CN101885488B - Porous silica - Google Patents
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- CN101885488B CN101885488B CN200910057225XA CN200910057225A CN101885488B CN 101885488 B CN101885488 B CN 101885488B CN 200910057225X A CN200910057225X A CN 200910057225XA CN 200910057225 A CN200910057225 A CN 200910057225A CN 101885488 B CN101885488 B CN 101885488B
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Abstract
The invention relates to porous silica which mainly solves the problems of greatly reduced pore volume of a carrier because silica solution particles permeate into a silica pore channel in a process of preparing the silica carrier by using the methods of rolling forming, extrusion forming and the like through using porous silica powder as raw materials and liquid containing silica solution as a bonding agent, and lower selectivity of a vinyl acetate catalyst prepared by the silica carrier. By adopting a pore channel protecting agent with weight percent of 5-40 percent in the porous silica, the invention better solves the problems and can be used for industrially producing the vinyl acetate fixed bed catalyst carrier by adopting an ethylene method, wherein the pore channel protecting agent is a residue obtained by roasting an organic matter under the existence of a fire retardant in an oxygen-containing atmosphere, the specific surface of the porous silica is 300-500m<2>/g, and the pore volume is 0.85-1.40ml/g.
Description
Technical field
The present invention relates to a kind of porous silica, especially a kind of protectant porous silica in duct that contains.
Background technology
The chance water that one Chinese patent application CN87100996 discloses adjusting porous structure is the method for making of split silicone not.This technology with the porous silica powder be raw material, with silicon sol rolling balling-up, make fixed bed catalyst carrier through operations such as gellings, drying, roasting, ionogen thermal treatment, washing, drying, roasting.But find in the practice; With the porous silica powder is raw material; The method that is sticker through molding bondeds such as rolling moulding, extrusion moldings with the liquid that contains silicon sol prepares in the silica supports process; The situation of duct obstruction is caused in the inside, duct that exists the silicon sol micelle to infiltrate porous silica, thereby significantly reduces the pore volume of carrier, has hindered the further performance of carrier property.
Summary of the invention
It is raw material that the present invention mainly solves in the past in the technology with the porous silica powder; With the liquid that contains silicon sol is sticker; Prepare in the silica supports process through methods such as rolling moulding, extrusion moldings; The silicon sol micelle infiltrates the silicon-dioxide duct, causes the carrier pore volume to reduce significantly and by the lower problem of vinyl acetate catalyst selectivity of said silica supports preparation, a kind of new porous silica is provided.Support of the catalyst with this porous silica material prepn has the big advantage of pore volume, and the vinyl acetate catalyst for preparing with this silica supports has the high advantage of selectivity.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of porous silica; It is characterized in that containing by weight percentage in the said porous silica 5～40% duct protective material, said duct protective material is that organism is in the presence of fire retardant and the residue that roasting obtains in the presence of oxygen-containing atmosphere; The specific surface area of wherein said porous silica is 300～500 meters
2/ gram, pore volume are 0.85～1.40 milliliter/gram.
In the technique scheme, the protectant content in duct preferable range by weight percentage is 10～40%; The fire retardant preferred version is a phosphorus flame retardant, and more preferably scheme is at least a in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, tri hexyl phosphate, phosphate toluene diphenyl ester, tripotassium phosphate (phenol) ester, tricresyl phosphate (YLENE) ester, p isopropylbenzoic acid phenyl diphenyl ester, phosphoric acid trimethylphenylmethane diphenyl ester or the phosphoric acid hexichol-2-ethylhexyl; The maturing temperature preferable range is 200～400 ℃; Fire retardant consumption preferable range is 5～30% of an organism weight, and more preferably scope is 10～20%; The oxygen-containing atmosphere preferred version is air or pure oxygen.
The concrete preparation process of porous silica of the present invention is following:
(1) porous silica dipping organism-phosphorous flame-retardant agent composition
Adopt equi-volume impregnating well known to those of ordinary skill in the art that porous silica is mixed with liquid organism and phosphorous flame-retardant agent composition each other.Organism and phosphorous flame-retardant agent composition can be used for direct impregnation for liquid at normal temperatures, are not that the liquid heating liquefaction back of can passing through is flooded under insulation under the normal temperature, perhaps through the solvent that adds said mixture said mixture liquefaction back are flooded.
The not special restriction of granularity to the porous silica of dipping usefulness needs the time long but the excessive dipping of particle reaches balance, and too small meeting causes dust, and in roasting process subsequently, is unfavorable for stirring, and general 40～80 orders are better.
To the not special restriction of organic chemical structure, they can be various hydro carbons (alkane, alkene, naphthenic hydrocarbon, aromatic hydrocarbons) and the organism that contains one or more following functional groups: hydroxyl, carboxyl, ester group, amino, carboxamido-group, ether etc.For example petroleum products (being the mixture of hydrocarbon), alcohols, carboxylic-acid, ester class, amine, amides, ethers.Be to reduce in the operating process problems such as volatilization loss, should select for use normal boiling point greater than 200 ℃ organism.Example with containing above-mentioned same functional group in a part has: boiling range is 200～350 ℃ diesel oil, the heavy gas oil that boiling range is 300～370 ℃, the lubricating oil that boiling range is 350～530 ℃; The above monohydroxy-alcohol of C9, the above divalent alcohol of C4 (butyleneglycol etc.), the above trivalent alcohol of C3 (glycerine, TriMethylolPropane(TMP) etc.), Xylitol, sorbyl alcohol; Positive enanthic acid, n-nonanoic acid, the above lipid acid of C10; Each vegetable oil (VT 18, peanut oil, rape oil, cottonseed wet goods), animal oil and fat; Amino dodecane, tetradecy lamine, stearylamine; Acrylic amide; Phenyl ether, dibenzyl ether.The organism instance that contains above-mentioned not functional group of the same race with a part has: glucose, fructose, sucrose, SANMALT-S, amino acid, lactic acid, trolamine etc.
The available phosphorus flame retardant can be the inorganic phosphorus fire retardant; Like phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate etc.; Also can be organophosphorous fire retardant, like tri hexyl phosphate (THP), phosphate toluene diphenyl ester (CDP), tripotassium phosphate (phenol) ester (TCP), tricresyl phosphate (YLENE) ester (TXP), p isopropylbenzoic acid phenyl diphenyl ester (IPPP), phosphoric acid trimethylphenylmethane diphenyl ester (BPDP), phosphoric acid hexichol-2-ethylhexyl (DPOP) etc.Fire retardant can be selected above-mentioned one or more mixture.The fire retardant of selecting will have good compatibility with the organism in the mixture, can be dispersed into mixture each other equably.Generally speaking, wetting ability, strong polar organism can mix with the inorganic phosphorus fire retardant preferably, and oleophilicity, low-pole organism can match with organophosphorous fire retardant.
(2) porous silica that contains organism-phosphorous flame-retardant agent composition is carried out roasting
Roasting can be carried out in being connected with the muffle furnace of airflow; Also can in being connected with the common tube furnace of airflow, carry out; But, be preferably in the rotary type tubular type stoving oven that is connected with airflow and carry out roasting in order air can fully to be contacted and evenly roasting with the porous silica that contains duct protective material precursor.Maturing temperature is controlled at 200～400 ℃, and roasting is overflowed to no longer including flue gas, promptly gets to contain the protectant porous silica in duct.
After organism and the roasting of phosphorous flame-retardant agent composition process aforesaid method; Remaining residue is formed complicated; Can't accurately provide concrete chemical constitution at present; But should contain in a large number in these residues, and possibly have certain pore structure, and the roasting residue of organism and phosphorous flame-retardant agent composition has constituted the duct protective material just structurally near the material of charcoal.
Contain in the protectant porous silica in duct, the protectant content assaying method in duct is: will contain the protectant porous silica in duct and descend dry 4 hours at 120 ℃, and put the mole sieve drier internal cooling to room temperature.Take by weighing cooled sample W with 100 ml beakers
1Gram (1.0000 gram); Add 10 milliliters of concentrated nitric acids (concentration is 96～98%), hot plate heating concentrating sample is added 5 milliliters of concentrated nitric acids and 5 milliliters of perchloric acid (concentration is 70～72%) to about 5 milliliters after the cooling; Be warming up to 100～110 ℃ and be incubated 1 hour gradually; Add 50 ml waters after the cooling, use the fast quantification filter paper filtering then, and be washed with water to filtrating for neutral.Filter cake is transferred at 120 ℃ down in dry 4 hours the known beakers of weight, in order to realize quantitative transfer, on the filter paper with filtration vessel on the silica dioxide granule water of adhering pour beaker.Beaker evaporate to dryness flowing water in 80～90 ℃ loft drier that will contain water and silica dioxide granule continues to put the mole sieve drier internal cooling to room temperature 120 ℃ of dryings 4 hours then, claim the heavy W of silica dioxide granule
2, the weight percentage that then contains duct protectant porous silica mesopore pipe protection agent is provided by following formula:
Duct protective material %=(W
1-W
2)/W
1* 100%
The vinyl acetate catalyst carrier pore volume that contains the protectant porous silica preparation in duct that provides with the inventive method is bigger; Can reach 1.17 milliliters/gram; Than do not contain the protectant silica supports pore volume in duct high 0.36 milliliter/gram, the vinyl acetate catalyst selectivity that makes is better, can reach 96.3%; Than high by 3%, obtained better technical effect with the vinyl acetate catalyst selectivity that does not contain the protectant silicon-dioxide preparation in duct.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
P isopropylbenzoic acid phenyl diphenyl ester (IPPP) and tricresyl phosphate (YLENE) ester (TXP) by weight 1: 1 mixing, are got this p isopropylbenzoic acid phenyl diphenyl ester of 25 weight parts and the VT 18 mixing of tricresyl phosphate (YLENE) ester mixed solution and 100 weight parts then and obtained organism-fire retardant mixed impregnant liquor.Stirring the granularity of slowly in this steeping fluid, progressively increasing down is that 40～80 orders, specific surface are 316 meters
2/ gram, pore volume are the porous silica of 1.38 milliliters/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 230 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 61.9% by weight percentage, duct protective material 38.1%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
The step a) molding bonded: the protectant porous silica in duct that contains that the 1.2nd part obtains is pulverized, and intercepting 200～300 purposes sieve part places in the stainless steel rotating disk as the spin raw material powder, and rotating disk rotates with 36 rev/mins speed.With concentration is that the silicon sol (silicon sol micelle median size 11 nanometers) of 15% (in silicon-dioxide) is sprayed onto on the powder through spray gun, processes the spin seed.Slowly add raw material powder then and spray into the silicon sol of 15% (in silicon-dioxide) slowly; When the mean diameter of a ball (getting 20 MV) of rolling stops adding silicon sol when being 7～8 millimeters; But continue to keep dial rotation 30 minutes, during for preventing that raw material powder is added in adhesion between the spheroid.The ball that will roll then changes in the medicinal coater, rotate with 36 rev/mins speed and carried out polishing in 20 minutes, with the floating powder of removing spherome surface with make spheroid have more slick outside surface.
The step b) gelling: spheroid places the encloses container inherence to leave standstill for 10 ℃ and carried out gelling in 240 hours after polishing.
Step c) is dry: spheroid is placed 110 ℃ baking oven inner drying 3 hours.
Step d) roasting: the spheroid that obtains 600 ℃ of roasting temperature step c) with muffle furnace 6 hours.
The electrolytical aqueous solution thermal treatment of step e): 1 kilogram of input of spheroid that will be cooled to room temperature fills in the autoclave of 2.5 kilograms of acetic acid-ammonium acetate mixed solution, handles 12 hours down at 150 ℃.
Step f) is dry: through the spheroid of washing with loft drier 80 ℃ of dryings 12 hours down.
Through measuring, the carrier specific surface is 213 meters
2/ gram, pore volume are 1.19 milliliters/gram.
For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Preparation of catalysts is according to U.S. Pat P4, and the equi-volume impregnating of 048,096 proposition carries out.
It is that 4～8 millimeters 1.1 liters in carrier is put 5 liters and changeed in the pot that sieve is got the part 2 particle diameter, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 3.43 gram Pd and 1.77 gram Au
2PdCl
4, HAuCl
4404 milliliters of the aqueous solution left standstill 1 hour, rotated 60 milliliters of thread shape addings down and contained 18.3 gram Na
2SiO
39H
2The ageing liquid of O, after static 12 hours, adding 62 ml concns under rotating is the Hydrazine Hydrate 80 of 85% (weight) under the room temperature, room temperature left standstill 12 hours, used deionized water rinsing then, and is negative to the reaction of 0.1 mol Silver Nitrate until elutant.100 ℃ dry 4 hours down, be cooled to after the room temperature with the 404 milliliters of dippings of the Potassium ethanoate aqueous solution that contain 28 gram Potassium ethanoates, obtained catalyst prod down in dry 5 hours at 80 ℃.
4, the performance evaluation of vinyl acetate catalyst
The catalyzer that aforesaid method makes is estimated with 900 milliliters of fixed-bed reactor, through calculating activity of such catalysts and selectivity.Concrete operation method is that the 900 milliliters of catalyzer of in 900 milliliters of fixed-bed reactor, packing into are earlier with ethene pressure testing leak test; After confirming not have leakage, the ethene flow is transferred to 82.8 mol, heat up simultaneously; When temperature in the beds reaches 120 ℃, drop into acetic acid, the acetic acid flow is 12.1 mol; Drop into oxygen after half a hour gradually, throw sufficient amount of oxygen after 2 hours and reach 5.63 mol, air speed is 2500 hours
-1Control bed hot(test)-spot temperature is 145 ℃ in the reaction process, reactor inlet pressure 0.67 MPa.
Each components contents in the gc analysis reaction product, and press following formula and calculate space-time yield and selectivity:
Through 900 milliliters of fixed-bed reactor evaluations, the space-time yield of this catalyzer is 281.1 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 95.9%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 1]
Adopt the used porous silica of embodiment 1 the 1.1st part; Through a pulverizing and intercepting 200～300 purposes sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 1.
The carrier specific surface that obtains is 185 meters
2/ gram, pore volume are 0.85 milliliter/gram.Through relatively knowing that the carrier that embodiment 1 obtains is bigger than the pore volume of comparative example 1 carrier, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 1 preparing carriers is 279.6 grams per liters hour, and selectivity is 93.4%, and the catalyzer of selectivity ratios embodiment 1 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 2]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
The lubricating oil (boiling range is 350～530 ℃) of 100 weight parts and phosphoric acid trimethylphenylmethane diphenyl ester (BPDP) mixing of 20 weight parts are obtained organism-fire retardant mixed impregnant liquor.Stirring the granularity of slowly in this steeping fluid, progressively increasing down is that 40～80 orders, specific surface are 347 meters
2/ gram, pore volume are the porous silica of 1.30 milliliters/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 300 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 65.4% by weight percentage, duct protective material 34.6%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
As embodiment 1 part 2, also successively according to from the step a) to the step f), operating.
Through measuring, the carrier specific surface is 203 meters
2/ gram, pore volume are 1.17 milliliters/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by embodiment 1 the 3rd part.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to embodiment 1 the 4th part.Through estimating, the space-time yield of this catalyzer is 280.6 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 96.3%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 2]
Adopt the used porous silica of embodiment 2 the 1.1st part; Through a pulverizing and intercepting 200～300 purposes sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 2.
The carrier specific surface that obtains is 177 meters
2/ gram, pore volume are 0.81 milliliter/gram.Through relatively knowing that the carrier that embodiment 2 the 3rd part obtains is bigger than the pore volume of comparative example 2 carriers, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 2 preparing carriers is 278.9 grams per liters hour, and selectivity is 93.3%, and the catalyzer of selectivity ratios embodiment 2 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 3]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
The phosphate toluene diphenyl ester (CDP) of getting lard and 18 weight parts of 100 weight parts is heated to 65 ℃ of mixings and obtains organism-fire retardant mixed impregnant liquor.The granularity of slowly in this steeping fluid, progressively increasing 65 ℃ of maintenances with under stirring is that 40～80 orders, specific surface are 407 meters
2/ gram, pore volume are the porous silica of 1.23 milliliters/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that part 1 is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 270 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 71.9% by weight percentage, duct protective material 28.1%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
As embodiment 1 part 2, also successively according to from the step a) to the step f), operating.Through measuring, the carrier specific surface is 187 meters
2/ gram, pore volume are 1.09 milliliters/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by embodiment 1 the 3rd part.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to embodiment 1 the 4th part.Through estimating, the space-time yield of this catalyzer is 282.0 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 96.5%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 3]
Used porous silica in the 1.1st part among the employing embodiment 3; Through a pulverizing and the intercepting 200-300 purpose sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 3.
The carrier specific surface that obtains is 172 meters
2/ gram, pore volume are 0.82 milliliter/gram.Through relatively knowing that the carrier that embodiment 3 the 3rd part obtains is bigger than the pore volume of comparative example 3 carriers, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 3 preparing carriers is 280.4 grams per liters hour, and selectivity is 94.0%, and the catalyzer of selectivity ratios embodiment 3 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 4]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
Tricresyl phosphate (YLENE) ester (TXP) of getting stearylamine and 15 weight parts of 100 weight parts is heated to 70 ℃ of mixings and obtains organism-fire retardant mixed impregnant liquor.The granularity of slowly in this steeping fluid, progressively increasing 70 ℃ of maintenances with under stirring is that 40～80 orders, specific surface are 431 meters
2/ gram, pore volume are the porous silica of 1.12 milliliters/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 330 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 75.6% by weight percentage, duct protective material 24.4%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
As part 2 among the embodiment 1, also successively according to from the step a) to the step f), operating.
Through measuring, the carrier specific surface is 196 meters
2/ gram, pore volume are 0.98 milliliter/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by the 3rd part among the embodiment 1.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to the 4th part among the embodiment 1.Through estimating, the space-time yield of this catalyzer is 281.6 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.4%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 4]
Adopt the used porous silica of the 1.1st part among the embodiment 4; Through a pulverizing and the intercepting 200-300 purpose sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 4.
The carrier specific surface that obtains is 178 meters
2/ gram, pore volume are 0.82 milliliter/gram.Through relatively knowing; The carrier that embodiment 4 the 3rd part obtains is bigger than the pore volume of comparative example 4 carriers; The duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process, for ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 4 preparing carriers is 279.9 grams per liters hour, and selectivity is 93.4%, and the catalyzer of selectivity ratios embodiment 4 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 5]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
The p isopropylbenzoic acid phenyl diphenyl ester (IPPP) of getting Triple Pressed Stearic Acid and 12 weight parts of 100 weight parts is heated to 70 ℃ of mixings and obtains organism-fire retardant mixed impregnant liquor.The granularity of slowly in this steeping fluid, progressively increasing 70 ℃ of maintenances with under stirring is that 40～80 orders, specific surface are 451 meters
2/ gram, pore volume are the porous silica of 1.15 milliliters/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 360 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 78.3% by weight percentage, duct protective material 21.7%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
As embodiment 1 part 2, also successively according to from the step a) to the step f), operating.
Through measuring, the carrier specific surface is 192 meters
2/ gram, pore volume are 1.09 milliliters/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～table 5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by embodiment 1 the 3rd part.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to embodiment 1 the 4th part.Through estimating, the space-time yield of this catalyzer is 278.8 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 96.1%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 5]
Adopt the used porous silica of embodiment 5 the 1.1st part; Through a pulverizing and intercepting 200～300 purposes sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 5.
The carrier specific surface that obtains is 179 meters
2/ gram, pore volume are 0.78 milliliter/gram.Through relatively knowing that the carrier that embodiment 5 the 3rd part obtains is bigger than the pore volume of comparative example 5 carriers, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 5 preparing carriers is 281.3 grams per liters hour, and selectivity is 92.7%, selectivity
Catalyzer than embodiment 5 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 6]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
Getting the phenyl ether of 100 weight parts and the phosphoric acid hexichol of 20 weight parts-2-ethylhexyl (DPOP) is heated to 50 ℃ of mixings and obtains organism-fire retardant mixed impregnant liquor.The granularity of slowly in this steeping fluid, progressively increasing 50 ℃ of maintenances with under stirring is that 40～80 orders, specific surface are 487 meters
2/ gram, pore volume are the porous silica of 0.96 milliliter/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 270 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 81.8% by weight percentage, duct protective material 18.2%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
Except adding the water-washing step all the other operation stepss such as embodiment 1 part 2 between step e) and the step f).
Water-washing step ground concrete operation method is: it is in 40 centimetres the synthetic glass post that the spheroid that will handle through step e), the internal diameter of packing into are 10 centimetres high, and with deionized water wash spheroid 12 hours, current advanced capital at the bottom of the post and go out with the flow velocity of 300 ml/min.
Through measuring, the carrier specific surface is 175 meters
2/ gram, pore volume are 0.91 milliliter/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by embodiment 1 the 3rd part.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to embodiment 1 the 4th part.Through estimating, the space-time yield of this catalyzer is 282.2 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.9%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 6]
Adopt the used porous silica of embodiment 6 the 1.1st part; Through a pulverizing and intercepting 200～300 purposes sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 6.
The carrier specific surface that obtains is 163 meters
2/ gram, pore volume are 0.75 milliliter/gram.Through relatively knowing that the carrier that embodiment 6 the 3rd part obtains is bigger than the pore volume of comparative example 6 carriers, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 6 preparing carriers is 279.8 grams per liters hour, and selectivity is 93.4%, and the catalyzer of selectivity ratios embodiment 6 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 7]
1.1 the mixture that porous silica dipping organism and fire retardant are formed
The concentration of getting TriMethylolPropane(TMP) and 5.9 weight parts of 100 weight parts is that 85% commercially available phosphoric acid (amounting to 100% pure phosphoric acid 5 weight parts) is heated to 70 ℃ of mixings and obtains organism-fire retardant mixed impregnant liquor.The granularity of slowly in this steeping fluid, progressively increasing 70 ℃ of maintenances with under stirring is that 40～80 orders, specific surface are 369 meters
2/ gram, pore volume are the porous silica of 0.87 milliliter/gram, until the infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 270 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 86.1% by weight percentage, duct protective material 13.9%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
Except after step f), increasing the calcination steps part 2 among all the other operation stepss such as the embodiment 1.The calcination steps that increases after the step f) carries out under the condition at 400 ℃ and 2 hours.
Through measuring, the carrier specific surface is 172 meters
2/ gram, pore volume are 0.82 milliliter/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by embodiment 1 the 3rd part.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to embodiment 1 the 4th part.Through estimating, the space-time yield of this catalyzer is 280.2 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 93.8%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 7]
Adopt the used porous silica of embodiment 7 the 1.1st part; Through a pulverizing and intercepting 200～300 purposes sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 7.
The carrier specific surface that obtains is 168 meters
2/ gram, pore volume are 0.75 milliliter/gram.Through relatively knowing that the carrier that embodiment 7 the 3rd part obtains is bigger than the pore volume of comparative example 7 carriers, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～table 5.
The catalyzer space-time yield that uses comparative example 7 preparing carriers is 279.5 grams per liters hour, and selectivity is 93.1%, and the catalyzer of selectivity ratios embodiment 7 is low.For ease of relatively the performance of catalyzer being listed in table 6.
[embodiment 8]
1, contains the preparation of the protectant porous silica in duct
1.1 the mixture that porous silica dipping organism and fire retardant are formed
Get the water of 43 weight parts, add 7 parts by weight of monoammonium phosphate stirring and dissolving, add the sucrose of 100 weight parts then, stir and be heated to 90 ℃ and make sucrose dissolved, obtain containing the steeping fluid of organism-flame-retardant mixture.The granularity of slowly in this steeping fluid, progressively increasing 90 ℃ of maintenances with under stirring is that 40～80 orders, specific surface are 382 meters
2/ gram, pore volume are the porous silica of 1.09 milliliters/gram, until the moisture infusion product that obtains inadherent good fluidity between the just not sticking wall of mixture, the particle.This is contained infusion product drying in 100 ℃ blast drier got the exsiccant infusion product in 12 hours.
1.2 the roasting of carrying out to the porous silica that is impregnated with the mixture that organism and fire retardant form
The exsiccant infusion product that the 1.1st part is obtained places in the rotary type tubular type stoving oven that is connected with airflow, overflows to no longer including flue gas 300 ℃ of following roastings, promptly gets to contain the protectant porous silica in duct.Through measuring, this contains the protectant porous silica in duct and contains porous silica 92.2% by weight percentage, duct protective material 7.8%.
For ease of comparing, the preparation technology and the result that will contain the protectant porous silica in duct list in table 1.
2, preparing carriers
Except between step e) and step f), adding water-washing step and after step f), increasing the calcination steps part 2 among all the other operation stepss such as the embodiment 1.
Water-washing step ground concrete operation method is: it is in 40 centimetres the synthetic glass post that the spheroid that will handle through step e), the internal diameter of packing into are 10 centimetres high, and with deionized water wash spheroid 12 hours, current advanced capital at the bottom of the post and go out with the flow velocity of 300 ml/min.
Roasting after the step f) is carried out under the condition of 300 ℃ and 4 hours.
Through measuring, the carrier specific surface is 210 meters
2/ gram, pore volume are 0.89 milliliter/gram.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
3, the preparation of vinyl acetate catalyst
Operation steps is undertaken by embodiment 1 the 3rd part.
4, the performance evaluation of vinyl acetate catalyst
Carry out according to embodiment 1 the 4th part.Through estimating, the space-time yield of this catalyzer is 277.9 grams per liters hour, and selectivity is 92.5%.For ease of relatively, the performance of catalyzer is listed in table 6.
[comparative example 8]
Adopt the used porous silica of embodiment 8 the 1.1st part; Through a pulverizing and the intercepting 200-300 purpose sieve part raw material as step a) molding bonded in the preparing carriers, and the evaluation of the preparation process of other step of preparing carriers, vinyl acetate catalyst and vinyl acetate catalyst is all identical with embodiment 8.
The carrier specific surface that obtains is 208 meters
2/ gram, pore volume are 0.78 milliliter/gram.Through relatively knowing that the carrier that embodiment 8 the 3rd part obtains is bigger than the pore volume of comparative example 8 carriers, the duct protective material has played the better protecting effect to the duct of carrier in the rolling moulding process.For ease of relatively, the processing condition and the result of preparing carriers listed in table 2～5.
The catalyzer space-time yield that uses comparative example 8 preparing carriers is 281.1 grams per liters hour, and selectivity is 91.2%, and the catalyzer of selectivity ratios embodiment 8 is low.For ease of relatively the performance of catalyzer being listed in table 6.
Table 2 preparing carriers step a)
Annotate: specific surface among the * embodiment and pore volume are meant the specific surface and the pore volume of the porous silica that adopts when preparation contains the duct protective material; "---" the expression no this item.
Table 3 preparing carriers step b)～step d)
Table 4 preparing carriers step e)
* compound method is: cooling and stirring slowly are added drop-wise to strong aqua in the aqueous solution of carboxylic acid, and are diluted to desired concn down, measure pH with Accurate pH trial-production, and embodiment 8 is that the acetate propionate mol ratio is 1: 1 a mixing acid with comparative example 8 used carboxylic acids.
Table 6 catalyst performance
Claims (8)
1. a porous silica is characterized in that containing by weight percentage in the said porous silica 5～40% duct protective material, and said duct protective material is the organism residue that roasting obtains in the presence of phosphorus flame retardant and oxygen-containing atmosphere; The specific surface area of wherein said porous silica is 300～500 meters
2/ gram, pore volume are 0.85～1.40 milliliter/gram; Said organism is selected from alkane, alkene, naphthenic hydrocarbon, aromatic hydrocarbons and contains at least a in the organism of one or more hydroxyls, carboxyl, ester group, amino, carboxamido-group or ether functional group.
2. porous silica according to claim 1 is characterized in that containing by weight percentage in the said porous silica 10～40% duct protective material.
3. porous silica according to claim 1 is characterized in that said phosphorus flame retardant is selected from least a in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, tri hexyl phosphate, phosphate toluene diphenyl ester, tritolyl phosphate, tricresyl phosphate (YLENE) ester, p isopropylbenzoic acid phenyl diphenyl ester, phosphoric acid trimethylphenylmethane diphenyl ester or the phosphoric acid hexichol-2-ethylhexyl.
4. porous silica according to claim 1 is characterized in that said organic boiling point is higher than 200 ℃.
5. porous silica according to claim 1 is characterized in that maturing temperature is 200～400 ℃.
6. porous silica according to claim 1, the consumption that it is characterized in that fire retardant is 5～30% of an organism weight.
7. porous silica according to claim 6, the consumption that it is characterized in that fire retardant is 10～20% of an organism weight.
8. porous silica according to claim 1 is characterized in that said oxygen-containing atmosphere is air or pure oxygen.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954327A (en) * | 1988-08-12 | 1990-09-04 | Blount David H | Production of silica aerogels |
| CN1124715A (en) * | 1994-11-07 | 1996-06-19 | 中国科学院化学研究所 | Process for preparing porous silicon dioxide microsphere |
| CN1681896A (en) * | 2002-08-02 | 2005-10-12 | 罗狄亚化学公司 | Liquid flame retardant composition, preparation and use thereof |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954327A (en) * | 1988-08-12 | 1990-09-04 | Blount David H | Production of silica aerogels |
| CN1124715A (en) * | 1994-11-07 | 1996-06-19 | 中国科学院化学研究所 | Process for preparing porous silicon dioxide microsphere |
| CN1681896A (en) * | 2002-08-02 | 2005-10-12 | 罗狄亚化学公司 | Liquid flame retardant composition, preparation and use thereof |
Non-Patent Citations (1)
| Title |
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| 杨运信等.新型醋酸乙烯酯催化剂研制.《金山油化纤》.2003,第22卷(第1期),1-6. * |
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