of an embodiment of the present invention also provides a system for producing 1, 3-propanediol, which is applied to the aforementioned method, and includes:
a dehydration reaction unit capable of performing a dehydration reaction of at least 1, 3-dichloropropanol and a dehydration catalyst to produce 1, 3-dichloropropene;
a hydrogenation reaction unit which can perform hydrogenation reaction on at least 1, 3-dichloropropene, hydrogen and a hydrogenation catalyst to prepare 1, 3-dichloropropane;
and a hydrolysis reaction unit capable of performing a hydrolysis reaction of at least 1, 3-dichloropropane and a hydrolysis agent to produce 1, 3-propanediol.
In some more specific embodiments, the dehydration reaction unit comprises a raw material conveying device, a preheating device, a dehydration reaction device and a condensing device.
Further, the preheating device is at least used for gasifying the 1, 3-dichloropropanol to react with the dehydration catalyst.
Further, the dehydration reaction device is a fixed bed reactor which is filled with the particles of the dehydration catalyst in the tubular reactor to form a dehydration catalyst bed layer.
Further, the dehydration reaction unit also comprises a first product storage device.
In some more specific embodiments, the hydrogenation reaction unit comprises a hydrogenation reaction unit.
Further, the hydrogenation reaction device comprises a fixed bed type reactor and/or a kettle type reactor.
Further, the fixed bed reactor is a tubular reactor filled with the particles of the hydrogenation catalyst to form a hydrogenation catalyst bed.
Furthermore, the kettle type reactor is provided with a stirring device and a baffle plate structure.
Further, the hydrolysis reaction unit comprises a hydrolysis reaction device, a condensing device and a second product storage device.
Furthermore, the hydrolysis reaction device adopts a kettle type reactor with a stirring device and a baffle plate structure
In some more specific embodiments of the present invention, the process for producing 1, 3-propanediol from 1, 3-dichloropropanol comprises (as shown in FIG. 1):
(1) dehydration of 1, 3-dichloropropanol
The raw material 1, 3-dichloropropanol 2 is conveyed to a preheating furnace 4 by a conveying pump 3 for preheating gasification treatment, and then is mixed with inert gasThe body 1 is mixed and transported to a dehydration reactor 5 loaded with a dehydration catalyst through a pipeline, and the temperature is 200 ℃ and 500 ℃, and the liquid hourly space velocity is 0.1-5.0h-1The raw materials pass through the dehydration reactor under the condition and undergo dehydration reaction, then are cooled by a condenser 6 and are conveyed to a dehydration product storage tank 7, so that a dehydration product consisting of 1, 3-dichloropropanol, 1, 3-dichloropropene, water and other organic matters is obtained, and the reaction formula is shown as the following formula:
(2) hydrogenation of 1, 3-dichloropropene:
conveying the 1, 3-dichloropropene obtained in the step (1) into a hydrogenation reactor 10 provided with a hydrogenation catalyst through a conveying pump 8 and hydrogen 9, wherein the pressure is 1-10MPa (gauge pressure), the temperature is 20-100 ℃, and the space velocity is 0.1-5h-1Under the condition of (1), passing through the hydrogenation reactor 10 and carrying out hydrogenation reaction to obtain 1, 3-dichloropropane, wherein the reaction formula is shown as the following formula:
(3) hydrolysis reaction of 1, 3-dichloropropane:
conveying the 1, 3-dichloropropane obtained in the step (2) to a hydrolysis reaction kettle 12 through a pipeline, simultaneously adding a proper amount of a carbonate aqueous solution 11, carrying out hydrolysis reaction for 2-10h under the conditions that the temperature is 50-150 ℃ and the pressure is 0-2MPa (gauge pressure), preparing a solution containing 1, 3-propanediol, cooling the solution by a condenser 13, and conveying the solution to a hydrolysate storage tank 14 for storage, wherein the reaction formula is shown as the following formula:
preferably, the dehydration reactor 5 in the step (1) is a fixed bed reactor filled with a static solid particle bed formed by a section of dehydration catalyst particles in a tubular reactor.
Preferably, the hydrogenation reactor 10 in step (2) is a fixed bed reactor in which a section of catalyst particles is filled in a tubular reactor to form a static solid particle bed, or a tank reactor with a stirring device and a baffle structure.
When the hydrogenation reactor 10 in the step (2) is a fixed bed reactor, the hydrogenation catalyst is a supported noble metal eggshell type catalyst using gamma-alumina as a carrier, in the supported noble metal eggshell type catalyst, noble metal is selected from platinum, palladium, ruthenium or rhodium, and an auxiliary agent is one or more of nickel, iron, cobalt, tin or zinc; the content of the noble metal in the supported noble metal catalyst is 1-20 wt%, and the content of the auxiliary agent is 5-30 wt%.
When the hydrogenation reactor 10 in the step (2) is a tank reactor, the hydrogenation catalyst is a raney nickel catalyst composed of fine nickel-aluminum alloy grains with a porous structure, or a supported noble metal eggshell catalyst taking gamma-alumina as a carrier, in the supported noble metal eggshell catalyst, the noble metal is selected from platinum, palladium, ruthenium or rhodium, and the auxiliary agent is one or more of nickel, iron, cobalt, tin or zinc; the content of the noble metal in the supported noble metal catalyst is 1-20 wt%, and the content of the auxiliary agent is 5-30 wt%.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Dehydration of 1, 3-dichloropropanol
Referring to FIG. 1, raw material 1, 3-dichloropropanol 2 is delivered to a preheating furnace 4 by a delivery pump 3, is subjected to preheating gasification treatment, is mixed with protective gas nitrogen and is delivered to a dehydration catalyst (Beta molecular sieve) loaded material through a pipelineIn a dehydration reactor 5, at 500 ℃ and a liquid hourly space velocity of 3.0h-1The product passes through the dehydration reactor under the condition and undergoes dehydration reaction, then is cooled by a condenser 6 and then is conveyed to a dehydration product storage tank 7 to obtain a dehydration product consisting of 1, 3-dichloropropanol, 1, 3-dichloropropene, water and other organic matters, and the product is analyzed by a gas chromatograph to obtain that the conversion rate of the 1, 3-dichloropropanol is 75 percent and the selectivity of the 1, 3-dichloropropene is 90 percent;
(2) hydrogenation of 1, 3-dichloropropene:
conveying the 1, 3-dichloropropene obtained in the step (1) to a hydrogenation catalyst (SnPd/Al in an eggshell type distribution) through a conveying pump 8 and hydrogen 92O3Catalyst) at a pressure of 4MPa (gauge pressure), a temperature of 80 ℃ and a space velocity of 5h-1The reaction product passes through the hydrogenation reactor 10 and undergoes hydrogenation reaction to prepare 1, 3-dichloropropane, the composition of the obtained product is analyzed by a gas chromatograph, the conversion rate of the 1, 3-dichloropropene is 91%, and the selectivity of the 1, 3-dichloropropane is 67%;
(3) hydrolysis reaction of 1, 3-dichloropropane:
conveying the 1, 3-dichloropropane obtained in the step (2) to a hydrolysis reaction kettle 12 through a pipeline, simultaneously adding a proper amount of ammonium carbonate aqueous solution, and carrying out hydrolysis reaction for 4 hours under the conditions that the temperature is 150 ℃ and the pressure is 2MPa (gauge pressure), wherein n isHydrolytic agent:n1, 3-dichloropropane=0.5,nWater (W):n1, 3-dichloropropaneA solution containing 1, 3-propanediol was prepared at 100, and then cooled by a condenser 13 and transferred to a hydrolysate storage tank 14 for storage, and the obtained product was analyzed by a gas chromatograph, and the conversion of the hydrolysis reaction of 1, 3-dichloropropane and the selectivity of 1, 3-propanediol were 90% and 100%.
Example 2
(1) Dehydration of 1, 3-dichloropropanol
Referring to FIG. 1, a raw material 1, 3-dichloropropanol 2 is delivered to a preheating furnace 4 by a delivery pump 3, is subjected to preheating gasification treatment, is mixed with a protective gas nitrogen and is delivered to a furnace loaded with a dehydration catalyst (Al) through a pipeline2O3Supported phosphotungstic acid, 30% HPW/Al2O3) Is/are as followsIn a dehydration reactor 5, at 200 ℃ and a liquid hourly space velocity of 0.1h-1The product passes through the dehydration reactor under the condition and undergoes dehydration reaction, then is cooled by a condenser 6 and then is conveyed to a dehydration product storage tank 7 to obtain a dehydration product consisting of 1, 3-dichloropropanol, 1, 3-dichloropropene, water and other organic matters, and the product is analyzed by a gas chromatograph to obtain that the conversion rate of the 1, 3-dichloropropanol is 83 percent and the selectivity of the 1, 3-dichloropropene is 93 percent;
(2) hydrogenation of 1, 3-dichloropropene:
conveying the 1, 3-dichloropropene obtained in the step (1) to a hydrogenation catalyst (CoPt/Al) through a conveying pump 8 and hydrogen 92O3Catalyst bed) at a pressure of 10MPa (gauge pressure), a temperature of 20 ℃ and a space velocity of 0.5h-1The reaction product passes through the hydrogenation reactor 10 and undergoes hydrogenation reaction to prepare 1, 3-dichloropropane, the composition of the obtained product is analyzed by a gas chromatograph, the conversion rate of the 1, 3-dichloropropene is 83 percent, and the selectivity of the 1, 3-dichloropropane is 54 percent;
(3) hydrolysis reaction of 1, 3-dichloropropane:
conveying the 1, 3-dichloropropane obtained in the step (2) to a hydrolysis reaction kettle 12 through a pipeline, simultaneously adding a proper amount of lithium carbonate aqueous solution, and carrying out hydrolysis reaction for 6 hours at the temperature of 90 ℃, wherein n isHydrolytic agent:n1, 3-dichloropropane=0.8,nWater (W):n1, 3-dichloropropaneA solution containing 1, 3-propanediol was prepared, cooled in the condenser 13 and transferred to the hydrolysate storage tank 14 for storage, and the obtained product was analyzed by gas chromatography with a conversion of the hydrolysis reaction of 1, 3-dichloropropane of 95% and a selectivity of 1, 3-propanediol of 100%.
Example 3
(1) Dehydration of 1, 3-dichloropropanol
Referring to FIG. 1, a raw material 1, 3-dichloropropanol 2 is delivered to a preheating furnace 4 by a delivery pump 3, subjected to preheating gasification treatment, mixed with a protective gas nitrogen and delivered to a furnace loaded with a dehydration catalyst (solid phosphoric acid, 10% H) through a pipeline3PO4/SiO2) In the dehydration reactor 5 at 300 ℃ and at a liquid hourly space velocityIs 2h-1The product passes through the dehydration reactor under the condition and undergoes dehydration reaction, then is cooled by a condenser 6 and then is conveyed to a dehydration product storage tank 7 to obtain a dehydration product consisting of 1, 3-dichloropropanol, 1, 3-dichloropropene, water and other organic matters, and the product is analyzed by a gas chromatograph to obtain that the conversion rate of the 1, 3-dichloropropanol is 63 percent and the selectivity of the 1, 3-dichloropropene is 85 percent;
(2) hydrogenation of 1, 3-dichloropropene:
conveying the 1, 3-dichloropropene obtained in the step (1) to a hydrogenation catalyst (NiRu/Al) through a conveying pump 8 and hydrogen 92O3Catalyst bed) at a pressure of 1MPa (gauge pressure), a temperature of 40 ℃ and a space velocity of 0.1h-1The reaction product passes through the hydrogenation reactor 10 and undergoes hydrogenation reaction to prepare 1, 3-dichloropropane, the composition of the obtained product is analyzed by a gas chromatograph, the conversion rate of the 1, 3-dichloropropene is 99%, and the selectivity of the 1, 3-dichloropropane is 63%;
(3) hydrolysis reaction of 1, 3-dichloropropane:
conveying the 1, 3-dichloropropane obtained in the step (2) to a hydrolysis reaction kettle 12 through a pipeline, simultaneously adding a proper amount of sodium carbonate aqueous solution, and carrying out hydrolysis reaction for 10 hours at the temperature of 50 ℃, wherein n isHydrolytic agent:n1, 3-dichloropropane=2.5,nWater (W):n1, 3-dichloropropaneA solution containing 1, 3-propanediol was prepared, cooled by a condenser 13, and transferred to a hydrolysate storage tank 14 for storage, and the obtained product was analyzed by a gas chromatograph, and the conversion of the hydrolysis reaction of 1, 3-dichloropropane and the selectivity of 1, 3-propanediol were 98% and 100%, respectively.
Example 4
(1) Dehydration of 1, 3-dichloropropanol
Referring to FIG. 1, raw material 1, 3-dichloropropanol 2 is delivered to a preheating furnace 4 by a delivery pump 3, is subjected to preheating gasification treatment, is mixed with protective gas nitrogen and is delivered to a furnace loaded with a dehydration catalyst (solid sulfuric acid, 10% H) through a pipeline2SO4/SiO2) In the dehydration reactor 5 at 350 ℃ and a liquid hourly space velocity of 5.0h-1Under the condition of said dehydration reactionCarrying out dehydration reaction in a reactor, cooling by a condenser 6, and conveying to a dehydration product storage tank 7 to obtain a dehydration product consisting of 1, 3-dichloropropanol, 1, 3-dichloropropene, water and other organic matters, and analyzing the product by a gas chromatograph to obtain that the conversion rate of the 1, 3-dichloropropanol is 72% and the selectivity of the 1, 3-dichloropropene is 94%;
(2) hydrogenation of 1, 3-dichloropropene:
conveying the 1, 3-dichloropropene obtained in the step (1) to a hydrogenation catalyst (ZnRh/Al) through a conveying pump 8 and hydrogen 92O3Catalyst bed) at a pressure of 3MPa (gauge pressure), a temperature of 60 ℃ and a space velocity of 1.0h-1The reaction product passes through the hydrogenation reactor 10 and undergoes hydrogenation reaction to prepare 1, 3-dichloropropane, the composition of the obtained product is analyzed by a gas chromatograph, the conversion rate of the 1, 3-dichloropropene is 95%, and the selectivity of the 1, 3-dichloropropane is 78%;
(3) hydrolysis reaction of 1, 3-dichloropropane:
conveying the 1, 3-dichloropropane obtained in the step (2) to a hydrolysis reaction kettle 12 through a pipeline, simultaneously adding a proper amount of potassium carbonate aqueous solution, and carrying out hydrolysis reaction for 2 hours at the temperature of 80 ℃, wherein n isHydrolytic agent:n1, 3-dichloropropane=3,nWater (W):n1, 3-dichloropropaneA solution containing 1, 3-propanediol was prepared, cooled by a condenser 13, and transferred to a hydrolysate storage tank 14 for storage, and the obtained product was analyzed by a gas chromatograph, and the conversion of the hydrolysis reaction of 1, 3-dichloropropane was 100% and the selectivity of 1, 3-propanediol was 100%.
And (3) performance characterization: table 1 shows the process conditions of examples 1-4, and Table 2 shows the results of the characterization of examples 1-4.
Table 1 process conditions in examples 1-4
Table 2 shows the results of the characterization in examples 1 to 4
As can be seen from tables 1-2: the invention adopts the intermediate product 1, 3-dichloropropanol in the process of preparing the epichlorohydrin by chlorinating the glycerin with low price as the raw material, and prepares the 1, 3-propanediol by the steps of dehydration, hydrogenation and hydrolysis, has the advantages of simple flow, relatively mild reaction conditions, high conversion efficiency and the like, and provides a new way for preparing the 1, 3-propanediol from the glycerin.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for producing 1, 3-propylene glycol from 1, 3-dichloropropanol is characterized by comprising the following steps:
continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst, and keeping the temperature at 200--1Carrying out dehydration reaction under the condition of (1) to prepare 1, 3-dichloropropene;
continuously feeding the 1, 3-dichloropropene into a reaction device provided with a hydrogenation catalyst, wherein the hydrogen pressure is 1-10MPa, the temperature is 20-100 ℃, and the space velocity is 0.1-5.0h-1Carrying out hydrogenation reaction under the condition of (1) to obtain 1, 3-dichloropropane;
and carrying out hydrolysis reaction on the mixed reaction system containing the 1, 3-dichloropropane, the hydrolysis agent and the solvent at the temperature of 50-150 ℃ for 2-10h to prepare the 1, 3-propylene glycol.
2. The method of claim 1, comprising: continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst, and controlling the temperature at 300--1Carrying out dehydration reaction under the condition of (1); preferably, the method further comprises: preheating and gasifying 1, 3-dichloropropanol, mixing with protective gas, continuously inputting into a reaction device provided with a dehydration catalyst, and performing dehydration reaction; preferably, the method further comprises: after the dehydration reaction is finished, condensing the obtained mixture to obtain the product1, 3-dichloropropene; further preferably, the protective gas comprises nitrogen;
and/or, the dehydration catalyst comprises a zeolite molecular sieve catalyst and/or a solid acid catalyst; preferably, the zeolitic molecular sieve catalyst comprises a Beta molecular sieve; preferably, the solid acid catalyst comprises a carrier and a solid acid supported on the carrier; preferably, the solid acid comprises any one or a combination of two or more of heteropolyacid, solid phosphoric acid, solid sulfuric acid, metal oxide, metal chloride and metal fluoride.
3. The method of claim 1, wherein: the hydrogenation catalyst comprises a Raney nickel catalyst and/or a supported noble metal catalyst; preferably, the raney nickel catalyst consists of fine nickel-aluminum alloy grains having a porous structure; preferably, the supported noble metal catalyst is a supported noble metal eggshell type catalyst.
4. The method of claim 3, wherein: the supported noble metal catalyst comprises a carrier, and a noble metal and an auxiliary agent which are supported on the carrier; preferably, the noble metal comprises any one or a combination of more than two of platinum, palladium, ruthenium and rhodium; preferably, the auxiliary agent comprises any one or a combination of more than two of nickel, iron, cobalt, tin and zinc; preferably, the carrier comprises any one or a combination of more than two of alumina, silicon dioxide and zirconium dioxide; particularly preferably gamma-alumina; preferably, the content of the noble metal in the supported noble metal catalyst is 1-20 wt%; preferably, the content of the auxiliary agent in the supported noble metal catalyst is 5-30 wt%.
5. The method of claim 3, wherein: the reaction device provided with the hydrogenation catalyst comprises a kettle type reaction device and/or a fixed bed type reaction device; preferably, when the reaction device is a fixed bed type reaction device, the hydrogenation catalyst is the supported noble metal catalyst; preferably, when the reaction device is a kettle-type reaction device, the raney nickel catalyst and/or a supported noble metal catalyst are/is selected as the hydrogenation catalyst.
6. The method of claim 1, wherein: the hydrolyzing agent comprises a carbonate and/or bicarbonate; preferably, the hydrolytic agent comprises any one or the combination of more than two of Li, Na, K, Ru, Cs, ammonium carbonate and/or bicarbonate;
and/or, the solvent comprises water.
7. The method of claim 1, wherein: the molar ratio of the hydrolytic agent to the 1, 3-dichloropropane is 0.5-3: 1;
and/or the molar ratio of the solvent to the 1, 3-dichloropropane is 10-100: 1.
8. A system for producing 1, 3-propanediol for use in the method of any one of claims 1-7, comprising:
a dehydration reaction unit capable of performing a dehydration reaction of at least 1, 3-dichloropropanol and a dehydration catalyst to produce 1, 3-dichloropropene;
a hydrogenation reaction unit which can perform hydrogenation reaction on at least 1, 3-dichloropropene, hydrogen and a hydrogenation catalyst to prepare 1, 3-dichloropropane;
and a hydrolysis reaction unit capable of performing a hydrolysis reaction of at least 1, 3-dichloropropane and a hydrolysis agent to produce 1, 3-propanediol.
9. The system of claim 8, wherein: the dehydration reaction unit comprises a raw material conveying device, a preheating device, a dehydration reaction device and a condensing device;
preferably, the preheating device is at least used for gasifying the 1, 3-dichloropropanol to react with the dehydration catalyst; preferably, the dehydration reaction device is a fixed bed reactor in which a tubular reactor is filled with the particles of the dehydration catalyst to form a dehydration catalyst bed layer.
10. The system of claim 8, wherein: the hydrogenation reaction unit comprises a hydrogenation reaction device;
preferably, the hydrogenation reaction device comprises a fixed bed reactor and/or a kettle reactor; preferably, the fixed bed reactor is a tubular reactor filled with the particles of the hydrogenation catalyst to form a hydrogenation catalyst bed layer; preferably, the tank reactor is a tank reactor with a stirring device and a baffle plate structure.
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