CN110172024B - Method for preparing anhydrous ethylenediamine from diamine hydrochloride serving as byproduct of bisaminosilane - Google Patents
Method for preparing anhydrous ethylenediamine from diamine hydrochloride serving as byproduct of bisaminosilane Download PDFInfo
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000006227 byproduct Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 18
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000004985 diamines Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000292 calcium oxide Substances 0.000 claims abstract description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 19
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 37
- 238000004821 distillation Methods 0.000 claims description 36
- 238000004321 preservation Methods 0.000 claims description 20
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 159000000007 calcium salts Chemical class 0.000 description 18
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004566 building material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to a method for preparing anhydrous ethylenediamine from a diamine hydrochloride byproduct of diamine silane, belonging to the technical field of fine chemical engineering. In the invention, diamine silane by-products, namely ethylenediamine hydrochloride and calcium oxide powder, are stirred and neutralized at 80-115 ℃ in the presence of an ethylenediamine solvent, the reaction is directly distilled to obtain water-containing ethylenediamine with the water content of 2-3% after the reaction is finished, the water-containing ethylenediamine is added with the calcium oxide powder under the action of a catalyst, the mixture is stirred and dehydrated at 100-115 ℃, and then the mixture is distilled to obtain anhydrous ethylenediamine with the water content of less than 0.2%. The method has the advantages of simple equipment and process, cheap and easily available raw materials, safety, environmental protection, high product content and low product moisture content, can be directly used as the raw materials, improves the economic benefit, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for preparing anhydrous ethylenediamine from a diamine hydrochloride byproduct of diamine silane, belonging to the technical field of fine chemical engineering.
Background
Diaminosilane is an important industrial additive which can be used for coupling organic high polymers and inorganic substances, as glass fiber finishing agents, as cross-linking and curing agents for silicone rubber and silicone resin, as textile finishing agents, coating additives, as amino-modified silicone oil, etc., and has an annual global yield of more than 20 ten thousand tons, which represents N- (beta-aminoethyl) -3-aminopropyltrimethoxysilane (KH-792) and N- (beta-aminoethyl) -3-aminopropylmethyldimethoxysilane (KH-602), which account for more than 90% of the total yield of the bisaminosilane. The industrial synthesis method of the diamine silane is completely prepared by adopting ethylenediamine and chlorohydrocarbon silane through aminolysis reaction, delamination and distillation, wherein a byproduct is ethylenediamine hydrochloride, and the molar ratio of the byproduct to a diamine silane product is 1: 1 quantitatively produced. According to theory, about 8.5 million tons of side product is formed as ethylenediamine hydrochloride calculated by 20 million tons of diamine silane yield per year. In China, the ethylenediamine hydrochloride is mostly treated by sodium hydroxide to form 70% of water-containing ethylenediamine which is used for other industrial purposes, the market price of the 70% of water-containing ethylenediamine is about 6000 yuan/ton, the market price of anhydrous ethylenediamine is 2-4 ten thousand, the price difference is huge, and the economic value of the water-containing ethylenediamine is extremely low, so that the production cost of the diamine silane is increased and the diamine silane is not environment-friendly. The production technology of anhydrous ethylenediamine is not complete in China, and is monopolized by several major foreign companies, such as Pasteur, Bayer and the like, and foreign technologies are introduced to make joint production in Jiangsu and Shandong in recent years in China.
The ethylenediamine in the diamine hydrochloride as the byproduct of the diamine silane is prepared and used as a raw material to produce the diamine silane, so that the increasingly severe environment-friendly situation can be solved, and the production cost can be reduced. There are two current industrial methods for treating the byproduct ethylenediamine hydrochloride: one method is to neutralize the by-product ethylenediamine hydrochloride with liquid (solid) alkali, then filter and distill to obtain hydrous ethylenediamine, and the method has the advantages of simple process and equipment, low economic value and high energy consumption, and the by-product sodium chloride salt needs to be treated. The second method is to use liquid (solid) sodium methoxide to neutralize, filter and rectify to obtain anhydrous ethylenediamine and anhydrous methanol, and the method has the advantages of simple process and certain economic benefit, and has the disadvantages of high equipment cost due to the need of a set of rectification device for separating methanol and ethylenediamine, and the by-product sodium chloride salt needs to be treated. There are also references to the treatment of ethylenediamine hydrochloride and aqueous ethylenediamine with calcium oxide, molecular sieves, sodium hydroxide, resins, etc., but all are analyzed theoretically and no description is given of the conditions after treatment, particularly the moisture content of the final ethylenediamine product.
Along with the expansion of the productivity of the bisaminosilane, the yield of the byproduct ethylenediamine hydrochloride is higher and higher, and the requirements on environmental protection and energy consumption are stricter and stricter, so that the problem of the byproduct ethylenediamine hydrochloride produced by the bisaminosilane is urgently solved. The ethylene diamine is used as one of raw materials for producing the diamine, the most important index is the water content, the moisture content of anhydrous ethylene diamine in industrial production is less than 0.2%, only the ethylene diamine with the moisture content of less than 0.3% can be used as the raw material for producing the diamine, the ethylene diamine with high moisture content can hydrolyze the produced diamine, the yield is reduced, the cost is increased, and the diamine product is hydrolyzed and polymerized when serious, so that the product is discarded.
Disclosure of Invention
The invention aims to: the method for preparing the anhydrous ethylenediamine from the diamine hydrochloride serving as the diamine byproduct is simple in process equipment, cheap and easily available in raw materials, safe and environment-friendly, solves the problem of the byproduct of the existing diamine, and can be used for directly producing the diamine, so that the raw material consumption is reduced, and the economic benefit is improved.
The technical scheme of the invention is as follows:
a method for preparing anhydrous ethylenediamine from a diamine hydrochloride byproduct of bisaminosilane is characterized in that: it comprises the following steps:
1) and mixing the diamine hydrochloride serving as a diamine silane by-product with calcium oxide powder and ethylenediamine according to the weight ratio of 2.3-2.5: the weight ratio of 1:2, putting the mixture into a reaction kettle with a stirrer, and neutralizing and reacting for 2 hours at the kettle temperature of 70-80 ℃ under stirring, wherein the stirring speed is 40 r/min;
2) after the neutralization reaction is carried out for 2 hours, the kettle is heated to 110-115 ℃ and the heat preservation reaction is continuously carried out for 6 hours;
3) after the reaction is carried out for 6 hours under the condition of heat preservation, distilling under vacuum at the distillation temperature of 160 ℃ and the pressure of-0.09-0.1 MPa to obtain the water-containing ethylenediamine with the water content of 2-3 percent;
4) putting aqueous ethylenediamine with the water content of 2% -3% into a reaction kettle with stirring, adding calcium oxide powder with the weight of 5% of that of the ethylenediamine and 0.1% of catalyst, carrying out heat preservation, stirring and dehydration reaction at the temperature of 100-115 ℃ for 4 hours, and stirring at the rotating speed of 90 r/m;
5) and after the heat preservation reaction is finished, distilling under the vacuum condition of-0.09-0.1 MPa to obtain anhydrous ethylenediamine with the water content of 0.2%, wherein the distillation temperature is 130 ℃.
The structural formula of the bisaminosilane is NH2CH2CH2NHC3H6Si（OCH3）3、NH2CH2CH2NHC3H6Si（OC2H5）3、NH2CH2CH2NHC3H6（CH3）Si（OCH3）2。
The main components of the diamine hydrochloride serving as the byproduct of the bisaminosilane are as follows: the weight ratio of the ethylenediamine to the ethylenediamine is 30-40%, and the weight ratio of the ethylenediamine hydrochloride to the ethylenediamine hydrochloride is 60-70%.
The catalyst is n-butyl lithium and potassium tert-butoxide according to the weight ratio of 1: 1 in weight ratio.
The anhydrous ethylenediamine with the moisture content of less than 0.3 percent can be directly used as a raw material of diamine silane.
The invention has the advantages that:
according to the invention, only two simple reaction distillation devices with stirring are needed, the equipment and the process are simple, the water content of the product is low, and the product can be directly returned as a production raw material of the diamine silane, so that the raw material consumption is reduced, and the production cost is further reduced; the by-product is solid mixture powder of calcium oxide, calcium hydroxide and calcium chloride, and can be used as building material, and the method is safe and environment-friendly.
Detailed Description
Preparing a catalyst: n-butyl lithium and potassium tert-butoxide are added in a ratio of 1: mixing the components in a weight ratio of 1, and shaking up to obtain the catalyst for later use.
Example 1:
in a 3-ton rake reactor, firstly pumping 1 ton of diamine silane by-product ethylenediamine hydrochloride and 0.8 ton of ethylenediamine solvent, opening stirring, stirring at 40 rpm, and then adding 0.4 ton of calcium oxide powder. After the materials are fed, the temperature of the rake reactor is firstly raised to 70 ℃, the stirring speed is 40 r/min, the neutralization reaction is carried out for 2 hours, and then the temperature of the reactor is raised to 115 ℃, and the heat preservation reaction is continuously carried out for 6 hours. After the reaction is finished, the neutralization reaction device is changed into a common distillation device, and the reaction is distilled under the vacuum condition of-0.09 MPa, the distillation temperature is 160 ℃ at most, so that 1.48 tons of hydrous ethylenediamine is obtained, the detected moisture content is 2.4 percent, and the product yield is 95.2 percent. 718 kg of the calcium salt powder mixture was discharged.
Pumping distilled 1.48 tons of ethylenediamine with the water content of 2.4 percent into a reaction kettle with a stirrer, adding 74 kilograms of calcium oxide powder and 1.48 kilograms of prepared catalyst under stirring, and stirring at the rotating speed of 90 r/m. Then the kettle is heated to 100 ℃ and stirred for dehydration reaction for 4 hours. After the heat preservation reaction is finished, the reaction device is changed into a common distillation device, the distillation is carried out under the vacuum condition of-0.1 MPa, the distillation temperature is up to 130 ℃, 1.44 tons of anhydrous ethylenediamine is obtained, the detected moisture content is 0.14 percent, and the yield of the two-step comprehensive product is 92.6 percent. 114 kg of calcium salt powder mixture is discharged.
The obtained ethylenediamine with the moisture content of 0.14% is used for synthesizing N- (beta-aminoethyl) -3-aminopropyltrimethoxysilane (KH-792), and the product quality and yield are normal. The calcium salt powder mixture is used as a building material.
Example 2.
In a 3-ton rake reactor, firstly 0.92 ton of diamine hydrochloride as a byproduct of bisaminosilane and 0.8 ton of ethylenediamine solvent are pumped, stirring is started, the stirring speed is 40 r/min, and then 0.4 ton of calcium oxide powder is added. After the materials are fed, the temperature of the rake reactor is firstly raised to 80 ℃, the stirring speed is 40 r/min, the neutralization reaction is carried out for 2 hours, and then the temperature of the reactor is raised to 110 ℃, and the heat preservation reaction is continuously carried out for 6 hours. After the reaction is finished, the neutralization reaction device is changed into a common distillation device, and the reaction is distilled under the vacuum condition of-0.1 MPa, the distillation temperature is 160 ℃ at most, so that 1.40 tons of hydrous ethylenediamine is obtained, the detected moisture content is 2.1 percent, and the product yield is 93.8 percent. 712 kg of calcium salt powder mixture was discharged.
Pumping distilled 1.4 tons of ethylenediamine with the water content of 2.1 percent into a reaction kettle with a stirrer, adding 70 kilograms of calcium oxide powder and 1.4 kilograms of prepared catalyst under stirring, and stirring at the rotating speed of 90 r/m. Then the kettle is heated to 115 ℃ and stirred for dehydration reaction for 4 hours. After the heat preservation reaction is finished, the reaction device is changed into a common distillation device, the distillation is carried out under the vacuum condition of-0.09 MPa, the distillation temperature is 130 ℃ at most, 1.371 tons of anhydrous ethylenediamine is obtained, the detected water content is 0.12 percent, and the two-step comprehensive product yield is 91.8 percent. 98 kg of calcium salt powder mixture was discharged.
The obtained ethylenediamine with the moisture content of 0.12 percent is used for synthesizing N- (beta-aminoethyl) -3-aminopropylmethyldimethoxysilane (KH-602), and the product quality and the yield are normal. The calcium salt powder mixture is used as a building material.
Comparative example 1.
In a 3-ton rake reactor, firstly pumping 1 ton of diamine silane by-product ethylenediamine hydrochloride and 0.8 ton of ethylenediamine solvent, opening stirring, stirring at 40 rpm, and then adding 0.4 ton of calcium oxide powder. After the materials are fed, the rake reactor is heated to 70 ℃ firstly and stirred for neutralization reaction for 2 hours, and then the kettle is heated to 115 ℃ for continuous heat preservation reaction for 6 hours. After the reaction is finished, the neutralization reaction device is changed into a common distillation device, and the reaction is distilled under the vacuum condition of-0.1 MPa, the distillation temperature is 160 ℃ at most, so that 1.47 tons of hydrous ethylenediamine is obtained, the detected moisture content is 2.5 percent, and the product yield is 94.6 percent. 724 kg of calcium salt powder mixture is discharged.
Pumping distilled 1.47 tons of ethylenediamine with the water content of 2.5 percent into a reaction kettle with a stirrer, adding 74 kilograms of calcium oxide powder under stirring, adding no catalyst, and stirring at the rotating speed of 90 r/min. Then the kettle is heated to 100 ℃ and stirred for dehydration reaction for 4 hours. After the heat preservation reaction is finished, the reaction device is changed into a common distillation device, the distillation is carried out under the vacuum condition of-0.1 MPa, the distillation temperature is up to 130 ℃, 1.45 tons of anhydrous ethylenediamine is obtained, the water content is detected to be 1.28 percent, and the yield of the two-step comprehensive product is 93.3 percent. 91 kg of calcium salt powder mixture was discharged.
The resulting 1.28% moisture ethylenediamine was used to synthesize N- (. beta. -aminoethyl) -3-aminopropyltrimethoxysilane (KH-792), which was hydrolyzed during the course of the experiment. The calcium salt powder mixture is used as a building material.
Comparative example 2.
In a 3-ton rake reactor, firstly pumping 1 ton of diamine silane by-product ethylenediamine hydrochloride and 0.8 ton of ethylenediamine solvent, opening stirring, stirring at 40 rpm, and then adding 0.4 ton of calcium oxide powder. After the materials are fed, the rake reactor is heated to 80 ℃ firstly and stirred for neutralization reaction for 2 hours, and then the kettle is heated to 110 ℃ for continuous heat preservation reaction for 6 hours. After the reaction is finished, the neutralization reaction device is changed into a common distillation device, and the reaction is distilled under the vacuum condition of-0.09 MPa, the distillation temperature is 160 ℃ at most, so that 1.48 tons of hydrous ethylenediamine is obtained, the detected moisture content is 2.4 percent, and the product yield is 95.2 percent. 719 kg of the calcium salt powder mixture was discharged.
Pumping the distilled 1.48 tons of ethylenediamine with the water content of 2.4 percent into a reaction kettle with a stirrer, adding 74 kilograms of calcium oxide powder and 1.48 kilograms of potassium hydroxide catalyst under stirring, and stirring at the rotating speed of 90 r/m. Then the kettle is heated to 115 ℃ and stirred for dehydration reaction for 4 hours. After the heat preservation reaction is finished, the reaction device is changed into a common distillation device, the distillation is carried out under the vacuum condition of-0.09 MPa, the distillation temperature is 130 ℃ at most, 1.45 tons of anhydrous ethylenediamine is obtained, the detected moisture content is 0.82 percent, and the yield of the two-step comprehensive product is 93.3 percent. 101 kg of calcium salt powder mixture is discharged.
When the obtained ethylenediamine with the moisture content of 0.82% is used for synthesizing N- (beta-aminoethyl) -3-aminopropyltrimethoxysilane (KH-792), the product yield is only 40% of the normal production yield. The calcium salt powder mixture is used as a building material.
Comparative example 3.
In a 3-ton rake reactor, firstly pumping 1.1 ton of bisaminosilane by-product ethylenediamine hydrochloride and 0.8 ton of ethylenediamine solvent, opening the stirring, stirring at the rotating speed of 40 r/min, and then adding 0.4 ton of calcium oxide powder. After the materials are fed, the rake reactor is heated to 70 ℃ firstly and stirred for neutralization reaction for 2 hours, and then the kettle is heated to 115 ℃ for continuous heat preservation reaction for 6 hours. After the reaction is finished, the neutralization reaction device is changed into a common distillation device, and the reaction is distilled under the vacuum condition of-0.1 MPa, the distillation temperature is 160 ℃ at most, so that 1.56 tons of hydrous ethylenediamine is obtained, the detected moisture content is 3.8 percent, and the product yield is 95.7 percent. 736 kg of the calcium salt powder mixture is discharged.
Pumping 1.58 tons of ethylenediamine with water content of 3.8% distilled from the above into a reaction kettle with a stirrer, adding 79 kg of calcium oxide powder and 1.58 kg of prepared catalyst under stirring, and stirring at 90 r/m. Then the kettle is heated to 100 ℃ and stirred for dehydration reaction for 4 hours. After the heat preservation reaction is finished, the reaction device is changed into a common distillation device, the distillation is carried out under the vacuum condition of-0.1 MPa, the distillation temperature is up to 130 ℃, 1.52 tons of anhydrous ethylenediamine is obtained, the detected water content is 1.06 percent, and the yield of the two-step comprehensive product is 93.2 percent. 137 kg of the calcium salt powder mixture was discharged.
The resulting 1.06% moisture ethylenediamine was used to synthesize N- (. beta. -aminoethyl) -3-aminopropyltrimethoxysilane (KH-792), which was hydrolyzed during the course of the experiment. The calcium salt powder mixture is used as a building material.
Comparative example 4.
In a 3-ton rake reactor, firstly 0.8 ton of bisaminosilane by-product ethylenediamine hydrochloride and 0.8 ton of ethylenediamine solvent are pumped, the stirring is started, the stirring speed is 40 r/min, and then 0.4 ton of calcium oxide powder is added. After the materials are fed, the rake reactor is heated to 80 ℃ firstly and stirred for neutralization reaction for 2 hours, and then the kettle is heated to 110 ℃ for continuous heat preservation reaction for 6 hours. After the reaction is finished, the neutralization reaction device is changed into a common distillation device, and the reaction is distilled under the vacuum condition of-0.09 MPa, the distillation temperature is 160 ℃ at most, so that 1.13 tons of hydrous ethylenediamine is obtained, the detected moisture content is 1.6 percent, and the product yield is 80.5 percent. 866 kg of calcium salt powder mixture was discharged.
Pumping 1.13 tons of ethylenediamine with water content of 1.6% distilled from the above into a reaction kettle with a stirrer, adding 56 kg of calcium oxide powder and 1.1 kg of prepared catalyst under stirring, and stirring at 90 r/m. Then the kettle is heated to 115 ℃ and stirred for dehydration reaction for 4 hours. After the heat preservation reaction is finished, the reaction device is changed into a common distillation device, the distillation is carried out under the vacuum condition of-0.1 MPa, the distillation temperature is up to 130 ℃, 1.11 tons of anhydrous ethylenediamine is obtained, the detected water content is 0.07 percent, and the yield of the two-step comprehensive product is 79.1 percent. 75 kg of calcium salt powder mixture is discharged.
The obtained ethylenediamine with the moisture content of 0.07 percent is used for synthesizing N- (beta-aminoethyl) -3-aminopropyltrimethoxysilane (KH-792), and the product quality and the yield are normal. The calcium salt powder mixture is used as a building material.
Claims (1)
1. A method for preparing anhydrous ethylenediamine from a diamine hydrochloride byproduct of bisaminosilane is characterized in that: it comprises the following steps:
1) and mixing the diamine hydrochloride serving as a diamine silane by-product with calcium oxide powder and ethylenediamine according to the weight ratio of 2.3-2.5: the weight ratio of 1:2, putting the mixture into a reaction kettle with a stirrer, and neutralizing and reacting for 2 hours at the kettle temperature of 70-80 ℃ under stirring, wherein the stirring speed is 40 r/min; the components of the diamine hydrochloride serving as a byproduct of the bisaminosilane are as follows: the weight ratio of the ethylenediamine to the ethylenediamine is 30-40%, and the weight ratio of the ethylenediamine hydrochloride to the ethylenediamine hydrochloride is 60-70%;
2) after the neutralization reaction is carried out for 2 hours, the kettle is heated to 110-115 ℃ and the heat preservation reaction is continuously carried out for 6 hours;
3) after the reaction is carried out for 6 hours under the condition of heat preservation, distilling under vacuum at the distillation temperature of 160 ℃ and under the pressure of-0.09 to-0.1 MPa to obtain the water-containing ethylenediamine with the water content of 2 to 3 percent;
4) putting aqueous ethylenediamine with the water content of 2% -3% into a reaction kettle with stirring, adding calcium oxide powder with the weight of 5% of that of the ethylenediamine and 0.1% of catalyst, carrying out heat preservation, stirring and dehydration reaction at the temperature of 100-115 ℃ for 4 hours, and stirring at the rotating speed of 90 r/m; the catalyst is n-butyl lithium and potassium tert-butoxide according to the weight ratio of 1: 1 in a weight ratio;
5) after the heat preservation reaction is finished, distilling under the vacuum condition of-0.09 to-0.1 MPa to obtain anhydrous ethylenediamine with the water content of 0.2 percent, wherein the anhydrous ethylenediamine can be directly used as a raw material of diamine silane; the distillation temperature is 130 ℃;
the structural formula of the bisaminosilane is NH2CH2CH2NHC3H6Si（OCH3）3、NH2CH2CH2NHC3H6Si（OC2H5）3、NH2CH2CH2NHC3H6（CH3）Si（OCH3）2。
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