CN101773851B - Dichloropropanol catalyst prepared by glycerol method - Google Patents
Dichloropropanol catalyst prepared by glycerol method Download PDFInfo
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- CN101773851B CN101773851B CN 200910028891 CN200910028891A CN101773851B CN 101773851 B CN101773851 B CN 101773851B CN 200910028891 CN200910028891 CN 200910028891 CN 200910028891 A CN200910028891 A CN 200910028891A CN 101773851 B CN101773851 B CN 101773851B
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Abstract
The invention relates to epoxy chloropropane intermediate dichloropropanol catalyst prepared by a glycerol method and improvement of a chlorination reaction method. The catalyst is characterized in that the catalyst for reaction is a mixed catalyst of organic carboxylic acid and strong acid, the organic carboxylic acid catalyst is monocarboxylic acid of C1-C12 or dicarboxylic acid of C2-C12, and the dosage is 0.5-5 percent of the content of a glycerol substance; the dosage of the strong acid catalyst is 0.5-15 percent of the content of the glycerol substance; the substance amount ratio of the organic carboxylic acid to the strong acid is 1:1.0-8.0, and the chlorination reaction is carried out in a reactor and a spray reaction tower with filler, which are connected in series. Compared with single catalyst, the invention has high catalytic activity, short reaction time, total reaction time of 6-8 hours and high dichloropropanol yield of larger than 96 percent; particularly, the chlorination reaction is carried out in the reactor and the spray reaction tower with the filler, which are connected in series, and the reaction time can be further shortened by 1-2 hours.
Description
Technical field
The present invention relates to the improvement of preparing epoxy chloropropane by using glycerol method intermediate dichlorohydrin catalyst and chlorination reaction method, it is big to relate in particular to a kind of catalytic activity, the catalyst that reaction yield is high.
Background technology
Epoxychloropropane has another name called chloropropylene oxide, is a kind of important Organic Chemicals and fine chemicals, and purposes is very extensive, and for example it is the important source material of preparation epoxy resin, synthetic elastomer, glue used in paper-making etc.Prior synthesizing method has propylene high-temperature chloridising and allyl acetate method, after develop preparing epoxy chloropropane by using glycerol method again, its course of reaction is following:
Course of reaction in two steps, (1) formula; Glycerin chlorination preparation 1,3-dichlorohydrin and 1, the 2-dichlorohydrin (owing to all generate epoxychloropropane after the two further hydrolysis, thereby this patent is 1,3-dichlorohydrin and 1, the 2-dichlorohydrin is referred to as dichlorohydrin, down with.); (2) formula:, obtain epoxychloropropane with the hydrolysis cyclisation under alkali condition of product dichlorohydrin.In the two step courses of reaction, reaction (2) technology is simple, operation is ripe, reaction yield is high, thereby the key of preparing epoxy chloropropane by using glycerol method is that (1) step glycerin chlorination prepares dichlorohydrin.
Belgium Su Wei (SOLVAY) company is in EP1760060, EP1762556, WO2005/054167, WO2007/054505, CN1882522A, CN1974511A, CN100999443A, CN101003614A, CN10168761, CN101066909 patent; Disclosed glycerine and HCl gas prepare the dichlorohydrin method continuously, and its catalyst of selecting for use is C
1～C
8Carboxylic acid, like polycarboxylic acids such as monocarboxylic acids such as formic acid, acetate, propionic acid, butyric acid, valeric acid or succinic acid, glutaric acid, adipic acids, catalyst amount is usually greater than 1mol/kg (catalyst concentration in every kilogram of liquid).This technology is because what adopt is single carboxylic acids catalyst, and is active relatively low, thereby the yield of dichlorohydrin and selectivity are lower, yield 76.6%, selectivity 77.3%; The operation time is longer, needs 9～16h.
Disclosedly among the Chinese patent CN101029000 prepare the method for dichlorohydrin, adopt organic nitrile compound to make catalyst by glycerin chlorination.Organic nitrile compound has: acetonitrile, propionitrile, acrylonitrile, positive valeronitrile, isobutyronitrile, hydroxyacetonitrile, chloro acetonitrile, succinonitrile, glutaronitrile, adiponitrile and composition thereof or benzonitrile, benzene acetonitrile, substituted benzonitrile, benzene acetonitrile and composition thereof.Catalyst need be used the 30%HCl activation before use, and the catalyst use amount is 1～10% (accounting for glycerine amount ratio), 1 to 10 hour this technological reaction time, and glycerol conversion yield 99%, the dichlorohydrin total recovery is greater than 90%.Because the organic nitrile compound catalyst needs to handle with 30%HCl before use, has increased reaction process; Secondly, through the HCl catalyst processed, in reacted raffinate, contain the CN of severe toxicity
-, environmental pollution is serious, the wastewater treatment difficulty.Simultaneously, these catalyst are met acid still can be transformed into the carboxylic acids catalyst, so the above-mentioned defective of carboxylic acids catalyst still exists.
In addition, glycerin chlorination reacts at present, mostly adopts the still formula blistering reaction of one or more levels series connection of agitated reactor; Because of reaction is the gas-liquid reaction system, HCl concentration is lower in the reaction system, and glycerine viscosity is higher again; HCl gas and glycerine reaction are abundant inadequately, and many stills cascade reaction energy consumption is high; Secondly, solution-air still reaction HCl concentration is low, has also caused the yield of dichlorohydrin and selectivity not high, and side reaction such as glycerine shrink takes place easily.
Therefore still having is worth improved place.
Summary of the invention:
The object of the invention is to overcome the deficiency of above-mentioned prior art, provides a kind of catalytic activity big, and reaction yield is high, the dichloropropanol catalyst prepared by glycerol method that the reaction time is short.
The object of the invention realizes that main the improvement is: in the glycerin chlorination reaction, change single organic carboxyl acid catalyst into organic carboxyl acid and strong acid mixed catalyst, thereby overcome the deficiency of above-mentioned prior art, realize the object of the invention.Specifically, glycerin chlorination of the present invention prepares dichlorohydrin and uses catalyst, it is characterized in that catalyst is organic carboxyl acid and strong acid mixed catalyst, and said organic carboxyl acid catalyst is C
1～C
12Monocarboxylic acid or C
2～C
12Dicarboxylic acids, consumption are 0.5～5% of glycerine amount of substance; Said strong acid catalyst consumption is 0.5～15% of a glycerine amount of substance; And organic carboxyl acid is 1: 1.0～8.0 with the ratio (mol ratio) of strong acid amount of substance.
The present invention is said
Monocarboxylic acid or dicarboxylic acids are identical with existing carboxylic acid catalyst.Be generally C
1～C
12Aliphatic carboxylic acid and aromatic carboxylic acid, wherein the monobasic aliphatic carboxylic acid is preferably acetate, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, sad, laurate; The monobasic aromatic carboxylic acid is generally F, Cl, the NO that the adjacency pair position is had sucting electronic effect
2In the substituted benzoic acid of group, be preferably: benzoic acid, salicylic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 4-nitrobenzoic acid, 4-fluobenzoic acid; Dicarboxylic acids is C
2～C
12Dibasic aliphatic carboxylic acid or binary aromatic carboxylic acid.Wherein the dibasic aliphatic carboxylic acid has: such as but not limited to like oxalic acid, succinic acid, adipic acid, azelaic acid, decanedioic acid etc.; The binary aromatic carboxylic acid has: such as but not limited to as a position being arranged on phthalic acid, terephthalic acid (TPA), the phenyl ring by F, the substituted phthalic acid of Cl and terephthalic acid (TPA), as: 2-chlorine terephthalic acid (TPA), 2-fluorine terephthalic acid (TPA) etc.Dicarboxylic acids of the present invention is preferably: succinic acid, adipic acid, azelaic acid, phthalic acid, terephthalic acid (TPA), 2-chlorine terephthalic acid (TPA).
Strong acid: a kind of commercially available general inorganic acid that can be the concentrated sulfuric acid, phosphoric acid, red fuming nitric acid (RFNA) etc.; Also can be to be selected from sulfonic group polystyrene resin, sulfonic group polyvinyl resin, p-methyl benzenesulfonic acid, phosphorus heteropoly tungstic acid, and anhydrous AlCl
3, SnCl
4, TiCl
4, ZnCl
2, FeCl
3A kind of Deng in the Lewis acid.If when selecting Lewis acid, preferred anhydrous AlCl
3, TiCl
4, ZnCl
2
The ratio of the amount of the compounding substances of above-mentioned two types of acid, be preferably 1: 1.0～5.0.
Chlorination reaction process of the present invention and raw material and prior art are basic identical, for example can be the said methods of Chinese patent CN100999443A, have no special requirements.Elementary process is: the mixed-acid catalyst of glycerine and aequum is fed in the agitated reactor, open and stir, for example 110 ℃ of heating feed anhydrous HCl gas from the agitated reactor bottom then and carry out chlorination reaction.Azeotropic steams from the agitated reactor top for water, unreacted HCl, part dichlorohydrin that course of reaction generates, and unnecessary HCl gets into agitated reactor again and recycles after condensation, dry pressurization; The dichlorohydrin that reaction generates, glycerine monochlorohydrin etc. flow out from the agitated reactor bottom.It is terminal point that reaction distillates with no azeotropic mixture in the condenser.After chlorination reaction was accomplished, the azeotropic mixture that contains HCl, water, dichlorohydrin that cat head is flowed out mixed with dichlorohydrin, the glycerine monochlorohydrin of generation, added for example Na of weak base or salt
2CO
3, CaCO
3, NaHCO
3Deng wherein HCl of neutralization, filter, standing demix carries out rectifying respectively with lower floor's organic facies and upper strata water, get final product the high-purity dichlorohydrin.The glycerine monochlorohydrin that does not steam in the tower bottoms gets into agitated reactor and recycles.
For simplifying production technology, further to enhance productivity, reactor and the spray reaction tower cascade reaction technology that filler is housed are adopted in a kind of more preferably glycerin chlorination reaction of the present invention.
Because the glycerin chlorination reaction is gas-liquid reaction, initial reaction stage, glycerine viscosity is bigger, through the first one-step chlorination of still formula, after reaction proceeds to certain hour, is mainly a chloropropyl alcohol and dichlorohydrin in the system, and system viscosity reduces greatly; Adopt the fountain reaction behind the viscosity reduction, the spray reaction tower of tower structure, filler all is equipped with in top and bottom; The space is left at the middle part, is equipped with to import and sprinkling equipment, and the spray reaction makes solution-air haptoreaction area increase; The time of staying prolongs, thereby has improved reaction efficiency.And in the chlorination reaction later stage, reaction is controlled by thermodynamics mainly, sprays tower reaction, can in time remove the water that reaction generates, and helps the carrying out that reacts.
Agitated reactor is connected with the spray reaction tower that filler is housed, and can be that an agitated reactor is connected with a spray reaction tower, also can be that a plurality of agitated reactors are connected with a plurality of spray reaction towers, still-still-Ta-Ta for example, or omit one of them.The present invention tests comparison, and preferably connecting of 1～2 agitated reactor and 1～2 spray reaction tower is both economical, and high reaction efficiency was arranged again.Said agitated reactor is the popular response still, has no special requirements.Filler in the spray column; Effect is to increase the gas-liquid reaction contact area; Prolonging the reaction time, so conventional packing in the chemical filler tower, all can be used; Such as but not limited to: entity fillers such as Raschig ring, Pall ring, cascade ring, berl saddle, square saddle screen filler, ripple packing also can be dictyosome fillers such as saddle type net, θ net, ripple net.Be preferably Raschig ring, Pall ring, cascade ring, saddle type net, θ net, ripple net, ripple packing among the present invention.
Glycerine method catalytic preparation dichlorohydrin of the present invention; Owing to adopt organic carboxyl acid and strong acid mixed catalyst; Have than the prior art single catalyst: catalytic activity is high, and the reaction time is short, and total reaction time is by 9～16h of the single employing carboxylic acids of prior art catalyst; Foreshorten to 6～8h, improved commercial production efficient greatly; And the dichlorohydrin yield is high, dichlorohydrin yield＞96%, and more former single acid catalyst improves 6～20%; The catalyst raw material is easy to get, and preparation is simple, use safety, advantage such as pollution-free.Particularly chlorination reaction adopts agitated reactor and the spray reaction tower cascade reaction that filler is housed, and can further enhance productivity, and the reaction time can further shorten 1-2 hour.
Below in conjunction with some specific embodiments, the present invention is further understood in exemplary illustration and help, but the embodiment detail only is for the present invention is described; Do not represent the present invention to conceive whole technical schemes down; Therefore should not be construed as the technical scheme qualification total to the present invention, some do not depart from the unsubstantiality of the present invention's design and change In the view of the technical staff; For example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Description of drawings:
Fig. 1 is a kind of optimization embodiment of the present invention process chart.
Fig. 2 is a spray reaction tower structural representation in Fig. 1 technology.
The specific embodiment:
Embodiment 1 (still reaction): each routine catalyst and proportioning are pressed 1,2,3,4,7 examples in the subordinate list respectively.
With reference to the said method of Chinese patent CN100999443A, the catalyst of glycerine and proportional quantity is joined in the agitated reactor, open and stir, be heated to 110 ℃, feed anhydrous HCl gas from the agitated reactor bottom, regulate the pressure and the flow of HCl gas, glycerine is fully reacted.Water that course of reaction generates and unreacted HCl, part dichlorohydrin steam from the top azeotropic of agitated reactor, and remaining dichlorohydrin, glycerine monochlorohydrin etc. flow out from the agitated reactor bottom.It is terminal point that reaction is flowed out with no cut in the condenser.Unnecessary HCl discharges from the agitated reactor top through condensation, concentrated sulfuric acid drying, gets into agitated reactor after the pressurization again and recycles.
Reacted still liquid and overhead distillate are squeezed in the neutralization reactor, add excessive N a slightly
2CO
3Or NaHCO
3Neutralization HCl wherein, the inorganic salts that elimination generates, standing demix.Tell lower floor's organic facies, get into the interior rectifying separation of rectifying column and obtain dichlorohydrin; The upper strata water is stayed the agitated reactor distillation dehydration, rectifying separation, and cat head can get highly purified dichlorohydrin.The still liquid that does not steam after the rectifying respectively turns back to and continues reaction in the agitated reactor.Reaction time, glycerol conversion yield and dichlorohydrin yield result see attached list.
Embodiment 2 (still adds the spray reaction): each routine catalyst and proportioning are pressed subordinate list 5,6,8 respectively.
Referring to Fig. 1,2, the mixed-acid catalyst feeding agitated reactor E3 with glycerine and proportional quantity among the head tank E1 is heated to 65 ℃, from steel cylinder E2, feeds HCl gas continuously to E3, and HCl feeds speed and is advisable not overflow.Behind the reaction 1h, material imported among the agitated reactor E4 continue chlorination, 90 ℃ of control reaction temperatures continue to feed HCl sustained response 1h.
Material behind the initial reaction imports and is equipped with among the spray reaction tower E8 of ripple net filler; Temperature continuously feeds HCl by E7 to spray reaction tower bottom at 110 ℃ in the control tower, regulates the pressure of HCl gas outlet; Make the glycerine complete reaction, it is terminal point that reaction is flowed out with no cut in the condenser E9.Unnecessary HCl discharges from condenser E9, gets into the spray reaction tower again after, E6 dry through E5 pressurizes.
After chlorination reaction was accomplished, the azeotropic mixture that contains HCl, water, dichlorohydrin with the E8 cat head distillates mixed among the adding E10 with spray reaction tower bottoms, adds Na
2CO
3Neutralization HCl wherein; Through E12 filtration, E13 standing demix, to tell dichlorohydrin and get into E15 rectifying, the upper strata water (steams gas through condenser E14 condensation income E17) behind the distillation dehydration in E13; Rectifying once more in E15, distillate through condenser E16 condensation and collection in E18.The higher boiling glycerine monochlorohydrin that does not steam in the rectifying column gets into agitated reactor and recycles.Reaction time, glycerol conversion yield and dichlorohydrin yield result see attached list.
Spray reaction tower E8 is vertical tower body, and by being divided into three layers down, top accounts for total height 10-30% packing area 3, and the middle and lower part accounts for total height 60-80% packing area 4, is placed with ripple net filler respectively, is reactant liquor spray district, built-in spray equipment 2 between two packing areas.Spray reaction tower spray is distinguished the liquid charging aperture 8 that responds, and discharging opening 1 is arranged at top, top, and tower still reuse liquid charging aperture 7, HCl air inlet 6, discharging opening 5 are arranged at the bottom.
To those skilled in the art, enlighten down some distortion that can directly derive or associate from this patent disclosure and general knowledge in this patent design and embodiment; Or use substituting of known technology in the prior art always, and the mutual various combination between characteristic, the for example change of combination catalyst kind; Change in catalyst amount, ratio range; Or the like unsubstantiality change, can be employed equally, can both realize and basic identical function of the foregoing description and effect; Launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Embodiment catalyst amount, response parameter and reaction result table
Annotate: catalyst amount is the percentage that accounts for the amount of substance of glycerine.
The result of the test explanation: at same process (for example still reaction), comparative example 7, single employing carboxylic acids catalyst, catalytic activity is low, and the reaction time is 15h, and the dichlorohydrin yield has only 76.7%.
Adopt organic carboxyl acid and strong acid mixed catalyst, catalytic activity obviously improves, and the chlorination reaction time is short, and chlorination reaction is merely 6～9h, and the dichlorohydrin yield can be increased to more than 96%, has improved commercial production efficient greatly.
Adopt still to add spray reaction tower tandem process, the reaction time can further shorten 1-3 hour, and the dichlorohydrin yield also has raising, than comparative example 8, shortens 7 hours, has further improved production efficiency.
Claims (8)
1. glycerin chlorination prepares dichlorohydrin and uses catalyst, it is characterized in that catalyst is organic carboxyl acid and strong acid mixed catalyst, and said organic carboxyl acid catalyst is C
1～C
12Monocarboxylic acid or C
2～C
12Dicarboxylic acids, consumption are 0.5～5% of glycerine amount of substance; Said strong acid catalyst consumption is 0.5～15% of a glycerine amount of substance; And organic carboxyl acid is 1 : 1.0～8.0 with the ratio of strong acid amount of substance, and described strong acid is the concentrated sulfuric acid, phosphoric acid, red fuming nitric acid (RFNA), sulfonic group polystyrene resin, sulfonic group polyvinyl resin, p-methyl benzenesulfonic acid, phosphorus heteropoly tungstic acid, AlCl
3, TiCl
4, ZnCl
2In a kind of.
2. prepare dichlorohydrin according to the said glycerin chlorination of claim 1 and use catalyst, it is characterized in that the organic carboxyl acid and the ratio of strong acid amount of substance are 1 : 1.0～5.0.
3. prepare dichlorohydrin according to glycerin chlorination described in claim 1 or 2 and use catalyst, it is characterized in that monocarboxylic acid is an acetate, propionic acid, butyric acid, valeric acid, benzoic acid, salicylic acid, 4-chlorobenzoic acid, 2, a kind of in the 4-dichlorobenzoic acid.
4. prepare dichlorohydrin according to claim 1 or 2 said glycerin chlorinations and use catalyst, it is characterized in that dicarboxylic acids is succinic acid, adipic acid, azelaic acid, phthalic acid, a kind of in terephthalic acid (TPA), the 2-chlorine terephthalic acid (TPA).
5. prepare dichlorohydrin according to claim 1 or 2 said glycerin chlorinations and use catalyst, it is characterized in that carrying out in glycerin chlorination agitated reactor that is reflected at series connection and the spray reaction tower that filler is housed.
6. prepare dichlorohydrin according to the said glycerin chlorination of claim 5 and use catalyst, carry out in it is characterized in that being reflected at 1～2 agitated reactor and 1～2 spray reaction tower being connected.
7. prepare dichlorohydrin according to the said glycerin chlorination of claim 5 and use catalyst, it is characterized in that spraying the reaction tower filler is Raschig ring, Pall ring, cascade ring, saddle type net, θ net, ripple net, ripple packing.
8. prepare dichlorohydrin according to the said glycerin chlorination of claim 6 and use catalyst, it is characterized in that spraying the reaction tower filler is Raschig ring, Pall ring, cascade ring, saddle type net, θ net, ripple net, ripple packing.
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|---|---|---|---|
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| CN102746119A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing dichlorohydrin from glycerol |
| CN109721474A (en) * | 2017-10-30 | 2019-05-07 | 中国石油天然气股份有限公司 | Method for synthesizing dichloroethyl ether and 2-chloroethoxy ethanol |
| CN108863718A (en) * | 2018-07-11 | 2018-11-23 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dichlorohydrin |
| CN109516901A (en) * | 2018-12-28 | 2019-03-26 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of 2,2 '-dichloroether |
| CN113831304B (en) * | 2021-10-09 | 2024-06-18 | 江苏索普工程科技有限公司 | Method for efficiently preparing epichlorohydrin by biomass glycerol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184715A (en) * | 2005-04-18 | 2008-05-21 | 阿塞尔有限责任公司 | Process for the production of alpha, gamma-dichlorohydrin from glycerin and hydrochloric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184715A (en) * | 2005-04-18 | 2008-05-21 | 阿塞尔有限责任公司 | Process for the production of alpha, gamma-dichlorohydrin from glycerin and hydrochloric acid |
Non-Patent Citations (2)
| Title |
|---|
| Direct preparation of dichloropropanol (DCP) from glycerol using heteropolyacid (HPA) catalysts: A catalyst screen study;Sang Hee Lee et al;《Catalysis Communications》;20080314;第9卷;1920-1923 * |
| Sang Hee Lee et al.Direct preparation of dichloropropanol (DCP) from glycerol using heteropolyacid (HPA) catalysts: A catalyst screen study.《Catalysis Communications》.2008,第9卷 |
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Address after: 210047 Jiangsu city of Nanjing province Nanjing Chemical Industrial Park, Bailong Road No. 2 Patentee after: Jiangsu Dena chemical Limited by Share Ltd Patentee after: Jiangsu Tianyin Chemical Industry Co., Ltd. Address before: 210047 Jiangsu city of Nanjing province Nanjing Chemical Industrial Park, Bailong Road No. 2 Patentee before: Dana (Nanjing) Chemical Co. Ltd. Patentee before: Jiangsu Tianyin Chemical Industry Co., Ltd. |