CN101671355A - Method for compositing trialkoxysilanes by adopting multistage fluidized bed - Google Patents
Method for compositing trialkoxysilanes by adopting multistage fluidized bed Download PDFInfo
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Abstract
A method for compositing trialkoxysilanesby adopting a multistage fluidized bed relates to a composite method of trialkoxysilanesby. The composite method solves the problems that in the existing composite technology of trialkoxysilanesby, catalytic agent is difficult to be recycled, reactive efficiency is low, products are difficult to be separated, silica powder and copper-based catalytic agent have poor contact, copper silicon contacts have slow productivity and low reactive activity, the catalytic agent loses effectiveness easily after meeting water, and the products are easily hydrolyzed after meeting water. The composite method of trialkoxysilanesby comprises the following steps: 1. preparing copper silicon contacts containing different cuprous chloride mass percents; 2. charging copper silicon contacts obtained in the step one to a reactor of the multistage fluidized bed in stages; and 3. introducing alcohol gas dried by ethyl orthosilicate into the reactor of the multistage fluidized bed to obtain trialkoxysilanesby after reaction and composition. By adopting the method for compositing trialkoxysilanes by adopting the multistage fluidized bed, the selectivity of trialkoxysilanesby reaches 95% and reactive transformation ratio reaches 95%.
Description
Technical field
The present invention relates to a kind of synthetic method of trialkoxy silane.
Background technology
The synthetic method of trialkoxy silane mainly adopts direct method at present, the still formula pulpous state reactors that adopt in the direct method more, reaction process needs solvent as suspension agent, 1., improve the running cost of reaction the problem that this brought has:, 2., the residue silica flour is difficult to reclaim after catalyzer and the reaction, 4., be unfavorable for the product separation purification 3., hinder silica flour and contact, with the direct of pure steam.And in reaction process because silicon powder surface oxidation meeting generates the layer of silicon dioxide film, cause silica flour and Cu-series catalyst loose contact, silicon bronze body contacts productivity is low, reactive behavior is low, and the existence of minor amount of water can cause problems such as catalyst failure, product hydrolysis in the reaction system.Trialkoxy silane, particularly triethoxyl silane mainly are to make by the trichlorosilane alcoholysis reaction industrial at present, this complex process, yield is low, produces etching apparatus in the reaction process with a large amount of HCl, contaminate environment, the cost height, and also product separates the difficulty of purifying.
Summary of the invention
The objective of the invention is for catalyzer in the synthesis technique that solves existing trialkoxy silane is difficult to reclaim, reaction efficiency is low, product is not easily separated, silica flour and Cu-series catalyst loose contact, silicon bronze body contacts productivity is low, reactive behavior is low, catalyzer is met the problem that water easily lost efficacy, product is met the water facile hydrolysis, the invention provides a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes.
The present invention is a kind of, and to adopt the method for multistage fluidized bed compositing trialkoxysilanes be to realize by following steps: one, the preparation of silicon bronze body contacts: a, under ultrasonication, place the mixing acid of hydrofluoric acid and nitric acid to carry out etching 100 orders～350 purpose metallurgical grade silica flours, etching time is 0.5～2min, then the silica flour after the etching is washed to neutral after drying, wherein, the ratio of the amount of substance of hydrofluoric acid and nitric acid is (1/10～10): 1;
B, will join in the Cu-series catalyst preliminary precipitation liquid through the silica flour of step a etching, vacuumize, then under ultrasonication, adding precipitation initiator to sediment-free in the mixed solution of silica flour and Cu-series catalyst preliminary precipitation liquid generates, filter then, vacuum drying obtains the silica flour complex body that Cu-series catalyst coats again, carry out pre-treatment 1～3h then under hydrogen or nitrogen atmosphere, 200 ℃～560 ℃ condition, perhaps pre-treatment 1～5min obtains the many and uniform silicon bronze body contacts of active site of active site quantity under the microwave of 2450MHz; Wherein, described Cu-series catalyst preliminary precipitation liquid is cuprous chloride preliminary precipitation liquid or copper hydroxide preliminary precipitation liquid, and the mass ratio of the silica flour of step a etching and Cu-series catalyst preliminary precipitation liquid is 1: 0.05～2;
This step is by changing silica flour and the Cu-series catalyst preliminary precipitation liquid blended mass ratio through step a etching, obtains containing the silicon bronze body contacts of the Cu-series catalyst of 0.1～2% (quality), 2～5% (quality), 3～8% (quality), 4～10% (quality) and 5～15% (quality) respectively;
Two, the composite charging of classification: a, the composite charging of silicon bronze body contacts classification that contains different mass per-cent Cu-series catalyst that step 1 is obtained is to multistage fluidized-bed reactor, concrete charging is: one-level gas distributor dress contains the silicon bronze body contacts of 5～15% (quality) Cu-series catalyst, secondary gas sparger dress contains the silicon bronze body contacts of 2～5% (quality) Cu-series catalyst, three grades of gas distributor dresses contain the silicon bronze body contacts of 4～10% (quality) Cu-series catalyst, level Four gas distributor dress contains the silicon bronze body contacts of 3～8% (quality) Cu-series catalyst, Pyatyi gas distributor dress contains the silicon bronze body contacts of 0.1～2% (quality) Cu-series catalyst, the uniform quality of the silicon bronze body contacts of the Cu-series catalyst of dosing on the gas distributors at different levels;
B, in the gas distributors at different levels of multistage fluidized bed reactor, add fluorochemical slowly-releasing etching agent and promotor again, wherein the add-on of fluorochemical slowly-releasing etching agent be Cu-series catalyst the silicon bronze body contacts quality 1%～10%, wherein, the preparation method of fluorochemical slowly-releasing etching agent is: to mass concentration is to add molecular sieve in 5%～30% fluoride aqueous solution, decompression is bled then, make in the duct of molecular sieve and be full of fluoride aqueous solution, dry again fluorochemical slowly-releasing etching agent, the mass ratio of molecular sieve and fluoride aqueous solution is 1: 10～17, the mass ratio of fluorochemical and molecular sieve is 0.5～5.1: 1 in the slowly-releasing etching agent, promotor is a zinc powder, the mixture of a kind of in the aluminium powder or two kinds, consumption is 3%～8% of a silicon bronze body contacts quality;
Three, compositing trialkoxysilanes: reaction system is heated to 180 ℃～320 ℃, feed pure bog then in the multistage fluidized bed reactor after the composite charging of classification through the tetraethoxy dehydration, the flow velocity of alcohol bog is 0.03～0.1m/s, reaction times 4～6h obtains trialkoxy silane.
Cu-series catalyst preliminary precipitation liquid described in the present invention and corresponding precipitation initiator are as follows:
The preparation method of cuprous chloride catalyst preliminary precipitation liquid: adopting wet method that cupric chloride, copper powder, sodium-chlor and concentrated hydrochloric acid are hybridly prepared into mass concentration is 2%～10% cuprous chloride preliminary precipitation liquid, the precipitation initiator is a deionized water, wherein the mass ratio of cupric chloride and copper powder is 1: 1～1.5, the ratio of cupric chloride and sodium-chlor is 1: 1.5～2.5, and the mass ratio of cupric chloride and concentrated hydrochloric acid is 1: 5～8.
The preparation method of copper hydroxide catalyzer preliminary precipitation liquid: copper sulfate is dissolved in the deionized water, be configured to massfraction and be 10%～20% copper-bath, be the copper hydroxide catalyzer preliminary precipitation liquid of preparation copper hydroxide catalyzer, the precipitation initiator is a sodium hydroxide solution.
The present invention utilizes the method for multistage fluidized bed compositing trialkoxysilanes to adopt the composite charging method of classification that silicon bronze body contacts is filled in the multistage fluidized bed, reaction does not need organic solvent, catalyst recovery is easy, product is easily separated, also have the advantage of this kind charging method to also have: 1., the composite silicon bronze body contacts of classification in reaction process, the active atomic copper of generation can generate Cu at silicon powder surface uniformly
3Si, and do not have can be brought into the fluidized-bed upper level along with exsiccant alcohol bog with the atom copper of silica flour effect, catalyzer is made full use of, help generating more Cu
3The Si active site, fast reaction speed improves raw material availability; 2., the excessive active atomic copper that produces in the reaction process is not free in the reaction system, can reduce even stop the problem of copper catalytic alcohol dehydrogenation, improve pure utilization ratio, also reduced adding alkali metalsulphide, dimethyl sulfide (DMS), carbonylsulfide (COS), thiomethyl alcohol (MSH or CH simultaneously
3SH), dithiocarbonic anhydride (CS
2), auxiliary agents such as Methyl disulfide (DMDS), thiophene, methyl chloride or monochloroethane suppress the expense of alcohol dehydrogenase, production cost reduces.
The a step can be removed the silicon-dioxide zone of oxidation of silicon powder surface by utilizing the mixing acid etching in the step 1 of the present invention, make fresh silicon face exposed, simultaneously by the mixing acid etching, can make silicon powder surface form a lot of scraggly micropores, help adhering to and coating of Cu-series catalyst, improve Cu-series catalyst and silica flour contact area, improved the productivity of silicon bronze body contacts, reactive behavior strengthens, and has further improved reaction efficiency.
The b step is in vacuum in the step 1 of the present invention, utilize negative pressure with the gas removal in the silicon powder surface micropore, make Cu-series catalyst preliminary precipitation liquid enter into the silicon powder surface micropore fully, utilize precipitation initiator deposited copper series catalysts in the micropore of silicon powder surface to obtain the silica flour of surface deposition Cu-series catalyst then, so also strengthened the contact area of silica flour and catalyzer greatly, improve the productivity of silicon bronze body contacts, improved reaction efficiency.
The water that the present invention is directed in the preparation technology of trialkoxy silane intermediate compound trace in the reaction system will cause the problem of catalyst failure, product hydrolysis, to after the vaporization of the alcohol behind the 3A molecular sieve dehydration, feed again in the tetraethoxy storage tank, the characteristic of utilizing tetraethoxy to be easy to hydrolysis further absorbs the water of ppm level, the water of trace is absorbed, and solved the problem that the water of trace in the reaction system causes catalyst failure and product hydrolysis.
The fluorochemical slowly-releasing etching agent that the present invention obtains fluoride load in the molecular sieve, in reaction process, can control the rate of decomposition of fluorochemical by the stirring velocity of control reaction temperature and reaction system, fluorochemical all can play in the absorption system because the effect of the newly-generated water molecules of side reaction in entire reaction course, the hydrofluoric acid that produces in the fluorochemical hydrolytic process simultaneously can play certain corrasion to silica flour, the thin layer of silicon dioxide on surface is etched away, promote speed of reaction with alcohol.
The selectivity height of trialkoxy silane of the present invention can reach 95%, and the transformation efficiency of reaction also reaches 95%.
Description of drawings
Fig. 1 is the infrared spectra spectrogram of the triethoxyl silane that obtains of embodiment 26 and the standard infrared spectra spectrogram of triethoxyl silane, curve a is the infrared spectra curve of the triethoxyl silane that obtains of embodiment one, and curve b is the standard infrared spectra curve of triethoxyl silane; Fig. 2 is the mass spectrum of the triethoxyl silane that obtains of embodiment 26; Fig. 3 is the gas-chromatography spectrogram of the triethoxyl silane that obtains of embodiment 26,1 is the alcoholic acid chromatographic peak among the figure, 2 is ethyl diethoxy silane chromatographic peak, 3 is the triethoxyl silane chromatographic peak, 4 is the tetraethoxysilane chromatographic peak, and 5 is triethoxyl silane polymerization dewatered product chromatographic peak.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for a kind of multistage fluidized bed compositing trialkoxysilanes of present embodiment realizes by following steps:
One, the preparation of silicon bronze body contacts: a, under ultrasonication, place the mixing acid of hydrofluoric acid and nitric acid to carry out etching 100 orders～350 purpose metallurgical grade silica flours, etching time is 0.5～2min, then the silica flour after the etching is washed to neutral after drying, wherein, the ratio of the amount of substance of hydrofluoric acid and nitric acid is (1/10～10): 1;
B, will join in the Cu-series catalyst preliminary precipitation liquid through the silica flour of step a etching, vacuumize, then under ultrasonication, adding precipitation initiator to sediment-free in the mixed solution of silica flour and Cu-series catalyst preliminary precipitation liquid generates, filter then, vacuum drying obtains the silica flour complex body that Cu-series catalyst coats again, carry out pre-treatment 1～3h then under hydrogen or nitrogen atmosphere, 200 ℃～560 ℃ condition, perhaps pre-treatment 1～5min obtains the many and uniform silicon bronze body contacts of active site of active site quantity under the microwave of 2450MHz; Wherein, described Cu-series catalyst preliminary precipitation liquid is cuprous chloride preliminary precipitation liquid or copper hydroxide preliminary precipitation liquid, and the mass ratio of the silica flour of step a etching and Cu-series catalyst preliminary precipitation liquid is 1: 0.05～2;
This step obtains containing the silicon bronze body contacts of 0.1～2% (quality), 2～5% (quality), 3～8% (quality), 4～10% (quality) and 5～15% (quality) Cu-series catalyst respectively by changing silica flour and the Cu-series catalyst preliminary precipitation liquid blended mass ratio through step a etching;
Two, the composite charging of classification: a, the composite charging of silicon bronze body contacts classification that contains different mass per-cent Cu-series catalyst that step 1 is obtained is to multistage fluidized-bed reactor, concrete charging is: one-level gas distributor dress contains the silicon bronze body contacts of 5～15% (quality) Cu-series catalyst, secondary gas sparger dress contains the silicon bronze body contacts of 2～5% (quality) Cu-series catalyst, three grades of gas distributor dresses contain the silicon bronze body contacts of 4～10% (quality) Cu-series catalyst, level Four gas distributor dress contains the silicon bronze body contacts of 3～8% (quality) Cu-series catalyst, Pyatyi gas distributor dress contains the silicon bronze body contacts of 0.1～2% (quality) Cu-series catalyst, the uniform quality of the silicon bronze body contacts of the Cu-series catalyst of dosing on the gas distributors at different levels;
B, in the gas distributors at different levels of multistage fluidized bed, add fluorochemical slowly-releasing etching agent and promotor again, wherein, the add-on of fluorochemical slowly-releasing etching agent be Cu-series catalyst the silicon bronze body contacts quality 1%～10%, the preparation method of fluorochemical slowly-releasing etching agent is: to mass concentration is to add molecular sieve in 5%～30% fluoride aqueous solution, decompression is bled then, make in the duct of molecular sieve and be full of fluoride aqueous solution, dry again fluorochemical slowly-releasing etching agent, the mass ratio of molecular sieve and fluoride aqueous solution is 1: 10～17, the mass ratio of fluorochemical and molecular sieve is 0.5～5.1: 1 in the slowly-releasing etching agent, promotor is a zinc powder, the mixture of a kind of in the aluminium powder or two kinds, consumption is 3%～8% of a silicon bronze body contacts quality;
Three, compositing trialkoxysilanes: reaction system is heated to 180 ℃～320 ℃, feed pure bog then in the multistage fluidized bed after the composite charging of classification through the tetraethoxy dehydration, the flow velocity of alcohol bog is 0.03～0.1m/s, reaction times 4～6h obtains trialkoxy silane.
The alkoxyl group of trialkoxy silane is that carbonatoms is 1～4 alkoxyl group in the present embodiment.
The reaction process of present embodiment does not need organic solvent, and catalyst recovery is easy, and product is easily separated, and production cost reduces.The contact area of silica flour and catalyzer increases, and makes the production rate of silicon bronze body contacts improve, and reaction efficiency improves.Water in the alcohol bog is reduced to the ppm level, has improved the utilization ratio of catalyzer and the productive rate of trialkoxy silane.
The selectivity height of present embodiment trialkoxy silane can reach 95%, and the transformation efficiency of reaction also reaches 95%.
Embodiment two: present embodiment and embodiment one are different is that the preparation method of cuprous chloride catalyst preliminary precipitation liquid is in the b step of step 1: adopt wet method that cupric chloride, copper powder, sodium-chlor and concentrated hydrochloric acid are hybridly prepared into cuprous chloride preliminary precipitation liquid, the precipitation initiator is a deionized water, wherein the mass ratio of cupric chloride and copper powder is 1: 1～1.5, the ratio of cupric chloride and sodium-chlor is 1: 1.5～2.5, and the mass ratio of cupric chloride and concentrated hydrochloric acid is 1: 5～8.Other step and parameter are identical with embodiment one.
The mass concentration of the cuprous chloride preliminary precipitation liquid of present embodiment preparation is 2%～10%.Present embodiment obtains the silicon bronze body contacts that cuprous chloride coats.
Embodiment three: present embodiment and embodiment one are different is the preparation method of copper hydroxide catalyzer preliminary precipitation liquid in the b step of step 1: copper sulfate is dissolved in the deionized water, be configured to massfraction and be 10%～20% copper-bath, be the copper hydroxide catalyzer preliminary precipitation liquid of preparation copper hydroxide catalyzer, the precipitation initiator is a sodium hydroxide.
Present embodiment obtains the silicon bronze body contacts that copper hydroxide coats.
Replace precipitation initiator sodium hydroxide with acetate or n-nonanoic acid in the present embodiment, obtain the silicon bronze body contacts that venus crystals or n-nonanoic acid copper catalyst coat.
Embodiment four: present embodiment and embodiment one, two or three are different is to place the mixing acid of hydrofluoric acid and nitric acid to carry out etching 200 orders～250 purpose metallurgical grade silica flours in a step of step 1.Other step and parameter are identical with embodiment one, two or three.
Silica flour is that Shanghai state pharmaceutical factory produces in the present embodiment.
Embodiment five: present embodiment and embodiment one to four are different is that the ultrasonic frequency of ultrasonication is 40-80KHz in a step of step 1.Other step and parameter are identical with embodiment one to four.
Embodiment six: present embodiment and embodiment one to five are different be in a step of step 1 under ultrasonication etching 0.8～1.5min.Other step and parameter are identical with embodiment one to five.
Etching time is decided according to the purity of silica flour and the thickness of oxide film in the present embodiment, and purity is low more, and oxide thickness is thick more, and etching time is long more.
Embodiment seven: present embodiment and embodiment one to five are different be in a step of step 1 under ultrasonication etching 1min.Other step and parameter are identical with embodiment one to five.
Embodiment eight: present embodiment and embodiment one to seven are different is that the silica flour of etching in the b step of step 1 and the mass ratio of Cu-series catalyst preliminary precipitation liquid are 1: 0.8～1.5.Other step and parameter are identical with embodiment one to seven.
Embodiment nine: present embodiment and embodiment one to eight are different is to carry out pre-treatment 2h in the b step of step 1 under nitrogen atmosphere, 300 ℃ condition, perhaps pre-treatment 3min under the microwave of 2450MHz.Other step and parameter are identical with embodiment one to eight.
Embodiment ten: present embodiment and embodiment one to nine are different is the copper silicon contact that the b step of step 1 obtains containing 0.8～1.5% (quality), 3～4% (quality), 4～6% (quality), 6～8% (quality) and 10～15% (quality) Cu-series catalyst respectively, and described Cu-series catalyst refers to cuprous chloride catalyst or copper hydroxide catalyzer.Other step and parameter are identical with embodiment one to nine.
Embodiment 11: present embodiment and embodiment one to nine are different is the copper silicon contact that the b step of step 1 obtains containing 1% (quality), 3.5% (quality), 5% (quality), 7% (quality) and 12% (quality) Cu-series catalyst respectively, and described Cu-series catalyst refers to cuprous chloride catalyst or copper hydroxide catalyzer.Other step and parameter are identical with embodiment one to nine.
Embodiment 12: present embodiment and embodiment one to 11 are different is that concrete charging is in a step of step 2: one-level gas distributor dress contains the silicon bronze body contacts of 10～15% (quality) Cu-series catalyst, secondary gas sparger dress contains the silicon bronze body contacts of 3～4% (quality) Cu-series catalyst, three grades of gas distributor dresses contain the silicon bronze body contacts of 6～8% (quality) Cu-series catalyst, level Four gas distributor dress contains the silicon bronze body contacts of 4～6% (quality) Cu-series catalyst, Pyatyi gas distributor dress contains the silicon bronze body contacts of 0.8～1.5% (quality) Cu-series catalyst, the uniform quality of the silicon bronze body contacts of the Cu-series catalyst of dosing on the gas distributors at different levels, described Cu-series catalyst refer to cuprous chloride catalyst or copper hydroxide catalyzer.Other step and parameter are identical with embodiment one to 11.
Embodiment 13: present embodiment and embodiment one to 11 are different is that concrete charging is in a step of step 2: one-level gas distributor dress contains the silicon bronze body contacts of 12% (quality) Cu-series catalyst, secondary gas sparger dress contains the silicon bronze body contacts of 3.5% (quality) Cu-series catalyst, three grades of gas distributor dresses contain the silicon bronze body contacts of 7% (quality) Cu-series catalyst, level Four gas distributor dress contains the silicon bronze body contacts of 5% (quality) Cu-series catalyst, Pyatyi gas distributor dress contains the silicon bronze body contacts of 1% (quality) Cu-series catalyst, the uniform quality of the silicon bronze body contacts of the Cu-series catalyst of dosing on the gas distributors at different levels, described Cu-series catalyst refer to cuprous chloride catalyst or copper hydroxide catalyzer.Other step and parameter are identical with embodiment one to 11.
Embodiment 14: present embodiment and embodiment one to 13 are different is that the add-on of fluorochemical slowly-releasing etching agent is 3%～7% of a silicon bronze body contacts quality in the b step of step 2.Other step and parameter are identical with embodiment one to 13.
Embodiment 15: present embodiment and embodiment one to 13 are different is that the add-on of fluorochemical slowly-releasing etching agent is 4%～5% of a silicon bronze body contacts quality in the b step of step 2.Other step and parameter are identical with embodiment one to 13.
Embodiment 16: present embodiment and embodiment one to 15 are different be in the b step of step 2 in the fluorochemical inhibiter fluorochemical be Sodium Fluoride, Potassium monofluoride or Neutral ammonium fluoride.Other step and parameter are identical with embodiment one to 15.
Embodiment 17: present embodiment and embodiment one to 16 are different is that molecular sieve is SBA-15 molecular sieve, 3A molecular sieve, 13X molecular sieve or carbonaceous molecular sieve-TDX in the b step of step 2.Other step and parameter are identical with embodiment one to 16.
Embodiment 18: present embodiment and embodiment one to 17 are different is that the preparation method of fluorochemical slowly-releasing etching agent is in the b step of step 2: to mass concentration is to add in 15% sodium fluoride aqueous solution in the SBA-15 molecular sieve, decompression is bled then, make in the duct of SBA-15 molecular sieve and be full of Fluorinse, dry again Sodium Fluoride slowly-releasing etching agent, the mass ratio of SBA-15 molecular sieve and sodium fluoride aqueous solution is 1: 10, and the mass ratio of fluorochemical and molecular sieve is 4: 1 in the slowly-releasing etching agent.Other step and parameter are identical with embodiment one to 17.
Present embodiment obtains Sodium Fluoride slowly-releasing etching agent.
Embodiment 19: present embodiment and embodiment one to 18 are different is that the blending ratio of zinc powder and aluminium powder is 1: 1～8 in the promotor described in the b step of step 2.Other step and parameter are identical with embodiment one to 18.
Embodiment 20: what present embodiment and embodiment one to 19 were different is that reaction system is heated to 200 ℃～280 ℃ in the step 3.Other step and parameter are identical with embodiment one to 19.
Embodiment 21: what present embodiment and embodiment one to 19 were different is that reaction system is heated to 240 ℃ in the step 3.Other step and parameter are identical with embodiment one to 19.
Embodiment 22: present embodiment and embodiment one to 21 are different is that the flow velocity of pure bog in the step 3 is 0.05～0.08m/s, reaction times 4.5～5.5h.Other step and parameter are identical with embodiment one to 21.
Embodiment 23: present embodiment and embodiment one to 21 are different is that the flow velocity of pure bog in the step 3 is 0.06m/s, reaction times 5h.Other step and parameter are identical with embodiment one to 21.
Embodiment 24: present embodiment and embodiment one to 23 are different is that alcohol is 1～4 alcohol for carbonatoms in the step 3.Other step and parameter are identical with embodiment one to 23.
Embodiment 25: what present embodiment and embodiment one to 23 were different is that alcohol is methyl alcohol or ethanol in the step 3.Other step and parameter are identical with embodiment one to 23.
Embodiment 26: present embodiment and embodiment one are different is to add in the cuprous chloride preliminary precipitation liquid in 1: 8 the ratio of mass ratio of the silica flour of etching and the cuprous chloride preliminary precipitation liquid that adopts embodiment eight the to obtain silica flour with etching in the b step of step 1, vacuumize then, and then under ultrasonication, in the mixed solution of silica flour and cuprous chloride catalyst preliminary precipitation liquid, add deionized water, until there not being throw out to produce, filter then, vacuum drying obtains the silica flour complex body that cuprous chloride catalyst coats again, then at nitrogen atmosphere, carry out pre-treatment 2h under 300 ℃ the condition and obtain the many and uniform silicon bronze body contacts of active site of active site quantity; In the step 3 reaction system is heated to 240 ℃, feeds the ethanol vapor oxidizing gases through the tetraethoxy dehydration then in the multistage fluidized bed after the composite charging of classification, the flow velocity of ethanol vapor oxidizing gases is 0.06m/s, and reaction times 5h obtains triethoxyl silane; Feeding the alcoholic acid mol ratio in silica flours at different levels and the entire reaction course is 1: 6.Other step and parameter are identical with embodiment one.
Present embodiment utilizes infrared spectrometer to carry out examination of infrared spectrum the triethoxyl silane that obtains, and the test result curve is shown in curve a among Fig. 1.More as can be known, the triethoxyl silane that present embodiment obtains is consistent with standard diagram, illustrates that present embodiment has obtained triethoxyl silane by a curve among Fig. 1 and b curve ratio.Wherein, examination of infrared spectrum adopts the AVATAR360 type Fourier transform infrared spectrometer that U.S. Nicolet company produces.
Present embodiment utilizes gas chromatograph-mass spectrometer (GC-MS) to test the triethoxyl silane that obtains, test mass spectrum as shown in Figure 2.Wherein, test is the 6089/5973N type gas chromatograph-mass spectrometer (GC-MS) that U.S.'s Agilent (Aglent) company produces with instrument.
Table 1 is the parameters of the gas chromatograph-mass spectrometer (GC-MS) that adopts when testing of present embodiment.
The gas chromatograph-mass spectrometer (GC-MS) parameters is as shown in table 1 when in the present embodiment triethoxyl silane being tested.
Table 1
| Project | Specification |
| Chromatographic column | Quartz capillary column (0.25mm * 30m * 0.25 μ m) |
| EI ion source (ev) | ??70 |
| Column temperature | The post case begins temperature: 50 ℃ keep 2min; Temperature rise rate is 20 ℃/min; Column temperature keeps 280 ℃ of hold-time 3min of temperature |
| The vaporizer temperature (℃) | ??300 |
| Sample size (μ L) | ??0.02 |
As shown in Figure 2, having a mass-to-charge ratio the highest (m/z) among the figure is 163, and this is the quasi-molecular ions after the Si-H bond rupture.Lose fragment-CH
3, the m/z value is 149; Fracture O-CH
2, generating new fragmention m/z value is 135; Lose O again, generating metastable unsaturated fragment m/z value is 119.The mass spectrum of synthetic triethoxyl silane and standard mass spectrum degree of fitting are 98%, illustrate that the synthetic triethoxyl silane is believable.
In the present embodiment triethoxyl silane that obtains is carried out the gas-chromatography test, test result as shown in Figure 3.As shown in Figure 3, triethoxyl silane is a primary product in the product of present embodiment, has minor by-products, and by product is mainly ethyl diethoxy silane, tetraethoxysilane and triethoxyl silane polymerization dewatered product.The selectivity of product triethoxyl silane reaches 95% in the present embodiment, and the transformation efficiency of reaction is 95%.
Embodiment 27: present embodiment and embodiment one are different is to add in the preliminary precipitation liquid of preparation n-nonanoic acid copper catalyst in 1: 8 the ratio of mass ratio of the silica flour of etching and the preliminary precipitation liquid of the preparation n-nonanoic acid copper catalyst that adopts embodiment nine the to obtain silica flour with etching in the b step of step 1, vacuumize then, and then under ultrasonication, in the mixed solution of the silica flour and the preliminary precipitation liquid of preparation n-nonanoic acid copper catalyst, add n-nonanoic acid, until there not being throw out to produce, filter then, vacuum drying obtains the silica flour complex body that the n-nonanoic acid copper catalyst coats again, and pre-treatment 3min obtains the many and uniform silicon bronze body contacts of active site of active site quantity under the microwave of 2450MHz then; In the step 3 reaction system is heated to 240 ℃, feeds the methanol vapor oxidizing gases through the tetraethoxy dehydration then in the multistage fluidized bed after the composite charging of classification, the flow velocity of methanol vapor oxidizing gases is 0.06m/s, and reaction times 5h obtains Trimethoxy silane; The mol ratio that feeds methyl alcohol in silica flours at different levels and the entire reaction course is 1: 6.Other step and parameter are identical with embodiment one.
The selectivity of product Trimethoxy silane reaches 87% in the present embodiment, and the transformation efficiency of reaction is 95%.
Claims (10)
1, a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes is characterized in that adopting the method for multistage fluidized bed compositing trialkoxysilanes to realize by following steps:
One, the preparation of silicon bronze body contacts: a, under ultrasonication, place the mixing acid of hydrofluoric acid and nitric acid to carry out etching 100 orders～350 purpose metallurgical grade silica flours, etching time is 0.5～2min, then the silica flour after the etching is washed to neutral after drying, wherein, the mass ratio of hydrofluoric acid and nitric acid is (1/10～10): 1;
B, will join in the Cu-series catalyst preliminary precipitation liquid through the silica flour of step a etching, vacuumize, then under ultrasonication, adding precipitation initiator to sediment-free in the mixed solution of silica flour and Cu-series catalyst preliminary precipitation liquid generates, filter then, vacuum drying obtains the silica flour complex body that Cu-series catalyst coats again, carry out pre-treatment 1～3h then under hydrogen or nitrogen atmosphere, 200 ℃～560 ℃ condition, perhaps pre-treatment 1～5min obtains the many and uniform silicon bronze body contacts of active site of active site quantity under the microwave of 2450MHz; Wherein, described Cu-series catalyst preliminary precipitation liquid is cuprous chloride preliminary precipitation liquid or copper hydroxide preliminary precipitation liquid, and the mass ratio of the silica flour of step a etching and Cu-series catalyst preliminary precipitation liquid is 1: 0.05～2;
This step obtains containing the silicon bronze body contacts of 0.1～2% (quality), 2～5% (quality), 3～8% (quality), 4～10% (quality) and 5～15% (quality) Cu-series catalyst respectively by changing silica flour and the Cu-series catalyst preliminary precipitation liquid blended mass ratio through step a etching;
Two, the composite charging of classification: a, the composite charging of silicon bronze body contacts classification that contains different mass per-cent Cu-series catalyst that step 1 is obtained is to multistage fluidized-bed, concrete charging is: one-level gas distributor dress contains the silicon bronze body contacts of 5～15% (quality) Cu-series catalyst, secondary gas sparger dress contains the silicon bronze body contacts of 2～5% (quality) Cu-series catalyst, three grades of gas distributor dresses contain the silicon bronze body contacts of 4～10% (quality) Cu-series catalyst, level Four gas distributor dress contains the silicon bronze body contacts of 3～8% (quality) Cu-series catalyst, Pyatyi gas distributor dress contains the silicon bronze body contacts of 0.1～2% (quality) Cu-series catalyst, the uniform quality of the silicon bronze body contacts of the Cu-series catalyst of dosing on the gas distributors at different levels;
B, on the gas distributors at different levels of multistage fluidized bed, add fluorochemical slowly-releasing etching agent and promotor again, wherein the add-on of fluorochemical slowly-releasing etching agent be Cu-series catalyst the silicon bronze body contacts quality 1%～10%, wherein, the preparation method of fluorochemical slowly-releasing etching agent is: to mass concentration is to add molecular sieve in 5%～30% fluoride aqueous solution, decompression is bled then, make in the duct of molecular sieve and be full of fluoride aqueous solution, dry again fluorochemical slowly-releasing etching agent, the mass ratio of molecular sieve and fluoride aqueous solution is 1: 10～17, the mass ratio of fluorochemical and molecular sieve is 0.5～5.1: 1 in the slowly-releasing etching agent, promotor is a zinc powder, the mixture of a kind of in the aluminium powder or two kinds, consumption is 3%～8% of a silicon bronze body contacts quality;
Three, compositing trialkoxysilanes: reaction system is heated to 180 ℃～320 ℃, feed pure bog then in the multistage fluidized bed after the composite charging of classification through the tetraethoxy dehydration, the flow velocity of alcohol bog is 0.03～0.1m/s, reaction times 4～6h obtains trialkoxy silane.
2, a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes according to claim 1, the preparation method who it is characterized in that cuprous chloride catalyst preliminary precipitation liquid in the b step of step 1 is: adopt wet method that cupric chloride, copper powder, sodium-chlor and concentrated hydrochloric acid are hybridly prepared into cuprous chloride preliminary precipitation liquid, the precipitation initiator is a deionized water, wherein the mass ratio of cupric chloride and copper powder is 1: 1～1.5, the mass ratio of cupric chloride and sodium-chlor is 1: 1.5～2.5, and the mass ratio of cupric chloride and concentrated hydrochloric acid is 1: 5～8.
3, a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes according to claim 1, the preparation method who it is characterized in that copper hydroxide catalyzer preliminary precipitation liquid in the b step of step 1: copper sulfate is dissolved in the deionized water, be configured to massfraction and be 10%～20% copper-bath, be the copper hydroxide catalyzer preliminary precipitation liquid of preparation copper hydroxide catalyzer, the precipitation initiator is a sodium hydroxide.
4,, it is characterized in that in a step of step 1 etching 0.8～1.5min under ultrasonication according to claim 1,2 or 3 described a kind of methods that adopt the multistage fluidized bed compositing trialkoxysilanes.
5, a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes according to claim 4 is characterized in that in the b step of step 2 that fluorochemical is Sodium Fluoride, Potassium monofluoride or Neutral ammonium fluoride in the fluorochemical inhibiter.
6, according to claim 1,2,3 or 5 described a kind of methods that adopt the multistage fluidized bed compositing trialkoxysilanes, it is characterized in that reaction system is heated to 200 ℃～280 ℃ in the step 3.
7, a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes according to claim 6, the flow velocity that it is characterized in that pure bog in the step 3 is 0.05～0.08m/s, reaction times 4.5～5.5h.
8, a kind of method that adopts the multistage fluidized bed compositing trialkoxysilanes according to claim 6, the flow velocity that it is characterized in that pure bog in the step 3 is 0.06m/s, reaction times 5h.
9,, it is characterized in that in the step 3 that alcohol is 1～4 alcohol for carbonatoms according to claim 1,2,3,5 or 7 described a kind of methods that adopt the multistage fluidized bed compositing trialkoxysilanes.
10,, it is characterized in that alcohol is methyl alcohol or ethanol in the step 3 according to claim 1,2,3,5 or 7 described a kind of methods that adopt the multistage fluidized bed compositing trialkoxysilanes.
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| CN104387413A (en) * | 2014-11-03 | 2015-03-04 | 湖北武大有机硅新材料股份有限公司 | Production method for preparing trialkoxysilane by adopting direct method |
| CN112342422A (en) * | 2020-10-27 | 2021-02-09 | 湖北新蓝天新材料股份有限公司 | Copper-silicon alloy material and preparation method and application thereof |
| CN113087736A (en) * | 2021-04-15 | 2021-07-09 | 宁夏胜蓝化工环保科技有限公司 | Synthesis method and reaction control method of ethyl silicate under microwave radiation |
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| CN101092426A (en) * | 2007-07-25 | 2007-12-26 | 哈尔滨工业大学 | Reaction system and synthetic method for producing chloropropyl triethoxy silicane continuously |
| CN101353356A (en) * | 2008-09-22 | 2009-01-28 | 哈尔滨工业大学 | Method for directly synthesizing trialkoxysilane |
| CN101519413B (en) * | 2009-04-08 | 2011-06-15 | 荆州市江汉精细化工有限公司 | Method for circularly producing silane coupling agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104387413A (en) * | 2014-11-03 | 2015-03-04 | 湖北武大有机硅新材料股份有限公司 | Production method for preparing trialkoxysilane by adopting direct method |
| CN104387413B (en) * | 2014-11-03 | 2017-03-15 | 湖北武大有机硅新材料股份有限公司 | A kind of direct method prepares the production method of trialkoxy silane |
| CN112342422A (en) * | 2020-10-27 | 2021-02-09 | 湖北新蓝天新材料股份有限公司 | Copper-silicon alloy material and preparation method and application thereof |
| CN113087736A (en) * | 2021-04-15 | 2021-07-09 | 宁夏胜蓝化工环保科技有限公司 | Synthesis method and reaction control method of ethyl silicate under microwave radiation |
| CN113087736B (en) * | 2021-04-15 | 2022-12-27 | 宁夏胜蓝化工环保科技有限公司 | Synthesis method and reaction control method of ethyl silicate under microwave radiation |
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