Background technology
Solvent naphtha is one of five large class oil products, and the purposes of solvent naphtha is very extensive, is the oils for Cucumber being played to the effects such as dissolving, dilution, washing and extracting.The first-elected paint solvent oil (being commonly called as paint naphtha) of consumption maximum, next has edible oil, printing-ink, leather, agricultural chemicals, pesticide, rubber, cosmetics, spices, medicine, electronic unit equal solvent oil.Approximately 2,000 ten thousand tons of all kinds of white spirits of the annual consumption in the whole world, its petroleum class white spirit accounts for wherein half.Before the eighties in 20th century, white spirit of less types, change of properties is also little.But enter the later stage eighties 20th century, along with environmental requirement increasingly stringent, the consideration of white spirit user of service's health and safety is more and more subject to people's attention.
At present domestic still take No. 6, No. 120, No. 200 solvent naphthas as main product.Due to the source difference of raw material, the quality of solvent naphtha product particularly sulfur content and arene content difference is wherein larger.The primary raw material that petroleum series white spirit is produced at present has three sources, and the one, crude oil straight-run, the 2nd, catalytic reforming is raffinated oil, and the 3rd, condensate.Alkene in white spirit and arene content are the leading indicators of weighing petroleum solvent oil quality, are also the gap places of current domestic base oil solvent naphtha and external high-grade white spirit.
The de-aromatic hydrocarbons technology of white spirit has four kinds at present: hydrogenation method, sulfonation method, extraction fractional distillation and adsorption method of separation.
White spirit hydrogenation aromatics-removing method is at home and abroad most widely used, and particularly with catalytic reforming, raffinates oil and produces white spirit into raw material, and convenient because of hydrogen source, multiplex hydrogenation method is refining.But for the refinery of hydrogen source deficiency, hydrogenation aromatics-removing technology is limited, and hydrogenation method be difficult to make arene content in solvent naphtha particularly heavy aromatics content drop to 100,000/several below.
Extraction fractional distillation is take 1-METHYLPYRROLIDONE as extractant, by the method for extracting rectifying, removes the benzene in white spirit No. 6, and the method is only limited to the de-aromatic hydrocarbons of white spirit No. 6 at present.Can make its benzene content drop to 2000-3000 μ g/g(Zhang Zhihong, low fragrant solvent naphtha present situation of production technology and development trend [J]. Anhui chemical industry, 2012,38 (5): 8-10).
The alkene removing in white spirit mainly contains hydrogenation hydrogenization method and two kinds of methods of absorption method at present.The alkene of hydrogenation hydrogenization method Arene removal in raffinating oil is by catalytic hydrogenation, and this method can reduce alkene and arene content greatly, then through boiling range cutting, can obtain corresponding high-quality white spirit.But catalytic hydrogenation reaction generally needs medium-pressure or high pressure, at least also want the pressure of several MPa, the requirement to equipment and the requirement of catalyst are all higher, and this brings certain difficulty with regard to the operation of giving workman, is difficult to be widely used in the middle of the operation of actual factory.
Removing the another kind of method of alkene in white spirit is absorption method, it is that a kind of active metal is supported on X-type molecular sieve that current conventional petroleum solvent oil adsorbent adopted more, aromatic hydrocarbons in white spirit, alkene have been had higher selective, reached removing to a certain degree.For example: Chinese patent CN1891792A has set forth treating adsorbent of a kind of white spirit and its production and use, by flooding X-type molecular sieve, the preferred I A-II of nitrate solution A, VIII with nitrate solution, the nitrate solution of I B-II B family metallic element, as KNO
3, AgNO
3, Mg (NO
3)
2, Co (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2.Can successfully remove the alkene in 6# and 120# white spirit, for 6# white spirit, bromine index can drop to below 400; For 120# white spirit, bromine index can drop to below 300, the arene engaging scraping rate in white spirit is reached more than 90% simultaneously, can make aromatic hydrocarbons drop to below 0.2%.
Obviously, for refining of the impurity such as deolefination aromatic hydrocarbons, still there is very large optimization space in existing petroleum solvent oil adsorbent, particularly, for improving adsorbent, with the white spirit that obtains " zero aromatic hydrocarbons zero olefin(e) centent ", be selectively a trend that meets productive life demand.
Summary of the invention
One object of the present invention is to provide a kind of preparation method of bimetallic white spirit treating adsorbent, is at normal temperatures two kinds of different metal nitrate to be loaded on X-type molecular sieve by equi-volume impregnating, through super-dry, roasting and obtain adsorbent.Compare with the adsorbent of prior art, in the close situation of other operating conditions, adsorbent use amount be bibliographical information value below 10% time, the de-fragrant rate of products obtained therefrom, de-alkene rate are suitable, and the adsorbent absorption life-span that this patent is announced is longer.
The bimetallic white spirit treating adsorbent that provides described method to prepare is provided.
A further object of the present invention is to provide the application of described bimetallic white spirit treating adsorbent in white spirit normal temperature absorption method deolefination and aromatic hydrocarbons.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of bimetallic white spirit treating adsorbent, described method comprises the steps:
(1) pre-treatment: by molecular sieve drying activation;
(2) ion-exchange: the molecular sieve after step (1) activation is mixed with metal-nitrate solutions and carries out ion-exchange, and the molecular sieve after exchange is dried;
(3) dipping: by step (2) another kind of metal-nitrate solutions incipient impregnation for dried molecular sieve, the molecular sieve after dipping is dried;
(4) roasting: by dried step (3) molecular sieve calcination process, obtain described bimetallic white spirit treating adsorbent.
According to preparation method of the present invention, described metal nitrate is selected from the lanthanide transition metal nitrate solution in nitrate solution and the IIIB family of IA, IIA, VIII, IB and IIB family metallic element;
Wherein further be preferably selected from KNO
3, AgNO
3, Co (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2and La (NO
3)
2;
Wherein further be preferably selected from AgNO
3, Ni (NO
3)
2and La (NO
3)
2.
The present invention supports such as Ag of active metallic ion on molecular sieve
+and Ni
2+, can provide certain acid centre for molecular sieve, suitable acid centre can with the unsaturated bond generation complexing of alkene and aromatic hydrocarbons, be beneficial to the absorption to aromatic hydrocarbons and alkene.Two kinds of metals in bimetallic sorbent are not independent role, between two kinds of components, can produce cooperative effect, after adding according to suitable ratio, will make its absorption property be greater than both independent role sums, and the stability of load bimetallic sorbent also can strengthen.Metal ion d hole is more, d in being with unappropriated d electronics or unoccupied orbital more, magnetic susceptibility can be larger.Magnetic susceptibility and metal catalytic activity have certain relation, with the structure of metal and alloy and loading condition and difference, from the angle of catalytic reaction, the existence of d with hole, make it to have and from the external world, accept electronics and adsorbing species the ability of Cheng Jian with it, but be not that d band hole is The more the better, adsorption capacity is crossed and can be caused by force the enrichment of adsorption matter to affect adsorption effect.Ag
+there is not d band hole, Ni
2+have d band hole, the two is combined use and is beneficial to aromatic hydrocarbons and the alkene in adsorption solvent oil.
According to preparation method of the present invention, step (1) is described to be dried as dry 4-6h at 80-150 ℃; Described activation for to activate 4-6h at 300 ℃.
According to preparation method of the present invention, step (2) is carried out ion-exchange for the molecular sieve after step (1) is activated mixes according to the ratio of mass ratio 1:8-15 with metal-nitrate solutions, then suction filtration, washing, then be dried;
Wherein the further preferred described metal-nitrate solutions concentration of the present invention is 0.1~0.4g/ml; More preferably 0.251g/ml;
Wherein further preferred described ion-exchange is to exchange 90-120min at 90 ℃;
Wherein further preferably at 90 ℃, exchange 100min;
Wherein also preferably described being dried at 90-120 ℃ is dried 12-24h;
Wherein can also preferred steps (2) repeat 3 times; That is to say, after the molecular sieve after step (1) activation is mixed with metal-nitrate solutions, carry out ion-exchange, then suction filtration, washing, then be dried; After mixing with metal nitrate after dry, carry out ion-exchange, then suction filtration, washing and dry, repeat 3 times again.
The metal nitrate that wherein the present invention can also preferred steps (2) is Ni (NO
3)
2.
According to preparation method of the present invention, the metal nitrate in step (3) and molecular sieve mass ratio are 2-10:100.
Wherein step (3) is incipient impregnation, and the metal-nitrate solutions concentration of the further preferred steps of the present invention (3) is 0.251g/ml.
The metal nitrate that wherein the present invention can also preferred steps (3) is AgNO
3.
Wherein the present invention further the mass ratio of preferred steps (2) and step (3) metal nitrate be separately 1:1~3.
According to preparation method of the present invention, the dipping of preferred steps of the present invention (3) is at room temperature to flood.
According to preparation method of the present invention, in step (3), be dried as dry 12-24h at 90-120 ℃;
Wherein more preferably at 110-120 ℃, be dried 12h.
According to preparation method of the present invention, in step (4), roasting is roasting 4-6h at 450-640 ℃;
Wherein preferably the dried molecular sieve of step (3) is warming up to 400 ℃ with 6-8 ℃/min speed by room temperature, then with 2-4 ℃/min speed, is warming up to 450-640 ℃ and carries out roasting.
According to preparation method of the present invention, described molecular sieve is X-type molecular sieve;
Wherein also be preferably 10X or 13X molecular sieve.
On the other hand, the present invention also provides the present invention bimetallic white spirit treating adsorbent prepared by any described method, and bimetallic white spirit treating adsorbent of the present invention is prepared by the method comprising the steps:
(1) pre-treatment: by molecular sieve drying activation;
(2) ion-exchange: the molecular sieve after step (1) activation is mixed with metal-nitrate solutions and carries out ion-exchange, and the molecular sieve after exchange is dried;
(3) dipping: by step (2) another kind of metal-nitrate solutions incipient impregnation for dried molecular sieve, the molecular sieve after dipping is dried;
(4) roasting: by dried step (3) molecular sieve calcination process, obtain described bimetallic white spirit treating adsorbent.
According to preparation method of the present invention, described metal nitrate is selected from the lanthanide transition metal nitrate solution in nitrate solution and the IIIB family of IA, IIA, VIII, IB and IIB family metallic element;
Wherein further be preferably selected from KNO
3, AgNO
3, Co (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2and La (NO
3)
2;
Wherein further be preferably selected from AgNO
3, Ni (NO
3)
2and La (NO
3)
2.
According to preparation method of the present invention, step (1) is described to be dried as dry 4-6h at 80-150 ℃; Described activation for to activate 4-6h at 300 ℃.
According to preparation method of the present invention, step (2) is carried out ion-exchange for the molecular sieve after step (1) is activated mixes according to the ratio of mass ratio 1:8-15 with metal-nitrate solutions, then suction filtration, washing, then be dried;
Wherein the further preferred described metal-nitrate solutions concentration of the present invention is 0.1~0.4g/ml; More preferably 0.251g/ml;
Wherein further preferred described ion-exchange is to exchange 90-120min at 90 ℃;
Wherein further preferably at 90 ℃, exchange 100min;
Wherein also preferably described being dried at 90-120 ℃ is dried 12-24h;
Wherein can also preferred steps (2) repeat 3 times; That is to say, after the molecular sieve after step (1) activation is mixed with metal-nitrate solutions, carry out ion-exchange, then suction filtration, washing, then be dried; After mixing with metal nitrate after dry, carry out ion-exchange, then suction filtration, washing and dry, repeat 3 times again.
The metal nitrate that wherein the present invention can also preferred steps (2) is Ni (NO
3)
2.
According to preparation method of the present invention, the metal nitrate in step (3) and molecular sieve mass ratio are 2-10:100.
Wherein step (3) is incipient impregnation, and the metal-nitrate solutions concentration of the further preferred steps of the present invention (3) is 0.251g/ml.
The metal nitrate that wherein the present invention can also preferred steps (3) is AgNO
3.
Wherein the present invention further the mass ratio of preferred steps (2) and step (3) metal nitrate be separately 1:1~3.
According to preparation method of the present invention, the dipping of preferred steps of the present invention (3) is at room temperature to flood.
According to preparation method of the present invention, in step (3), be dried as dry 12-24h at 90-120 ℃;
Wherein more preferably at 110-120 ℃, be dried 12h.
According to preparation method of the present invention, in step (4), roasting is roasting 4-6h at 450-640 ℃;
Wherein preferably the dried molecular sieve of step (3) is warming up to 400 ℃ with 6-8 ℃/min speed by room temperature, then with 2-4 ℃/min speed, is warming up to 450-640 ℃ and carries out roasting.
According to preparation method of the present invention, described molecular sieve is X-type molecular sieve;
Wherein also be preferably 10X or 13X molecular sieve.
One side again, the application of the bimetallic white spirit treating adsorbent described in the present invention also provides in white spirit normal temperature absorption method deolefination and aromatic hydrocarbons;
Wherein preferred described white spirit is 6#, 120# or 200# white spirit.
In sum, the invention provides a kind of bimetallic white spirit treating adsorbent and its preparation method and application.Bimetallic white spirit treating adsorbent tool of the present invention has the following advantages:
Bimetallic white spirit treating adsorbent of the present invention is applicable to 6#, 120#, 200# white spirit and carries out at normal temperatures the refining of the impurity such as deolefination, aromatic hydrocarbons, and treatment process is simple, deolefination and de-aromatic hydrocarbons successful.
The specific embodiment
By specific embodiment, describe below the beneficial effect of implementation process of the present invention and generation in detail, be intended to help reader to understand better essence of the present invention and feature, not as restriction that can practical range to this case.
Embodiment 1
Use AgNO
3solution floods 10X type molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 4:100, the molecular sieve after dipping at 120 ℃ dry 12 hours, then with room temperature~400 ℃, with 6 ℃/min, 400~550 ℃ of speed with 2 ℃/min, be raised to 550 ℃ after roasting 4 hours.
Embodiment 2
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:8, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use Cu (NO
3)
2solution floods dried molecular sieve, Cu (NO
3)
2the mass ratio of solid and molecular sieve is 4:100, the molecular sieve after dipping at 120 ℃ dry 12 hours, then with room temperature~400 ℃, with 6 ℃/min, 400~550 ℃ of speed with 2 ℃/min, be raised to 550 ℃ after roasting 4 hours.
Embodiment 3
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:8, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use AgNO
3solution floods dried molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 4:100, the molecular sieve after dipping at 120 ℃ dry 12 hours, then with room temperature~400 ℃, with 6 ℃/min, 400~550 ℃ of speed with 2 ℃/min, be raised to 550 ℃ after roasting 4 hours.
Embodiment 4
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:8, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use AgNO
3solution floods dried molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 4:100, the molecular sieve after dipping at 120 ℃ dry 20 hours, then with room temperature~400 ℃, with 8 ℃/min, 400~600 ℃ of speed with 4 ℃/min, be raised to 600 ℃ after roasting 4 hours.
Embodiment 5
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:5, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use AgNO
3solution floods dried molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 10:100, the molecular sieve after dipping at 120 ℃ dry 12 hours, then with room temperature~400 ℃, with 6 ℃/min, 400~550 ℃ of speed with 2 ℃/min, be raised to 550 ℃ after roasting 4 hours.
Embodiment 6
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:5, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use AgNO
3solution floods dried molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 10:100, the molecular sieve after dipping at 120 ℃ dry 20 hours, then with room temperature~400 ℃, with 8 ℃/min, 400~600 ℃ of speed with 4 ℃/min, be raised to 600 ℃ after roasting 4 hours.
Embodiment 7
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:18, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use AgNO
3solution floods dried molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 2:100, the molecular sieve after dipping at 120 ℃ dry 12 hours, then with room temperature~400 ℃, with 6 ℃/min, 400~550 ℃ of speed with 2 ℃/min, be raised to 550 ℃ after roasting 4 hours.
Embodiment 8
Use Ni (NO
3)
2solution carries out ion-exchange 100min to 10X type molecular sieve at 90 ℃, molecular sieve and Ni (NO
3)
2the mass ratio of solution is 1:18, Ni (NO
3)
2solution concentration is 0.251g/ml, and the mixture obtaining after ion-exchange is with being dried 20 hours after deionized water washing at 100 ℃.Use AgNO
3solution floods dried molecular sieve, AgNO
3the mass ratio of solid and molecular sieve is 2:100, the molecular sieve after dipping at 120 ℃ dry 20 hours, then with room temperature~400 ℃, with 8 ℃/min, 400~600 ℃ of speed with 4 ℃/min, be raised to 600 ℃ after roasting 4 hours.
Embodiment 9
The present embodiment is the use experiment that embodiment 1, embodiment 2, embodiment 3 obtain adsorbent.
Adopt micro-duplex plunger pump that pending white spirit is passed into from continuous micro-anti-column device bottom, through previously prepared good adsorbent layer in post, when first white spirit flows out from micro-anti-column device top, as zero timing point, later every sample of getting a time through after an hour.Molecular sieve admission space 8ml, air speed 0.5-1.5h
-1, the aromatic hydrocarbons of sample and the chromatogram of olefin(e) centent employing Beijing Analytical Instrument Factory 3420 models are flowed out in experiment, and the capillary gasoline PONA post of the OV101 of Shi Ke institute detects.Experimental result: 120# white spirit arene content 3.195% before not removing, olefin(e) centent 0.979%, utilize adsorbent can successfully remove aromatic hydrocarbons and the alkene in this white spirit, adsorbent in embodiment 1 can make olefin(e) centent be down to 0.035%, aromatic hydrocarbons is down to 0.157%, its adsorption effect is better, but service life is shorter.Adsorbent in embodiment 2 can make olefin(e) centent be down to below 0.033%, and aromatic hydrocarbons is down to 0.154%, and its service life is long but adsorption effect is poor.Adsorbent in embodiment 3 but can make olefin(e) centent be down to 0.012%, aromatic hydrocarbons is down to 0.065%, aromatic hydrocarbons in white spirit and olefin removal rate have all been reached more than 95%, long service life compared with other two kinds of molecular sieves, advantages of good adsorption effect, the adsorbent that therefore supports Ni and Ag is optimal adsorbent.Detailed results is in Table 1.
Table 1120# white spirit is at the alkene arene content of different delivery times
Embodiment 10
The present embodiment is the use experiment that embodiment 3, embodiment 5, embodiment 7 obtain adsorbent.
Adopt micro-duplex plunger pump that pending white spirit is passed into from continuous micro-anti-column device bottom, through previously prepared good adsorbent layer in post, when first white spirit flows out from micro-anti-column device top, as zero timing point, later every sample of getting a time through after an hour.Molecular sieve admission space 8ml, air speed 0.5-1.5h
-1, the aromatic hydrocarbons of sample and the chromatogram of olefin(e) centent employing Beijing Analytical Instrument Factory 3420 models are flowed out in experiment, and the capillary gasoline PONA post of the OV101 of Shi Ke institute detects.Experimental result: 120# white spirit arene content 3.195% before not removing, olefin(e) centent 0.979%, utilize adsorbent can successfully remove aromatic hydrocarbons and the alkene in this white spirit, adsorbent in embodiment 3 can make olefin(e) centent be down to 0.012%, aromatic hydrocarbons is down to 0.065%, and the aromatic hydrocarbons in white spirit and olefin removal rate have all been reached more than 95%.Adsorbent in embodiment 5 can make olefin(e) centent be down to 0.054%, and aromatic hydrocarbons is down to 0.154%.Adsorbent in embodiment 7 can make olefin(e) centent be down to 0.03%, and aromatic hydrocarbons is down to 0.178%.The experimental data contrast of three kinds of molecular sieves can find, its adsorption effect is best compared with two kinds of molecular sieves of the molecular sieve in embodiment 3 and other, and service life is the longest, and therefore the adsorbent in embodiment 3 is optimal adsorbent.Detailed results is in Table 2.
Table 2120# white spirit is at the alkene arene content of different delivery times