CN111961074B - Continuous production method of gamma-aminopropyl triethoxy silane - Google Patents
Continuous production method of gamma-aminopropyl triethoxy silane Download PDFInfo
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- CN111961074B CN111961074B CN201910418793.1A CN201910418793A CN111961074B CN 111961074 B CN111961074 B CN 111961074B CN 201910418793 A CN201910418793 A CN 201910418793A CN 111961074 B CN111961074 B CN 111961074B
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010924 continuous production Methods 0.000 title claims abstract description 13
- 238000004176 ammonification Methods 0.000 claims abstract description 144
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 131
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims description 74
- 230000008025 crystallization Effects 0.000 claims description 74
- 239000012043 crude product Substances 0.000 claims description 65
- 238000001704 evaporation Methods 0.000 claims description 43
- 230000001105 regulatory effect Effects 0.000 claims description 32
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 28
- 230000008020 evaporation Effects 0.000 claims description 23
- 238000004064 recycling Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 17
- 230000001276 controlling effect Effects 0.000 claims description 16
- 238000003780 insertion Methods 0.000 claims description 13
- 230000037431 insertion Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 40
- 239000006227 byproduct Substances 0.000 abstract description 19
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 description 30
- 238000009835 boiling Methods 0.000 description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 150000003335 secondary amines Chemical class 0.000 description 18
- 150000003512 tertiary amines Chemical class 0.000 description 18
- 235000019270 ammonium chloride Nutrition 0.000 description 11
- 208000012839 conversion disease Diseases 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- -1 casting Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical compound O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to a continuous production method of gamma-aminopropyl triethoxy silane, which takes liquid ammonia and chloropropyl triethoxy silane as raw materials, the reaction is carried out in three ammonification kettles connected in series, a premixer is arranged in front of a third ammonification kettle, and a certain amount of ethylenediamine and the discharged materials of the second ammonification kettle enter the third ammonification kettle after being mixed in the premixer. By adjusting the feeding proportion of the raw materials and the process conditions (temperature, pressure and residence time) of the ammonification kettle, the optimized production process is achieved, and the stable and high-quality product is obtained. The method can realize continuous and automatic production of the aminopropyl triethoxy silane, and has the advantages of high conversion rate, few byproducts, stable product quality, high yield, safety and environmental protection.
Description
Technical Field
The application relates to a production method of organic silicon, in particular to a continuous production method of a silane coupling agent gamma-aminopropyl triethoxy silane.
Background
The silane coupling agent has been developed from the middle of the 20 th century, and has reached thousands of varieties, and the number of silane coupling agents which are commercially available as an industrial product is tens of, and the silane coupling agent has become a class of organosilicon products which have been developed faster in recent years, wherein the silane coupling agent containing amino groups has a considerable specific gravity. The gamma-aminopropyl triethoxysilane (silane coupling agent KH-550) is a general silane coupling agent, is widely used in the industries of glass fiber reinforced plastics, adhesives, casting, textile printing and dyeing, adhesives and the like, has the excellent performances of enhancing the cohesiveness, improving the mechanical property, water resistance, ageing resistance and the like of products, and rapidly increases the market demand of aminosilane along with the rapid development of the industrial level.
Currently, most existing manufacturers adopt a batch method for ammonification of chloropropyl triethoxysilane to produce gamma-aminopropyl triethoxysilane. For example, the processes are adopted in the patents CN104961762A, CN101768180A and CN108456223A, the process method is mature, but the intermittent production can lead to unstable product quality, more reaction byproducts, the product yield is always kept at a lower level, the production cost is higher, and the intermittent production is not easy to realize automatic control, the pressure control in the reaction process is unstable, a large amount of ammonia tail gas is caused, so that the environmental protection is greatly polluted; the intermittent method has the advantages of high labor intensity, high energy consumption, low yield, more unsafe factors in production and annual yield below 1000 tons.
Patent CN105669739a mentions a method of directly adding allylamine and triethoxysilane, in which a large amount of beta-site and gamma-site isomerised products are easily produced during hydrosilylation due to higher activity of allylamine, and are difficult to separate from the products, resulting in low product yield; and the raw material triethoxysilane is difficult to obtain, so that the method is difficult to industrialize.
Patent 205275502U discloses a reaction apparatus for producing aminopropyl triethoxysilane, but does not mention how to suppress occurrence of side reactions, nor discloses specific process conditions. In fact, in the absence of process conditions, it is difficult to achieve continuous production meeting the industrial requirements.
Therefore, the continuous production method of gamma-aminopropyl triethoxysilane is continuously developed, the occurrence of side reaction can be restrained, the product purity is high, and the production efficiency and the economic value are ensured.
Disclosure of Invention
The application aims to overcome the defects that the gamma-aminopropyl triethoxysilane prepared by the prior art is low in efficiency, low in yield, low in purity and incapable of comprehensively utilizing byproducts, and provides a continuous synthesis method of gamma-aminopropyl triethoxysilane, which is stable in product quality, high in reaction conversion rate, high in yield, few in byproducts, safe and environment-friendly.
The synthesis principle of gamma-aminopropyl triethoxysilane is as follows:
the aminopropyl triethoxysilane is prepared by substitution reaction of chloropropyl triethoxysilane and liquid ammonia, and simultaneously produces by-product ammonium chloride, and the main reaction formula is as follows:
ClCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 +2NH 3 →NH 2 CH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 +NH 4 Cl
the aminopropyl triethoxysilane produced by the reaction can also continue to react with chloropropyl triethoxysilane to form secondary amino and even tertiary amino derivatives, and HCl is produced, and side reactions are as follows:
and (3) neutralizing hydrogen chloride generated by side reaction with liquid ammonia to generate ammonium chloride:
NH 3 +HCl→NH 4 Cl
the reaction residence time is controlled under the condition of excessive ammonia and pressurization, which is favorable for the main reaction and inhibits the side reaction of secondary and tertiary amino groups.
The ethylenediamine and the chloropropyl triethoxysilane also carry out substitution reaction to prepare N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, and the reaction formula is as follows:
ClCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 +NH 2 CH 2 CH 2 NH 2 →NH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 +HCl
meanwhile, by-product hydrogen chloride is generated, and the reaction of the hydrogen chloride and the liquid ammonia generates ammonium chloride due to the large excess of the liquid ammonia in the system, and the reaction equation is the same.
In order to achieve the above purpose, the application adopts the following technical scheme:
a continuous production method of gamma-aminopropyl triethoxysilane comprises the following steps: the preparation method comprises the steps of (1) carrying out an ammonification reaction by taking chloropropyl triethoxysilane and liquid ammonia as raw materials, wherein the ammonification reaction is carried out in three ammonification kettles which are connected in series; materials sequentially enter a first ammonification kettle and a second ammonification kettle, a static premixer is arranged between the second ammonification kettle and a third ammonification kettle, the effluent materials of ethylenediamine and the second ammonification kettle are mixed in the static premixer and then enter the third ammonification kettle, ethylenediamine and chloropropyl triethoxysilane react in the third ammonification kettle to generate N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, and the materials of the third ammonification kettle are respectively evaporated, crystallized, centrifuged, settled and rectified to obtain the high-purity product gamma-aminopropyl triethoxysilane and the high-purity byproduct N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane.
In the application, each ammoniation kettle is connected through an interface with a certain overflow height difference, stirring is not needed in the process, the mobility and compatibility of homogeneous materials are good, ammonium chloride generated by reaction is fully dissolved in liquid ammonia, the mobility is good, and the materials of the reaction kettle are uniform in a certain time after the liquid ammonia is continuously vaporized and condensed.
The three ammonification kettles of the reaction system used in the application have the height-diameter ratio of 10-15:1, preferably 12-13:1, and particularly can be reaction kettles with the diameter of about 1m and the height of about 12 m. Each ammonification kettle is internally provided with a heating coil and is provided with a reflux condenser, and a tubular reflux condenser is preferably adopted, so that the temperature of the ammonification kettle can be regulated, excessive liquid ammonia can be rapidly condensed from a system after evaporation, and then flows into the next ammonification kettle from an overflow port, and the reaction efficiency is improved.
Preferably, the process conditions of each reaction kettle are that the temperature of the ammonification kettle is controlled to be 60-90 ℃, preferably 70-85 ℃ and the pressure is controlled to be 3.0-5.0MPa, preferably 3.5-4.5MPa by controlling the heating coil steam and the reflux condenser; the pressure of the evaporating kettle is controlled to be 0.8-1.0MPa by a pressure reducing valve, the temperature is controlled to be 50-65 ℃, the pressure of the crystallizing kettle is controlled to be 0-0.2MPa, the temperature of the first crystallizing kettle is controlled to be 10-20 ℃, and the temperature of the second crystallizing kettle is controlled to be 50-65 ℃.
Preferably, the addition amount of ethylenediamine is controlled to be 1-3wt% of the amount of chloropropyl triethoxysilane by controlling a regulating valve of the feeding, and the ethylenediamine is uniformly mixed with the material discharged from the second ammonification kettle and directly enters the third ammonification kettle to rapidly react, if the ethylenediamine is excessive, such as more than 3wt%, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is excessive, so that the product aminopropyl triethoxysilane is less; if the amount of ethylenediamine is less than 1wt%, the inhibition of secondary and tertiary amino byproducts is not remarkable, and the byproduct content is remarkably increased. Preferably, the liquid ammonia is added in an amount of 25 to 40wt% based on the amount of chloropropyl triethoxysilane. In the specific embodiment of the application, considering the size of the ammonification kettle, the liquid ammonia feeding amount is controlled to be 6.0-7.5t/h, the chloropropyl triethoxysilane feeding amount is controlled to be 2.0-2.5t/h, and the ethylenediamine feeding amount is controlled to be 0.02-0.075t/h, and preferably 0.04-0.05t/h.
Preferably, when the liquid ammonia and the chloropropyl triethoxysilane enter the ammonification kettle, the inlets are provided with insertion pipes with a certain length (about 0.8-0.9 times of the height of the ammonification kettle, for example, the height of the ammonification kettle is 12 meters, and the insertion length is 9.6-10.8 meters), so that the residence time of the raw materials in the ammonification kettle is ensured, and the raw materials cannot directly enter the next ammonification kettle after short circuit. The circulating water outlet of each vertical ammonification kettle condenser is provided with three ports, different condensing areas are corresponding to different ports, in the ammonification reaction process, in order to ensure the stability of reaction and operation and the smoothness of overflow of an ammonification system, the ammonification temperature needs to be controlled, the ammonification pressure is stabilized, at this time, the steam quantity of a coil pipe and the effective use area of the ammonification kettle condenser need to be adjusted at the same time, the ammonification kettle condenser adopts different condensing areas, and the liquid temperature under the condition of liquid ammonia gasification condensation reflux is related to the temperature and the pressure of the whole ammonification kettle. The application adopts the ammonification reflux tube condenser, which not only can adjust the temperature of the ammonification kettle, but also can lead excessive liquid ammonia to be quickly condensed after evaporating from the system and flow into the next ammonification kettle from the overflow port, thereby improving the reaction efficiency.
Preferably, the material stays in the first ammonification kettle for about 0.8-1.2h, the material comes out of the first reaction kettle, 30-35% of gamma-chloropropyl triethoxysilane is detected to be unreacted, and the secondary amine, tertiary amine and high boiling point only account for 0.6-1% of the total crude product; the retention time of the materials in the second ammonification kettle is 0.8-1.2h, the materials are discharged from the second ammonification kettle, and 8-12% of gamma-chloropropyl triethoxysilane is detected to be remained without reaction, at the moment, secondary amine, tertiary amine and high boiling account for 1.2-1.8% of the total crude product; the mixed crude product and ethylenediamine conveyed by a pump enter a third ammonification kettle after passing through a static mixer, the residence time in the third ammonification kettle is about 0.9-1h, the third ammonification kettle is out, the chloropropyl triethoxysilane is detected to be basically completely reacted, the content of secondary amine, tertiary amine and high-boiling undesired byproducts is extremely small and accounts for about 1.4-5.0% of the total crude product, and in the preferred embodiment of the application, the secondary amine, tertiary amine and high-boiling residues account for about 1.4-2.2% of the total crude product, and the percentages are all mass percentages.
In the continuous production method provided by the application, the liquid ammonia and the ethylenediamine can be recycled, and particularly, ammonia tail gas distilled from an evaporation kettle and a crystallization kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; and (3) evaporating excessive ethylenediamine in the third ammoniation kettle in the first rectifying tower, condensing the ethylenediamine by a tower top condenser, and returning the ethylenediamine to the ethylenediamine intermediate tank for recycling.
In the continuous production method, the effect of low content of secondary amine, tertiary amine, high boiling and other undesirable products can be achieved, by introducing a certain amount of ethylenediamine into a third ammonification kettle, side reaction is inhibited, the content of secondary amine, tertiary amine and high boiling is reduced, and meanwhile, another additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane with high purity and high economic value is obtained. The ethylenediamine is a primary amine with very high activity, and reacts with gamma-chloropropyl triethoxysilane rapidly under normal pressure, and the reaction is extremely rapid under high pressure, so that N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane (a double-amino silane coupling agent has the advantages of large market usage amount, high added value and good market prospect) is generated. When the reaction is carried out in excess of liquid ammonia, chloropropyl triethoxysilane and liquid ammonia are fully contacted for reaction, so that secondary amine, tertiary amine and high boiling point serving as byproducts are very few, 88-92% of gamma-chloropropyl triethoxysilane is consumed in total by the first ammonification kettle and the second ammonification kettle, and the reaction is carried out; in the third ammonification kettle, the concentration of liquid ammonia is reduced, the concentration of the product aminopropyl triethoxysilane is increased, and at the moment, the product is easy to further react with the residual 8-12% chloropropyl triethoxysilane to generate secondary amine, tertiary amine and high boiling point; according to the application, ethylenediamine is introduced into a third ammonification kettle, and is an active primary amine, and is extremely easy to react with chloropropyl triethoxysilane under high pressure to generate a small amount of high-purity additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, so that further reaction of chloropropyl triethoxysilane and the product is sufficiently inhibited. Through the reaction of the third ammonification kettle, the chloropropyl triethoxysilane is basically consumed, and secondary amine, tertiary amine and high boiling point byproducts are few.
Preferably, the evaporation kettle is of an elongated design, is internally provided with a heating coil, has an aspect ratio of 2-4:1, and is provided with an ammonia condenser; the crystallization kettles are provided with a first crystallization kettle and a second crystallization kettle, stirring and temperature control coil pipes are arranged in the kettles, the two crystallization kettles are connected in series and are connected through an overflow port, and the height-diameter ratio of the crystallization kettles is 1-3:1.
The application adopts a preferable technical scheme that: the production process of gamma-aminopropyl triethoxy silane includes the reaction of chloropropyl triethoxy silane and liquid ammonia to produce aminopropyl triethoxy silane, and the ammonification of chloropropyl triethoxy silane and liquid ammonia in three ammonification kettles with inner coil pipe and independent condensing reflux unit; firstly, liquid ammonia and chloropropyl triethoxysilane respectively enter a first ammonification kettle through a pump and a regulating valve group to control the feeding quantity of a certain proportion, the temperature is controlled to be 70-85 ℃ by regulating the steam flow of a coil pipe of the first ammonification kettle and the circulating water flow of a condenser of the first ammonification kettle, the chloropropyl triethoxysilane and the liquid ammonia are subjected to reflux reaction in the first ammonification kettle, and after full mass transfer and heat transfer, the liquid ammonia enters a second ammonification kettle through an overflow port at the upper end side; controlling the temperature to be 70-85 ℃ by adjusting the steam flow of the coil pipe of the second ammonification kettle and the circulating water flow of the condenser of the second ammonification kettle, carrying out reflux reaction in the second ammonification kettle, entering a static premixer through an overflow port at the upper end side of the second ammonification kettle after staying for a certain time, and entering a third ammonification kettle after premixing together with ethylenediamine with a certain flow controlled by a pump through a regulating valve, and carrying out mass transfer and heat transfer in the third ammonification kettle to fully carry out reflux reaction; the temperature of the third ammonification kettle is controlled at 70-85 ℃ by the same measure, the mass transfer and the heat transfer of the chloropropyl triethoxysilane and the liquid ammonia continuously pass through the first ammonification kettle and the second ammonification kettle, about 88-92% of the chloropropyl triethoxysilane is reacted after the reflux reaction, the rest about 8-12% of the chloropropyl triethoxysilane is statically mixed with the ethylenediamine and then enters the third ammonification kettle to rapidly react, the side reaction of the chloropropyl triethoxysilane and the product is greatly inhibited, and the chloropropyl triethoxysilane is basically reacted completely; the crude product mixed solution is decompressed to 0.8-1.0MPa from the side opening of the upper end of the third ammoniation kettle through a decompression regulating valve and then enters an evaporation kettle; the liquid ammonia is greatly separated out during decompression, the liquid ammonia is recycled to a liquid ammonia feeding intermediate tank through a liquid ammonia recycling condenser, and meanwhile, the temperature is controlled to be 50-65 ℃ by adjusting the heating temperature of coil pipes in an evaporation kettle, so that part of liquid ammonia is ensured to exist in a system while ammonia is further distilled off, and part of ammonium chloride in a crude product is dissolved; after evaporating most of liquid ammonia, the crude product mixed solution is depressurized to 0-0.2MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the first crystallization kettle is provided with a stirring pipe and a coil pipe, circulating water is connected in the coil pipe, the temperature of the first crystallization kettle is controlled to be 10-20 ℃ through the circulating water, most of liquid ammonia in the crude product mixed solution is separated out after the pressure is reduced, and ammonium chloride dissolved in the liquid ammonia is also gradually separated out; the crude product mixed solution further overflows into a second crystallization kettle through a side opening at the upper end of the first crystallization kettle, the second crystallization kettle is also provided with a stirring pipe and a coil pipe, steam is connected in the coil pipe, the temperature of the second crystallization kettle is controlled to be 50-65 ℃ through the steam, and liquid ammonia in the mixed crude product is further distilled off; ammonia tail gas distilled from the first crystallization kettle and the second crystallization kettle is compressed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; and (3) evaporating excessive ethylenediamine in the third ammoniation kettle in the first rectifying tower, condensing the ethylenediamine by a tower top condenser, and returning the ethylenediamine to the ethylenediamine intermediate tank for recycling. The crude mixed solution enters a centrifugal machine from the side opening at the upper end of the second crystallization kettle, and crude clear liquid from the centrifugal machine enters a crude sedimentation tank and is pumped into a continuous rectifying device, so that a gamma-aminopropyl triethoxysilane product with high purity (more than 99 wt%) and a byproduct N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane with high purity (more than 99 wt%) can be obtained, and the conversion rate is high and is more than 96%. In addition, the ammonium chloride solid obtained by the centrifugal machine can be conveniently and directly packaged for take-out. The preparation method provided by the application has the advantages that the efficiency is high, the defect of intermittent production is avoided, the product purity is high, the byproducts can be effectively utilized, the procedure of treating the byproducts is reduced, and the cost is further reduced.
In the system, because ethylenediamine reacts with chloropropyl triethoxysilane, the generated hydrogen chloride and liquid ammonia produce ammonium chloride in the same way except that additional products are produced, and no other byproducts are introduced into the system. And the boiling point of ethylenediamine is 116 ℃, the boiling point of the product aminopropyl triethoxysilane is 217 ℃, the boiling point of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 274 ℃, the boiling points of byproduct secondary amine, tertiary amine and high boiling point are above 300 ℃, the boiling point difference is large, each component with high purity can be easily separated in sequence through rectification, the separation effect is good, and the purity of each obtained product is high without more complicated rectification or other separation methods.
The two crystallization kettles are connected in series, both the two crystallization kettles are designed with stirring and an inner coil pipe, when the mixed liquid of most of liquid ammonia after being steamed enters the first crystallization kettle, the pressure is reduced to 0-0.2MPa, a large amount of liquid ammonia is gasified and separated out, heat is absorbed, the temperature of the first crystallization kettle can be rapidly reduced, circulating water is introduced into the coil pipe for heat preservation, the temperature is controlled to be 10-20 ℃, firstly, the further separation of ammonia is facilitated, secondly, the crystallization speed of ammonium chloride can be controlled, and meanwhile, the mixed liquid can be uniformly dispersed by stirring of the first crystallization kettle; the dispersed mixed solution overflows into a second crystallization kettle, the temperature of the second crystallization kettle is controlled to be 50-65 ℃, and the temperature is further raised so as to facilitate ammonia evaporation and ammonium chloride crystallization.
Compared with the prior art, the application has the beneficial effects that:
1. the application adopts three kettles to connect in series and introduces ethylenediamine at a specific stage to realize continuous production of gamma-aminopropyl triethoxy silane, and the arrangement is also beneficial to automatic control, ensures the stability of product quality, improves the yield by 8-10 percent, reduces energy consumption, greatly reduces production cost and ensures the production safety.
2. And adding ethylenediamine into the third ammonification kettle, fully mixing the ethylenediamine with the discharged materials of the second ammonification kettle, and then entering the third ammonification kettle, wherein the introduced ethylenediamine reacts with chloropropyl triethoxysilane, so that the chloropropyl triethoxysilane and gamma-aminopropyl triethoxysilane are inhibited from continuously reacting, and a byproduct N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane with high economic value can be obtained.
3. Through calculation and repeated experiments, the optimal raw material feed amount ratio is 1-3wt% of the feed amount of the ethylene diamine, the size of the ammoniation kettle is particularly suitable for the embodiment of the application, the liquid ammonia feed amount is controlled to be 6.0-7.5t/h, the feed amount of the chloropropyl triethoxysilane is controlled to be 2.0-2.5t/h, the ethylene diamine feed amount is 0.02-0.075t/h, preferably 0.04-0.05t/h, and the optimal screening is carried out in combination with the residence time of the materials in each ammoniation kettle.
4. Wherein, excessive liquid ammonia and ethylenediamine are recycled, and a small amount of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane with high added value is directly packaged and sold; the ammonium chloride solid centrifuged by the centrifuge is automatically discharged and directly packaged for takeaway; the ammonia tail gas in the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then recycled, and excessive ethylenediamine is distilled out and condensed in the first rectifying tower and then returned to the ethylenediamine intermediate tank for recycling. The method can realize continuous and automatic production of the aminopropyl triethoxy silane, and has the advantages of high reaction conversion rate, few byproducts, stable product quality, high yield (short reaction time), safety and environmental protection.
Drawings
FIG. 1 is a schematic diagram of a continuous process for the production of gamma-aminopropyl triethoxysilane.
Detailed Description
The continuous production method of the present application is further described below with reference to specific examples. In these examples, all fractions and percentages are by mass unless otherwise indicated.
The purity of the product is the mass percentage of the product obtained.
By conversion is meant the ratio of the mass of the product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane converted by a chemical reaction to the total mass of the crude product.
The crude product content refers to the content of the mixed crude product obtained from the tower kettle after low components such as ammonia, ethylenediamine and the like are distilled out from the first rectifying tower for chromatographic analysis.
The ammonification kettle adopted in the embodiment of the application has the height-to-diameter ratio of about 12:1, and a reaction kettle with the diameter of about 1m and the height of about 12m can be specifically selected in the embodiment. The material inlet of the ammonification kettle is provided with a certain length of insertion pipe (about 0.8-0.9 times of the height of the ammonification kettle, for example, the height of the ammonification kettle is 12 meters, and the insertion length is 9.6-10.8 meters), so that the residence time of the raw materials in the ammonification kettle is ensured.
The evaporation kettle adopted in the embodiment of the application is of an elongated design, is internally provided with a heating coil, has an aspect ratio of 3:1, and is provided with an ammonia condenser; the crystallization kettles are a first crystallization kettle and a second crystallization kettle, stirring and temperature control coil pipes are arranged in the kettles, the two crystallization kettles are connected in series and are connected through an overflow port, and the height-diameter ratio of the crystallization kettles is 2.2:1.
Example 1
Liquid ammonia and chloropropyl triethoxysilane are respectively fed into the first ammonification kettle by a pump through a regulating valve group at the same time by controlling the feeding amount of a certain proportion, wherein the feeding amount of the liquid ammonia is 6t/h, the feeding amount of the chloropropyl triethoxysilane is 2t/h, and the feeding amount of ethylenediamine is 0.04t/h; and adjusting the heating quantity of the coil steam of the ammonification system and the condensing water quantity of the reflux condenser, and controlling the temperature of the three ammonification systems to be 80 ℃ and the pressure to be 3.9MPa. The residence time is regulated and controlled by adjusting the length of an insertion pipe at the inlet of the ammonification kettle, the residence time of the first ammonification kettle and the second ammonification kettle is 1h, and the residence time of the third ammonification kettle is 0.9h. The crude product mixed solution is decompressed to 0.8MPa through a decompression regulating valve from the side opening of the upper end of the third ammoniation kettle and then enters an evaporation kettle; the temperature is controlled to be 60 ℃ by adjusting the heating of coil steam in the evaporating kettle; after most of liquid ammonia is distilled off from the crude product mixed solution, the crude product mixed solution is depressurized to 0.1MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the temperature of the first crystallization kettle is controlled to be 10 ℃ through circulating water, crude product mixed liquor further overflows into a second crystallization kettle through a side port at the upper end of the first crystallization kettle, the temperature of the second crystallization kettle is controlled to be 60 ℃ through steam, and liquid ammonia in the mixed crude product is further distilled off; the ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; the excessive ethylenediamine in the third ammoniation kettle is distilled out in the first rectifying tower, condensed by the tower top condenser and returned to the ethylenediamine intermediate tank for recycling; and the crude product mixed solution enters a centrifugal machine from a side opening at the upper end of the second crystallization kettle, and the centrifuged crude product is further settled and then is sent into a tower for continuous rectification. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 90.4 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 7.7 percent, and the secondary amine and tertiary amine have high boiling point content of 1.9 percent; the conversion rate after the conversion reaction is 98.1 percent; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 99.6%, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 99.2%.
Example 2
Liquid ammonia and chloropropyl triethoxysilane are respectively fed into the first ammonification kettle by a pump through a regulating valve group while controlling the feeding amount of the liquid ammonia to be 7.5t/h, the feeding amount of the chloropropyl triethoxysilane to be 2t/h and the feeding amount of ethylenediamine to be 0.04t/h; and adjusting the heating quantity of the coil steam of the ammonification system and the condensing water quantity of the reflux condenser, and controlling the temperature of the three ammonification systems to be 80 ℃ and the pressure to be 3.9MPa. The residence time is regulated and controlled by adjusting the length of an insertion pipe at the inlet of the ammonification kettle, the residence time of the first ammonification kettle and the second ammonification kettle is 1.1h, and the residence time of the third ammonification kettle is 0.9h. The crude product mixed solution is decompressed to 0.8MPa through a decompression regulating valve from the side opening of the upper end of the third ammoniation kettle and then enters an evaporation kettle; the temperature is controlled to be 60 ℃ by adjusting the heating of coil steam in the evaporating kettle; after most of liquid ammonia is distilled off from the crude product mixed solution, the crude product mixed solution is depressurized to 0.1MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the temperature of the first crystallization kettle is controlled to be 10 ℃ through circulating water, crude product mixed liquor further overflows into a second crystallization kettle through a side port at the upper end of the first crystallization kettle, the temperature of the second crystallization kettle is controlled to be 60 ℃ through steam, and liquid ammonia in the mixed crude product is further distilled off; the ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; the excessive ethylenediamine in the third ammoniation kettle is distilled out in the first rectifying tower, condensed by the tower top condenser and returned to the ethylenediamine intermediate tank for recycling; and the crude product mixed solution enters a centrifugal machine from a side opening at the upper end of the second crystallization kettle, and the centrifuged crude product is further settled and then is sent into a tower for continuous rectification. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 90.6 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 7.6 percent, and the secondary amine and tertiary amine have high boiling point content of 1.8 percent; the conversion rate after the conversion reaction is 98.2 percent; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 99.4%, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 99.3%.
Example 3
Liquid ammonia and chloropropyl triethoxysilane are respectively fed into the first ammonification kettle by a pump through a regulating valve group at the same time by controlling the feeding amount of a certain proportion, wherein the feeding amount of the liquid ammonia is 6t/h, the feeding amount of the chloropropyl triethoxysilane is 2.5t/h, and the feeding amount of ethylenediamine is 0.05t/h; and adjusting the heating quantity of the coil steam of the ammonification system and the condensing water quantity of the reflux condenser, and controlling the temperature of the three ammonification systems to be 80 ℃ and the pressure to be 3.9MPa. The residence time is regulated and controlled by adjusting the length of an insertion pipe at the inlet of the ammonification kettle, the residence time of the first ammonification kettle and the second ammonification kettle is 1h, and the residence time of the third ammonification kettle is 0.9h. The crude product mixed solution is decompressed to 0.8MPa through a decompression regulating valve from the side opening of the upper end of the third ammoniation kettle and then enters an evaporation kettle; the temperature is controlled to be 60 ℃ by adjusting the heating of coil steam in the evaporating kettle; after most of liquid ammonia is distilled off from the crude product mixed solution, the crude product mixed solution is depressurized to 0.1MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the temperature of the first crystallization kettle is controlled to be 10 ℃ through circulating water, crude product mixed liquor further overflows into a second crystallization kettle through a side port at the upper end of the first crystallization kettle, the temperature of the second crystallization kettle is controlled to be 60 ℃ through steam, and liquid ammonia in the mixed crude product is further distilled off; the ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; the excessive ethylenediamine in the third ammoniation kettle is distilled out in the first rectifying tower, condensed by the tower top condenser and returned to the ethylenediamine intermediate tank for recycling; and the crude product mixed solution enters a centrifugal machine from a side opening at the upper end of the second crystallization kettle, and the centrifuged crude product is further settled and then is sent into a tower for continuous rectification. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 89.2 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 8.7 percent, and the secondary amine, tertiary amine and high boiling point content are 2.1 percent; the conversion rate after the conversion reaction is 97.9%; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 99.4%, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 99.4%.
Example 4
Liquid ammonia and chloropropyl triethoxysilane are respectively fed into the first ammonification kettle by a pump through a regulating valve group at the same time by controlling the feeding amount of a certain proportion, wherein the feeding amount of the liquid ammonia is 6t/h, the feeding amount of the chloropropyl triethoxysilane is 2.5t/h, and the feeding amount of ethylenediamine is 0.04t/h; and adjusting the heating quantity of the coil steam of the ammonification system and the condensing water quantity of the reflux condenser, and controlling the temperature of the three ammonification systems to be 80 ℃ and the pressure to be 3.9MPa. The residence time is regulated and controlled by adjusting the length of an insertion pipe at the inlet of the ammonification kettle, the residence time of the first ammonification kettle and the second ammonification kettle is 1h, and the residence time of the third ammonification kettle is 0.9h. The crude product mixed solution is decompressed to 0.8MPa through a decompression regulating valve from the side opening of the upper end of the third ammoniation kettle and then enters an evaporation kettle; the temperature is controlled to be 60 ℃ by adjusting the heating of coil steam in the evaporating kettle; after most of liquid ammonia is distilled off from the crude product mixed solution, the crude product mixed solution is depressurized to 0.1MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the temperature of the first crystallization kettle is controlled to be 10 ℃ through circulating water, crude product mixed liquor further overflows into a second crystallization kettle through a side port at the upper end of the first crystallization kettle, the temperature of the second crystallization kettle is controlled to be 60 ℃ through steam, and liquid ammonia in the mixed crude product is further distilled off; the ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; the excessive ethylenediamine in the third ammoniation kettle is distilled out in the first rectifying tower, condensed by the tower top condenser and returned to the ethylenediamine intermediate tank for recycling; and the crude product mixed solution enters a centrifugal machine from a side opening at the upper end of the second crystallization kettle, and the centrifuged crude product is further settled and then is sent into a tower for continuous rectification. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 89.6 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 7.8 percent, and the secondary amine and tertiary amine and the high boiling point content are 2.2 percent; the conversion rate after the conversion reaction is 97.4 percent; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 99.5%, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 99.4%.
Example 5
Liquid ammonia and chloropropyl triethoxysilane are respectively fed into an ammonification A kettle by a pump through a regulating valve group at the same time by controlling the feeding amount of a certain proportion, wherein the feeding amount of the liquid ammonia is 7.5t/h, the feeding amount of the chloropropyl triethoxysilane is 2t/h, and the feeding amount of ethylenediamine is 0.06t/h; and adjusting the heating quantity of the coil steam of the ammonification system and the condensing water quantity of the reflux condenser, and controlling the temperature of the three ammonification systems to be 80 ℃ and the pressure to be 3.9MPa. The residence time is regulated and controlled by adjusting the length of an insertion pipe at the inlet of the ammonification kettle, the residence time of the first ammonification kettle and the second ammonification kettle is 1h, and the residence time of the third ammonification kettle is 0.9h. The crude product mixed solution is decompressed to 0.8MPa through a decompression regulating valve from the side opening of the upper end of the third ammoniation kettle and then enters an evaporation kettle; the temperature is controlled to be 60 ℃ by adjusting the heating of coil steam in the evaporating kettle; after most of liquid ammonia is distilled off from the crude product mixed solution, the crude product mixed solution is depressurized to 0.1MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the temperature of the first crystallization kettle is controlled to be 10 ℃ through circulating water, crude product mixed liquor further overflows into a second crystallization kettle through a side port at the upper end of the first crystallization kettle, the temperature of the second crystallization kettle is controlled to be 60 ℃ through steam, and liquid ammonia in the mixed crude product is further distilled off; the ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; the excessive ethylenediamine in the third ammoniation kettle is distilled out in the first rectifying tower, condensed by the tower top condenser and returned to the ethylenediamine intermediate tank for recycling; and the crude product mixed solution enters a centrifugal machine from a side opening at the upper end of the second crystallization kettle, and the centrifuged crude product is further settled and then is sent into a tower for continuous rectification. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 87.5 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 10.8 percent, and the secondary amine and tertiary amine have high boiling point content of 1.7 percent; the conversion rate after the conversion reaction is 98.3 percent; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 99.3 percent, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 99.2 percent.
Example 6
Liquid ammonia and chloropropyl triethoxysilane are respectively fed into the first ammonification kettle by a pump through a regulating valve group while controlling the feeding amount of the liquid ammonia to be 7.5t/h, the feeding amount of the chloropropyl triethoxysilane to be 2t/h and the feeding amount of ethylenediamine to be 0.02t/h; and adjusting the heating quantity of the coil steam of the ammonification system and the condensing water quantity of the reflux condenser, and controlling the temperature of the three ammonification systems to be 80 ℃ and the pressure to be 3.9MPa. The residence time is regulated and controlled by adjusting the length of an insertion pipe at the inlet of the ammonification kettle, the residence time of the first ammonification kettle and the second ammonification kettle is 1h, and the residence time of the third ammonification kettle is 0.9h. The crude product mixed solution is decompressed to 0.8MPa through a decompression regulating valve from the side opening of the upper end of the third ammoniation kettle and then enters an evaporation kettle; the temperature is controlled to be 60 ℃ by adjusting the heating of coil steam in the evaporating kettle; after most of liquid ammonia is distilled off from the crude product mixed solution, the crude product mixed solution is depressurized to 0.1MPa through a depressurization regulating valve from an overflow port at the upper end side of the evaporation kettle and then enters a first crystallization kettle; the temperature of the first crystallization kettle is controlled to be 10 ℃ through circulating water, crude product mixed liquor further overflows into a second crystallization kettle through a side port at the upper end of the first crystallization kettle, the temperature of the second crystallization kettle is controlled to be 60 ℃ through steam, and liquid ammonia in the mixed crude product is further distilled off; the ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; the excessive ethylenediamine in the third ammoniation kettle is distilled out in the first rectifying tower, condensed by the tower top condenser and returned to the ethylenediamine intermediate tank for recycling; and the crude product mixed solution enters a centrifugal machine from a side opening at the upper end of the second crystallization kettle, and the centrifuged crude product is further settled and then is sent into a tower for continuous rectification. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 91.6 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 5.2 percent, and the secondary amine and tertiary amine and the high boiling point content are 3.2 percent; the conversion rate after the conversion reaction is 96.8 percent; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 99.2%, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 99.4%.
Example 7
The other conditions were the same as in example 1, except that no insertion tube was provided for the material inlet of the ammonification tank, i.e., the residence time of the material in each ammonification tank was not controlled. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 87.5 percent, the content of N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 7.8 percent, and the secondary amine and tertiary amine and the high boiling point content are 4.7 percent; the conversion rate after the conversion reaction is 95.3 percent; and the purity of the final product gamma-aminopropyl triethoxysilane after rectification is 97.3%, and the purity of the additional product N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane is 95.2%.
Comparative example 1
The ethylenediamine valve was closed, i.e., ethylenediamine was not introduced, and the other conditions were the same as in example 1. After the system is continuously operated for 72 hours, the crude product is detected by sampling chromatography, the content of gamma-aminopropyl triethoxysilane is 92.3 percent, and the secondary amine, tertiary amine and high boiling point content are 7.7 percent; the conversion rate after the conversion reaction is 92.3 percent; and the purity of the gamma-aminopropyl triethoxysilane as a final product after rectification is 95.7 percent. The conversion rate and purity of the product are reduced.
Claims (5)
1. A continuous production method of gamma-aminopropyl triethoxysilane comprises the following steps: the preparation method comprises the steps of (1) carrying out an ammonification reaction by taking chloropropyl triethoxysilane and liquid ammonia as raw materials, wherein the ammonification reaction is carried out in three ammonification kettles which are connected in series; materials sequentially enter a first ammonification kettle and a second ammonification kettle, a static premixer is arranged between the second ammonification kettle and a third ammonification kettle, the effluent materials of ethylenediamine and the second ammonification kettle are mixed in the static premixer and then enter the third ammonification kettle, ethylenediamine and chloropropyl triethoxysilane react in the third ammonification kettle to generate N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, and the materials of the third ammonification kettle are respectively evaporated, crystallized, centrifuged, settled and rectified to obtain gamma-aminopropyl triethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane;
each ammonifying kettle is connected through an interface with a certain overflow height difference, and materials overflow into the next ammonifying kettle through a side opening at the upper end of the ammonifying kettle; when materials enter the ammonification kettles, an insertion pipe is arranged at the inlet of each ammonification kettle, and the length of the insertion pipe is 0.8-0.9 times of the height of the ammonification kettle;
the height-diameter ratio of the ammonification kettle is 12-13:1;
the process conditions of each ammonification kettle are that the temperature of the ammonification kettle is controlled to be 70-85 ℃ and the pressure is controlled to be 3.5-4.5Mpa;
the addition amount of ethylenediamine is controlled to be 1-3wt% of the amount of chloropropyl triethoxysilane by controlling a feed regulating valve; the addition amount of the liquid ammonia is 25-40wt% of the amount of the chloropropyl triethoxysilane;
the residence time of the materials in the first ammonification kettle and the second ammonification kettle is 0.8-1.2h, the mixed crude product of the second ammonification kettle and ethylenediamine enter the third ammonification kettle after passing through the static mixer, and the residence time of the materials in the third ammonification kettle is 0.9-1h.
2. The process according to claim 1, wherein the ammoniation reactor is provided with a heating coil and a reflux condenser.
3. The process according to claim 1, wherein the pressure of the evaporation vessel is controlled to be 0.8-1.0MPa, the temperature is controlled to be 50-65 ℃, the pressure of the crystallization vessel is controlled to be 0-0.2MPa, the temperature of the first crystallization vessel is controlled to be 10-20 ℃, and the temperature of the second crystallization vessel is controlled to be 50-65 ℃.
4. The production method of claim 1, wherein ammonia tail gas distilled from the evaporating kettle and the crystallizing kettle is compressed and condensed by an ammonia compressor and then enters a liquid ammonia intermediate tank for recycling; and (3) evaporating excessive ethylenediamine in the third ammoniation kettle in the first rectifying tower, condensing the ethylenediamine by a tower top condenser, and returning the ethylenediamine to the ethylenediamine intermediate tank for recycling.
5. The production method as claimed in claim 4, wherein the evaporation kettle is of an elongated design and is internally provided with a heating coil, the height-to-diameter ratio is 2-4:1, and an ammonia condenser is arranged on the evaporation kettle; the crystallization kettles are a first crystallization kettle and a second crystallization kettle, stirring and temperature control coil pipes are arranged in the kettles, the two crystallization kettles are connected in series and are connected through an overflow port, and the height-diameter ratio of the crystallization kettles is 1-3:1.
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| CN102596972A (en) * | 2009-10-16 | 2012-07-18 | 道康宁公司 | Method of producing an aminoalkylalkoxysilane |
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