CN111875508A - Preparation method of low-cost cationic etherifying agent - Google Patents
Preparation method of low-cost cationic etherifying agent Download PDFInfo
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- CN111875508A CN111875508A CN202010780039.5A CN202010780039A CN111875508A CN 111875508 A CN111875508 A CN 111875508A CN 202010780039 A CN202010780039 A CN 202010780039A CN 111875508 A CN111875508 A CN 111875508A
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 239000006227 byproduct Substances 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 33
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000007670 refining Methods 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000005086 pumping Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 iron ions Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000005703 Trimethylamine hydrochloride Substances 0.000 abstract description 3
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 25
- 238000001514 detection method Methods 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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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 preparation method of a low-cost cationic etherifying agent, which comprises the following steps of (1) preparing trimethylamine hydrochloride; (2) introducing epoxy chloropropane to prepare a crude product; (3) and (5) refining the crude product. The reaction steps are as follows: (1) pumping the byproduct hydrochloric acid into a reaction kettle with good air tightness under the condition of stirring, and then slowly introducing trimethylamine; (2) slowly adding epoxy chloropropane into the reaction kettle through an overhead tank to obtain a crude product of the cationic etherifying agent; (3) refining to obtain a qualified product. The method uses the byproduct hydrochloric acid to replace the industrial synthetic hydrochloric acid, thereby reducing the treatment cost of the byproduct hydrochloric acid, protecting the environment and reducing the production cost of the cationic etherifying agent. And the prepared crude product has less raw material residue and less organic byproduct generation, improves the quality of the cationic etherifying agent, improves the competitiveness of the product in the market and enlarges the enterprise benefit.
Description
Technical Field
The invention relates to the technical field of production of cationic etherifying agents, in particular to a preparation method of a low-cost cationic etherifying agent.
Background
The cationic etherifying agent is widely applied to the field of fine chemical engineering and is a multifunctional chemical product. Commercially available products are divided into two categories, one being solid and the other being aqueous. The water solution is colorless transparent liquid, and is mostly 69% water solution at normal temperature, and the product can be quickly converted into an epoxidation structure with high reaction activity under the alkaline condition, so that the product can easily perform chemical reaction with a compound containing active hydrogen to obtain the multifunctional chemical containing the quaternary ammonium group.
The cationic etherifying agent is widely applied to the fields of paper making industry, daily chemical industry, petroleum industry, water treatment industry and the like. The product is used for preparing cationic starch, cationic polyacrylamide, modified guar gum, electroplating additives, textile printing and dyeing auxiliaries, antistatic agents, papermaking auxiliaries and the like, and can also be used as industries of cationic surfactants, water treatment flocculants, textiles, conductive coatings, electroplating, cosmetics and the like.
The three patents of CN107353213A, CN107349869A and CN205556516U all use synthetic hydrochloric acid, trimethylamine and epichlorohydrin as raw materials, and a series of process steps such as preparing trimethylamine hydrochloride, dripping epichlorohydrin at low temperature, reacting at normal temperature, refining products and the like are carried out. Although the process is mature, the product price is higher, and the application range of the product cannot be expanded.
Therefore, there is a need for a low-cost method for preparing cationic etherifying agents, so as to expand the application range of the cationic etherifying agents.
Disclosure of Invention
In order to solve the problems in the prior art, the invention develops a preparation method of a low-cost liquid cationic etherifying agent, improves the quality of the cationic etherifying agent, enlarges the application scale of products, enhances the product competitiveness and improves the production benefit.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a low-cost cationic etherifying agent, which comprises the following steps:
pumping byproduct hydrochloric acid into a reaction kettle, stirring, and slowly introducing trimethylamine to react; when all trimethylamine is added into the reaction kettle, reacting for 30-90 min at normal temperature;
after the reaction is finished, dropwise adding epoxy chloropropane into the reaction kettle for reaction; after 1-2 hours from the beginning of the dropwise adding, adding an acidic catalyst to adjust the pH value;
after the dropwise addition of the epoxy chloropropane is finished, heating to 30-40 ℃, and continuously reacting for 1-4 hours to obtain a crude product;
transferring the crude product to a refining device for refining to obtain a refined product;
and step five, adjusting the content and the pH value of the refined product, cooling and discharging to obtain the cationic etherifying agent.
Further, the feeding molar ratio of trimethylamine, byproduct hydrochloric acid and epichlorohydrin is 1: (1-1.2): (1-1.3).
Furthermore, the concentration of the byproduct hydrochloric acid in the first step is more than 20%, and the content of metal ions in the byproduct hydrochloric acid is less than 100ppm in terms of iron ions.
Further preferably, the concentration of the by-product hydrochloric acid in the step one is 20-31%.
Further, the reaction temperature in the first step is controlled to be 20-50 ℃ when trimethylamine is slowly introduced, and preferably 30-40 ℃; the introduction time of trimethylamine is 1 to 3 hours, preferably 2 to 3 hours.
Further, in the second step, the reaction temperature is controlled to be 5-20 ℃, and preferably 5-15 ℃; and (3) dropwise adding the epoxy chloropropane by using a metering pump, wherein the dropwise adding time is controlled to be 2-8 hours.
Further, in the second step, the acid catalyst is one or a mixture of 5-20% of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid.
More preferably, the acidic catalyst in the second step is a by-product hydrochloric acid diluent of 10% to 15%.
Furthermore, the adding amount of the acid catalyst is 0.7-1.5% of the total mass of the raw materials.
More preferably, the adding amount of the acid catalyst is 0.9-1.3% of the total mass of the raw materials.
Further, in the second step, the pH value is adjusted to 8-10.
Further, the refining device in the fourth step is a stripping tower, and the parameters are as follows: the gas-liquid ratio is controlled to be 1.30-1.90, and the steam pressure is controlled to be 0.3-0.6 MPa.
Further preferably, the gas-liquid ratio of the stripping tower is controlled to be 1.50-1.90, and the steam pressure is controlled to be 0.4-0.6 MPa.
And further, in the fifth step, the content of the refined product is adjusted to be more than 69%, and the pH value is 4-7.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) the byproduct hydrochloric acid is used as a byproduct in the production process of various chemical products, has huge annual output, but has narrow applicable range, less annual consumption, difficult direct treatment and high cost, occupies stock after being stored for a long time, and causes huge pressure on environmental protection. Not only the production potential of enterprises is limited, but also the continuous development of the enterprises is limited. In addition, the byproduct hydrochloric acid is low in price, and has huge excavation potential on the contrary of reducing the cost of the product. Based on the reasons, the hydrochloric acid used in the reaction process is replaced by the byproduct hydrochloric acid or the diluted aqueous solution, and the qualified cationic etherifying agent product is obtained under the condition that the existing production process and equipment are not subjected to large-scale transformation through technical optimization.
(2) Multiple experiments prove that the method has better matching property with the existing mature process, and does not need to carry out large-scale modification on production equipment.
(3) The prepared trimethylamine hydrochloride can directly react with the epichlorohydrin without treatment.
(4) The prepared crude product has less raw material residue and less organic by-product generation.
(5) The detection and application effects prove that various indexes of the cationic etherifying agent prepared by the method are within the standard requirement range, and the application effect is not different from that of the product prepared by the original process. The specific detection result, appearance: a colorless transparent liquid; effective content: not less than 69%; pH value: 4 to 7; residual amount of epichlorohydrin: less than or equal to 5 ppm; 1, 3-dichloropropanol content: less than or equal to 10ppm and the product yield is more than 90 percent.
Detailed Description
The invention provides a preparation method of a low-cost cationic etherifying agent, which reduces the production cost, improves the quality of the cationic etherifying agent and improves the production benefit.
The preparation method comprises the following steps:
pumping byproduct hydrochloric acid into a reaction kettle, stirring, and slowly introducing trimethylamine to react; when all trimethylamine is added into the reaction kettle, reacting for 30-90 min at normal temperature;
after the reaction is finished, dropwise adding epoxy chloropropane into the reaction kettle for reaction; after 1-2 hours from the beginning of the dropwise adding, adding an acidic catalyst to adjust the pH value;
after the dropwise addition of the epoxy chloropropane is finished, heating to 30-40 ℃, and continuously reacting for 1-4 hours to obtain a crude product;
transferring the crude product to a refining device for refining to obtain a refined product;
and step five, adjusting the content and the pH value of the refined product, cooling and discharging to obtain the cationic etherifying agent.
In a preferred embodiment of the present invention, the feed molar ratio of trimethylamine, by-product hydrochloric acid, and epichlorohydrin is 1: (1-1.2): (1-1.3).
In a preferred embodiment of the present invention, the concentration of the by-product hydrochloric acid in the first step is greater than 20%, wherein the content of metal ions is less than 100ppm calculated by iron ions. Preferably, the concentration of the by-product hydrochloric acid in the step one is 20-31%. The by-product hydrochloric acid is colorless and transparent liquid in appearance, and has no mechanical impurities, alcohol, phenols, carboxylic acids and other organic impurities which can react with the epichlorohydrin.
In a preferred embodiment of the invention, the reaction temperature in the first step is controlled to be 20-50 ℃, preferably 30-40 ℃ when trimethylamine is slowly introduced; the introduction time of trimethylamine is 1 to 3 hours, preferably 2 to 3 hours.
In a preferred embodiment of the present invention, the reaction temperature in the second step is controlled to be 5-20 ℃, preferably 5-15 ℃; and (3) dropwise adding the epoxy chloropropane by using a metering pump, wherein the dropwise adding time is controlled to be 2-8 hours.
In a preferred embodiment of the invention, in the second step, the acid catalyst is one or a mixture of more of 5% to 20% of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid; preferably 10-15% by-product hydrochloric acid diluent.
In a preferred embodiment of the invention, the amount of the acidic catalyst added is 0.7-1.5% of the total mass of the raw materials. Preferably, the adding amount of the acid catalyst is 0.9-1.3% of the total mass of the raw materials.
In a preferred embodiment of the present invention, in the second step, the pH value is adjusted to 8-10.
In a preferred embodiment of the invention, the refining unit in step four is a stripping column, the parameters of which are set as follows: the gas-liquid ratio is controlled to be 1.30-1.90, and the steam pressure is controlled to be 0.3-0.6 MPa. Preferably, the gas-liquid ratio of the stripping tower is controlled to be 1.50-1.90, and the steam pressure is controlled to be 0.4-0.6 MPa.
In a preferred embodiment of the invention, the content of the refined product in the step five is adjusted to be more than 69%, and the pH value is 4-7.
The present invention will now be described in detail and with particular reference to certain embodiments thereof for the purpose of providing a better understanding of the present invention. The present invention includes, but is not limited to, the following examples.
Example 1
The embodiment provides a preparation method of a low-cost cationic etherifying agent, which specifically comprises the following steps:
cleaning a reaction device to ensure that the device meets production requirements;
pumping 550kg of 20% by-product hydrochloric acid into a reaction kettle, starting stirring, slowly introducing 180kg of trimethylamine within 3 hours, and keeping the temperature at 40 ℃ in the reaction process; after all trimethylamine is added into the reaction kettle, the reaction is continued for 60min at room temperature by taking the trimethylamine as a node;
step three, keeping the temperature of the material at 15 ℃, starting a metering pump, and dropwise adding 300kg of epoxy chloropropane into the reaction kettle within 4 hours; after 2 hours from the beginning of dripping, adding a byproduct hydrochloric acid accounting for 1.2 percent of the total mass of the raw materials, and adjusting the pH to 9 to keep the materials in a rapid reaction environment all the time;
after the dropwise addition of the epoxy chloropropane is finished, raising the temperature to 40 ℃, and keeping the temperature to continue reacting for 2 hours;
transferring the material to a stripping device, and controlling parameters: controlling the gas-liquid ratio at 1.60 and the steam pressure at 0.5MPa, and refining the crude product;
sixthly, transferring the refined product to an adjusting kettle, and adjusting the content of the material to be more than or equal to 69% and the pH value to be 4-7;
and step seven, cooling and discharging the materials.
Example 2
The embodiment provides a preparation method of a low-cost cationic etherifying agent, which specifically comprises the following steps:
cleaning a reaction device to ensure that the device meets production requirements;
pumping 350kg of 31% by-product hydrochloric acid into a reaction kettle, starting stirring, slowly introducing 590kg of 30% trimethylamine aqueous solution within 3 hours, and keeping the temperature at 40 ℃ in the reaction process; after the trimethylamine aqueous solution is completely added into the reaction kettle, the reaction is continued for 60min at room temperature by taking the trimethylamine aqueous solution as a node;
step three, keeping the material at 15 ℃, starting a metering pump, and dropwise adding 330kg of epoxy chloropropane into the reaction kettle within 4 hours; after 2 hours from the beginning of dripping, adding a byproduct hydrochloric acid accounting for 1.2 percent of the total mass of the raw materials, and adjusting the pH to 9 to keep the materials in a rapid reaction environment all the time;
after the dropwise addition of the epoxy chloropropane is finished, raising the temperature to 40 ℃, and keeping the temperature to continue reacting for 2 hours;
transferring the material to a stripping device, and controlling parameters: controlling the gas-liquid ratio at 1.90 and the steam pressure at 0.6MPa, and refining the crude product;
sixthly, transferring the refined product to an adjusting kettle, and adjusting the content of the material to be more than or equal to 69% and the pH value to be 4-7;
and step seven, cooling and discharging the materials.
Example 3
The embodiment provides a preparation method of a low-cost cationic etherifying agent, which specifically comprises the following steps:
cleaning a reaction device to ensure that the device meets production requirements;
pumping 350kg of 31% by-product hydrochloric acid into a reaction kettle, starting stirring, slowly introducing 180kg of trimethylamine within 3 hours, and keeping the temperature at 40 ℃ in the reaction process; after all trimethylamine is added into the reaction kettle, the reaction is continued for 60min at room temperature by taking the trimethylamine as a node;
step three, keeping the temperature of the material at 15 ℃, starting a metering pump, and dropwise adding 330kg of epoxy chloropropane into the reaction kettle within 4 hours; after 2 hours from the beginning of dripping, adding a byproduct hydrochloric acid accounting for 1.2 percent of the total mass of the raw materials, and adjusting the pH to 9 to keep the materials in a rapid reaction environment all the time;
after the dropwise addition of the epoxy chloropropane is finished, raising the temperature to 40 ℃, and keeping the temperature to continue reacting for 2 hours;
transferring the material to a stripping device, and controlling parameters: controlling the gas-liquid ratio at 1.60 and the steam pressure at 0.5MPa, and refining the crude product;
sixthly, transferring the refined product to an adjusting kettle, and adjusting the content of the material to be more than or equal to 69% and the pH value to be 4-7;
and step seven, cooling and discharging the materials.
Example 4
The embodiment provides a preparation method of a low-cost cationic etherifying agent, which specifically comprises the following steps:
cleaning a reaction device to ensure that the device meets production requirements;
pumping 440kg of 25% by-product hydrochloric acid into a reaction kettle, starting stirring, slowly introducing 180kg of trimethylamine within 3 hours, and keeping the temperature at 40 ℃ in the reaction process; after all trimethylamine is added into the reaction kettle, the reaction is continued for 60min at room temperature by taking the trimethylamine as a node;
step three, keeping the temperature of the materials at 15 ℃, starting a metering pump, and dropwise adding 280kg of epoxy chloropropane into the reaction kettle within 4 hours; after 2 hours from the beginning of dripping, adding a byproduct hydrochloric acid accounting for 1.2 percent of the total mass of the raw materials, and adjusting the pH to 9 to keep the materials in a rapid reaction environment all the time;
after the dropwise addition of the epoxy chloropropane is finished, raising the temperature to 40 ℃, and keeping the temperature to continue reacting for 2 hours;
transferring the material to a stripping device, and controlling parameters: controlling the gas-liquid ratio at 1.60 and the steam pressure at 0.5MPa, and refining the crude product;
sixthly, transferring the refined product to an adjusting kettle, and adjusting the content of the material to be more than or equal to 69% and the pH value to be 4-7;
and step seven, cooling and discharging the materials.
Comparative example
The comparative example provides a preparation method of a conventional cationic etherifying agent, and the specific preparation method comprises the following steps:
cleaning a reaction device to ensure that the device meets production requirements;
pumping 350kg of 31% synthetic hydrochloric acid into a reaction kettle, starting stirring, slowly introducing 180kg of trimethylamine within 3 hours, and keeping the temperature at 40 ℃ in the reaction process; after all trimethylamine is added into the reaction kettle, the reaction is continued for 60min at room temperature by taking the trimethylamine as a node;
step three, keeping the temperature of the materials at 15 ℃, starting a metering pump, and dropwise adding 280kg of epoxy chloropropane into the reaction kettle within 4 hours; after 2 hours from the beginning of dripping, dilute hydrochloric acid accounting for 1.2 percent of the total mass of the raw materials is added, and the pH value is adjusted to 9, so that the materials are always kept in a rapid reaction environment;
after the dropwise addition of the epoxy chloropropane is finished, raising the temperature to 40 ℃, and keeping the temperature to continue reacting for 2 hours;
transferring the material to a stripping device, and controlling parameters: controlling the gas-liquid ratio at 1.60 and the steam pressure at 0.5MPa, and refining the crude product;
sixthly, transferring the refined product to an adjusting kettle, and adjusting the content of the material to be more than or equal to 69% and the pH value to be 4-7;
and step seven, cooling and discharging the materials.
The following detection experiments were carried out on the cationic etherifying agents provided in examples 1 to 4 and the cationic etherifying agent of the comparative example:
1. and (3) effective content detection: detecting the effective content by a hydrochloric acid back titration method;
2. detecting the content of organic impurities: detection by gas chromatography;
and 3, pH value detection: a thunder magnet PHS-2F type pH meter was used.
The results are shown in Table 1.
TABLE 1 Experimental results for the detection of the cationic etherifying agent component
The detection experiment results show that various indexes of the cationic etherifying agent prepared by the method are within the standard requirement range, and the application effect is not different from that of the product prepared by the original process. The specific detection result, appearance: a colorless transparent liquid; effective content: not less than 69%; pH value: 4 to 7; residual amount of epichlorohydrin: less than or equal to 5 ppm; 1, 3-dichloropropanol content: less than or equal to 10ppm and the product yield is more than 90 percent. The hydrochloric acid used in the invention is a byproduct hydrochloric acid with low price, so the cost can be saved and the environment can be protected.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a low-cost cationic etherifying agent is characterized by comprising the following steps:
pumping byproduct hydrochloric acid into a reaction kettle, stirring, and slowly introducing trimethylamine to react; when all trimethylamine is added into the reaction kettle, reacting for 30-90 min at room temperature;
after the reaction is finished, dropwise adding epoxy chloropropane into the reaction kettle for reaction; after 1-2 hours from the beginning of the dropwise adding, adding an acidic catalyst to adjust the pH value;
step three, after the dropwise addition of the epoxy chloropropane is finished, heating to 30-40 ℃, and continuously reacting for 1-4 hours to obtain a crude product;
transferring the crude product to a refining device for refining to obtain a refined product;
and step five, adjusting the content and the pH value of the refined product, cooling and discharging to obtain the cationic etherifying agent.
2. The method for producing a low-cost cationic etherifying agent as set forth in claim 1, wherein the molar ratio of the trimethylamine, by-product hydrochloric acid, and epichlorohydrin is: 1: (1-1.2): (1-1.3).
3. The method for producing a low-cost cationic etherifying agent as recited in claim 1, wherein said concentration of by-product hydrochloric acid in the first step is more than 20%; wherein the content of metal ions is less than 100ppm calculated by iron ions.
4. The method for preparing the low-cost cationic etherifying agent as set forth in claim 1, wherein the reaction temperature in the first step is controlled to 20-50 ℃; the introduction time of the trimethylamine is 1-3 hours.
5. The method for preparing the low-cost cationic etherifying agent as recited in claim 1, wherein the reaction temperature in the second step is controlled to 5-20 ℃; and (3) dropwise adding the epoxy chloropropane by using a metering pump, wherein the dropwise adding time is controlled to be 2-8 hours.
6. The method for preparing the low-cost cationic etherifying agent as recited in claim 1, wherein the acidic catalyst is one or more of diluted hydrochloric acid, diluted sulfuric acid and diluted nitric acid with a concentration of 5% to 20%.
7. The method for preparing a low-cost cationic etherifying agent as recited in claim 1, wherein an amount of said acidic catalyst added is 0.7% to 1.5% of a total mass of raw materials.
8. The method for preparing a low-cost cationic etherifying agent as set forth in claim 1, wherein the pH is adjusted to 8-10 in the second step.
9. The method for preparing a low-cost cationic etherifying agent as set forth in claim 1, wherein the refining apparatus in the fourth step is a stripping tower having parameters set as follows: the gas-liquid ratio is controlled to be 1.30-1.90, and the steam pressure is controlled to be 0.3-0.6 MPa.
10. The method for preparing a low-cost cationic etherifying agent as recited in claim 1, wherein the content of the refined product in the step five is adjusted to be greater than 69%, and the pH value is 4-7.
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| CN202010780039.5A Pending CN111875508A (en) | 2020-08-05 | 2020-08-05 | Preparation method of low-cost cationic etherifying agent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61130281A (en) * | 1984-11-30 | 1986-06-18 | Kao Corp | Stabilized aqueous solution of glycidyl quaternary ammonium salt |
| CN1043135A (en) * | 1989-10-13 | 1990-06-20 | 茹国军 | The production method of highgrade cationic starch |
| CN105669473A (en) * | 2016-04-01 | 2016-06-15 | 山东国丰君达化工科技股份有限公司 | Key node temperature control method in high-quality cationic etherifying agent production process |
| CN105669472A (en) * | 2016-04-01 | 2016-06-15 | 山东国丰君达化工科技股份有限公司 | High-quality cationic etherifying agent production process pH value dynamic control method |
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2020
- 2020-08-05 CN CN202010780039.5A patent/CN111875508A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61130281A (en) * | 1984-11-30 | 1986-06-18 | Kao Corp | Stabilized aqueous solution of glycidyl quaternary ammonium salt |
| CN1043135A (en) * | 1989-10-13 | 1990-06-20 | 茹国军 | The production method of highgrade cationic starch |
| CN105669473A (en) * | 2016-04-01 | 2016-06-15 | 山东国丰君达化工科技股份有限公司 | Key node temperature control method in high-quality cationic etherifying agent production process |
| CN105669472A (en) * | 2016-04-01 | 2016-06-15 | 山东国丰君达化工科技股份有限公司 | High-quality cationic etherifying agent production process pH value dynamic control method |
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Application publication date: 20201103 |