Background technology
Carbon molecular sieve is 20th century a kind of new adsorbents of growing up of the seventies, it is a kind of good nonpolar carbon materials, nitrogen-preparing carbon molecular sieves (CarbonMolecularSieves, CMS) for separating of air enrichment nitrogen, adopt normal temperature low pressure nitrogen producing craft, have investment cost than traditional deep cooling high pressure nitrogen producing craft few, product nitrogen speed is fast, nitrogen low cost and other advantages. Therefore, it is pressure-variable adsorption (being called for short P.S.A) the air separation nitrogen-enriching adsorbent of current engineering circles first-selection, and this nitrogen is in aspect extensive uses such as chemical industry, industrial gas oil, electronics industry, food industry, coal industry, medical industry, cable industry, metal heat treatmet, transport and storages.
The raw materials of carbon molecular sieve mainly contains at present: various coals, brown coal; Plant shell; Organic high molecular polymer, as phenolic resins, saran etc., different raw materials can affect the final performance of product. Prepare carbon molecular sieve taking coal as raw material because its cost is higher, use Gu little; Adopting plant shell is that raw material is prepared carbon molecular sieve, and therefore the poor-performing of product also should not be promoted the use of. Compare the above two, organic high molecular polymer has definite macromolecular structure, and impurity content is low, is suitable as the raw material of preparing carbon molecular sieve, is raw material but all adopt phenolic resins, and its cost is also high.
Summary of the invention
The technical problem that the present invention mainly solves: for current carbon molecular sieve in air when oxygen separation and nitrogen, denitrification production rate is not high, the problem that nitrogen gas purity is low, provide and utilized discarded greasy filth to prepare carbon molecular sieve, carbon molecular sieve prepared by the present invention has higher permeability and selective, can prepare highly purified nitrogen, can be widely used in gas and separate, take full advantage of scrap feed material simultaneously, make its required cost expending low.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention:
(1) collect discarded oily mud in oil refinery, by itself and running water in mass ratio 1:1 be uniformly mixed, make its dispersed with stirring 10～15min, and the sal volatile that is 2% by mass concentration and the mass concentration coconut acid diethanol amine condensation product that is 1% is after 3:1 is uniformly mixed in mass ratio, be placed in the turbid liquid of above-mentioned mixing, make it fully disperse 20～30min, be prepared into and disperse turbid liquid;
(2) turbid the dispersion of above-mentioned preparation liquid is passed into high-temperature steam and is heated to 55～65 DEG C, after having heated up, under 1500～1800r/min high-speed stirred, then apply the ultrasonic dispersion of 200～300W, make its abundant dispersion treatment 1～2h;
(3) after having disperseed, staticly settle and process 1～2h, tentatively make greasy filth layering, collect upper strata sump oil and start sump (waste oil) pump, the mixed liquor of the sump oil in agitator and parting liquid is separated, collect the greasy filth disperseing, be placed on dry 6～8h at 100～110 DEG C;
(4) after to be dried completing, by its pulverizing and sieve, be prepared into 60～80 object greasy filth particles, meter by weight subsequently, chooses 80～90 parts of greasy filth particles, 1 of the waterglass of 3～8 parts and 7～12 parts, 4-butanediol, to be mixed evenly after, on forming machine, being squeezed into diameter is 2mm, the cylinder greasy filth particle that height is 3～4mm;
(5) choose the cylinder greasy filth particle of above-mentioned preparation, be placed in Muffle furnace, heat up and be heated to 400 DEG C with the heating rate of 7 DEG C/min, be incubated subsequently carbonization 25～30min, leave standstill and be cooled to 20～30 DEG C subsequently, pulverized and sieve, be prepared into the pre-charing greasy filth of 180～200 object particle;
(6) count by weight, choose the pre-charing greasy filth particle of 45～65 parts, the cellulose of 10～15 parts and the deionized water of 25～40 parts, be uniformly mixed and be placed in stainless steel mould extrusion modling, be prepared into diameter 3mm, height is the cylindrical particles of 4mm;
(7) cylindrical particles of being prepared by above-mentioned extruding is placed in rotary carbide furnace; under nitrogen protection; it is heated to 650～700 DEG C; heating rate is 7 DEG C/min; after temperature has heated up; insulation charing 25～30min, stops subsequently heating and is cooled to 20～30 DEG C, can be prepared into carbon molecular sieve prepared by a kind of waste oil sludge.
Application of the present invention: carbon molecular sieve prepared by a kind of waste oil sludge of above-mentioned preparation is as adsorbent, pass through pressure swing adsorption system, by air separation nitrogen and oxygen, the denitrification production rate of isolated nitrogen is 150～200L/kgh, and the purity of nitrogen reaches more than 99.9%.
The invention has the beneficial effects as follows:
(1) carbon molecular sieve of preparing has higher permeability and selective, can prepare highly purified nitrogen, can be widely used in gas and separate;
(2) have higher specific area, specific area is 1000～1200m2/g；
(3) take full advantage of scrap feed material, make its required cost expending low.
Detailed description of the invention
First collect discarded oily mud in oil refinery, by itself and running water in mass ratio 1:1 be uniformly mixed, make its dispersed with stirring 10～15min, and the sal volatile that is 2% by mass concentration and the mass concentration coconut acid diethanol amine condensation product that is 1% is after 3:1 is uniformly mixed in mass ratio, be placed in the turbid liquid of above-mentioned mixing, make it fully disperse 20～30min, be prepared into and disperse turbid liquid; Again turbid the dispersion of above-mentioned preparation liquid is passed into high-temperature steam and is heated to 55～65 DEG C, after having heated up, under 1500～1800r/min high-speed stirred, then apply the ultrasonic dispersion of 200～300W, make its abundant dispersion treatment 1～2h; After having disperseed, staticly settle and process 1～2h, tentatively make greasy filth layering, collect upper strata sump oil and start sump (waste oil) pump, the mixed liquor of the sump oil in agitator and parting liquid is separated, collect the greasy filth disperseing, be placed on dry 6～8h at 100～110 DEG C; After to be dried completing, by its pulverizing and sieve, be prepared into 60～80 object greasy filth particles, meter by weight subsequently, chooses 80～90 parts of greasy filth particles, 1 of the waterglass of 3～8 parts and 7～12 parts, 4-butanediol, to be mixed evenly after, on forming machine, being squeezed into diameter is 2mm, the cylinder greasy filth particle that height is 3～4mm; Then the cylinder greasy filth particle of choosing above-mentioned preparation, is placed in Muffle furnace, heats up and is heated to 400 DEG C with the heating rate of 7 DEG C/min, be incubated subsequently carbonization 25～30min, leave standstill and be cooled to 20～30 DEG C subsequently, pulverized and sieve, be prepared into the pre-charing greasy filth of 180～200 object particle; Meter, chooses the pre-charing greasy filth particle of 45～65 parts, the cellulose of 10～15 parts and the deionized water of 25～40 parts by weight, is uniformly mixed and is placed in stainless steel mould extrusion modling, is prepared into diameter 3mm, and height is the cylindrical particles of 4mm; Cylindrical particles prepared by above-mentioned extruding is placed in rotary carbide furnace; under nitrogen protection; it is heated to 650～700 DEG C; heating rate is 7 DEG C/min; after temperature has heated up; insulation charing 25～30min, stops subsequently heating and is cooled to 20～30 DEG C, can be prepared into carbon molecular sieve prepared by a kind of waste oil sludge.
Example 1
First collect discarded oily mud in oil refinery, by itself and running water in mass ratio 1:1 be uniformly mixed, make its dispersed with stirring 15min, and the sal volatile that is 2% by mass concentration and the mass concentration coconut acid diethanol amine condensation product that is 1% is after 3:1 is uniformly mixed in mass ratio, be placed in the turbid liquid of above-mentioned mixing, make it fully disperse 30min, be prepared into and disperse turbid liquid; Again turbid the dispersion of above-mentioned preparation liquid is passed into high-temperature steam and is heated to 65 DEG C, after having heated up, under 1800r/min high-speed stirred, then apply the ultrasonic dispersion of 300W, make its abundant dispersion treatment 2h; After having disperseed, staticly settle and process 2h, tentatively make greasy filth layering, collect upper strata sump oil and start sump (waste oil) pump, the mixed liquor of the sump oil in agitator and parting liquid is separated, collect the greasy filth disperseing, be placed on dry 8h at 110 DEG C; After to be dried completing, by its pulverizing and sieve, be prepared into 80 object greasy filth particles, subsequently meter by weight, choose 90 parts of greasy filth particles, the waterglass of 3 parts and 7 parts of BDOs, to be mixed evenly after, on forming machine, being squeezed into diameter is 2mm, height is the cylinder greasy filth particle of 4mm; Then the cylinder greasy filth particle of choosing above-mentioned preparation, is placed in Muffle furnace, heats up and is heated to 400 DEG C with the heating rate of 7 DEG C/min, be incubated subsequently carbonization 30min, leave standstill and be cooled to 30 DEG C subsequently, pulverized and sieve, be prepared into the pre-charing greasy filth of 200 object particle; Meter, chooses the pre-charing greasy filth particle of 65 parts, the cellulose of 10 parts and the deionized water of 25 parts by weight, is uniformly mixed and is placed in stainless steel mould extrusion modling, is prepared into diameter 3mm, and height is the cylindrical particles of 4mm; Cylindrical particles prepared by above-mentioned extruding is placed in rotary carbide furnace; under nitrogen protection; it is heated to 700 DEG C; heating rate is 7 DEG C/min; after temperature has heated up; insulation charing 30min, stops subsequently heating and is cooled to 30 DEG C, can be prepared into carbon molecular sieve prepared by a kind of waste oil sludge. Carbon molecular sieve prepared by a kind of waste oil sludge of above-mentioned preparation is as adsorbent, and by pressure swing adsorption system, by air separation nitrogen and oxygen, the denitrification production rate of isolated nitrogen is 200L/kgh, and the purity of nitrogen reaches 99.98%.
Example 2
First collect discarded oily mud in oil refinery, by itself and running water in mass ratio 1:1 be uniformly mixed, make its dispersed with stirring 10min, and the sal volatile that is 2% by mass concentration and the mass concentration coconut acid diethanol amine condensation product that is 1% is after 3:1 is uniformly mixed in mass ratio, be placed in the turbid liquid of above-mentioned mixing, make it fully disperse 20min, be prepared into and disperse turbid liquid; Again turbid the dispersion of above-mentioned preparation liquid is passed into high-temperature steam and is heated to 65 DEG C, after having heated up, under 1500r/min high-speed stirred, then apply the ultrasonic dispersion of 200W, make its abundant dispersion treatment 1h; After having disperseed, staticly settle and process 1h, tentatively make greasy filth layering, collect upper strata sump oil and start sump (waste oil) pump, the mixed liquor of the sump oil in agitator and parting liquid is separated, collect the greasy filth disperseing, be placed on dry 6h at 100 DEG C; After to be dried completing, by its pulverizing and sieve, be prepared into 60 object greasy filth particles, subsequently meter by weight, choose 80 parts of greasy filth particles, the waterglass of 8 parts and 12 parts of BDOs, to be mixed evenly after, on forming machine, being squeezed into diameter is 2mm, height is the cylinder greasy filth particle of 4mm; Then the cylinder greasy filth particle of choosing above-mentioned preparation, is placed in Muffle furnace, heats up and is heated to 400 DEG C with the heating rate of 7 DEG C/min, be incubated subsequently carbonization 25min, leave standstill and be cooled to 20 DEG C subsequently, pulverized and sieve, be prepared into the pre-charing greasy filth of 180 object particle; Meter, chooses the pre-charing greasy filth particle of 45 parts, the cellulose of 15 parts and the deionized water of 40 parts by weight, is uniformly mixed and is placed in stainless steel mould extrusion modling, is prepared into diameter 3mm, and height is the cylindrical particles of 4mm; Cylindrical particles prepared by above-mentioned extruding is placed in rotary carbide furnace; under nitrogen protection; it is heated to 650 DEG C; heating rate is 7 DEG C/min; after temperature has heated up; insulation charing 25min, stops subsequently heating and is cooled to 30 DEG C, can be prepared into carbon molecular sieve prepared by a kind of waste oil sludge. Carbon molecular sieve prepared by a kind of waste oil sludge of above-mentioned preparation is as adsorbent, and by pressure swing adsorption system, by air separation nitrogen and oxygen, the denitrification production rate of isolated nitrogen is 150L/kgh, and the purity of nitrogen reaches 99.97%.
Example 3
First collect discarded oily mud in oil refinery, by itself and running water in mass ratio 1:1 be uniformly mixed, make its dispersed with stirring 12min, and the sal volatile that is 2% by mass concentration and the mass concentration coconut acid diethanol amine condensation product that is 1% is after 3:1 is uniformly mixed in mass ratio, be placed in the turbid liquid of above-mentioned mixing, make it fully disperse 25min, be prepared into and disperse turbid liquid; Again turbid the dispersion of above-mentioned preparation liquid is passed into high-temperature steam and is heated to 60 DEG C, after having heated up, under 1700r/min high-speed stirred, then apply the ultrasonic dispersion of 250W, make its abundant dispersion treatment 1h; After having disperseed, staticly settle and process 1h, tentatively make greasy filth layering, collect upper strata sump oil and start sump (waste oil) pump, the mixed liquor of the sump oil in agitator and parting liquid is separated, collect the greasy filth disperseing, be placed on dry 7h at 105 DEG C; After to be dried completing, by its pulverizing and sieve, be prepared into 70 object greasy filth particles, subsequently meter by weight, choose 85 parts of greasy filth particles, the waterglass of 5 parts and 10 parts of BDOs, to be mixed evenly after, on forming machine, being squeezed into diameter is 2mm, height is the cylinder greasy filth particle of 3mm; Then the cylinder greasy filth particle of choosing above-mentioned preparation, is placed in Muffle furnace, heats up and is heated to 400 DEG C with the heating rate of 7 DEG C/min, be incubated subsequently carbonization 27min, leave standstill and be cooled to 25 DEG C subsequently, pulverized and sieve, be prepared into the pre-charing greasy filth of 190 object particle; Meter, chooses the pre-charing greasy filth particle of 50 parts, the cellulose of 12 parts and the deionized water of 30 parts by weight, is uniformly mixed and is placed in stainless steel mould extrusion modling, is prepared into diameter 3mm, and height is the cylindrical particles of 4mm; Cylindrical particles prepared by above-mentioned extruding is placed in rotary carbide furnace; under nitrogen protection; it is heated to 660 DEG C; heating rate is 7 DEG C/min; after temperature has heated up; insulation charing 27min, stops subsequently heating and is cooled to 25 DEG C, can be prepared into carbon molecular sieve prepared by a kind of waste oil sludge. Carbon molecular sieve prepared by a kind of waste oil sludge of above-mentioned preparation is as adsorbent, and by pressure swing adsorption system, by air separation nitrogen and oxygen, the denitrification production rate of isolated nitrogen is 180L/kgh, and the purity of nitrogen reaches 99.96%.