CN104707596A - Use of Pb-Al-based hydrotalcite-like compound as sweetening catalyst - Google Patents

Use of Pb-Al-based hydrotalcite-like compound as sweetening catalyst Download PDF

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CN104707596A
CN104707596A CN201310681690.7A CN201310681690A CN104707596A CN 104707596 A CN104707596 A CN 104707596A CN 201310681690 A CN201310681690 A CN 201310681690A CN 104707596 A CN104707596 A CN 104707596A
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houghite
mole ratios
elemental mole
mercaptan
order
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CN104707596B (en
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鲁学文
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The just clean science and technology limited Company in Sichuan
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Abstract

The invention provides a use and use method of a Pb-Al-based hydrotalcite-like compound as a sweetening catalyst and belongs to the field of chemical engineering. The invention provides the use and use method of the Pb-Al-based hydrotalcite-like compound as a sweetening catalyst. The Pb-Al-based hydrotalcite-like compound is used as a catalyst for mercaptan catalytic oxidation, utilizes a Pb/Al composite metal oxide as an active unit and has a mole ratio of Pb to Al of 5-20: 5, or the Pb-Al-based hydrotalcite-like compound can form a novel multielement hydrotalcite-like compound by use of other metals based on the Pb/Al. The invention also comprises a sweetening method. The Pb-Al-based hydrotalcite-like compound has outstanding sweetening effects and can be recycled so that a cost is reduced.

Description

Houghite based on Pb-Al is as the purposes of mercaptan-eliminating catalyst
Technical field
The present invention relates to the houghite based on Pb-Al as the purposes of mercaptan-eliminating catalyst and using method, belong to chemical field.
Background technology
Hydrotalcite is originally the anionic clay ore deposit with layer structure of natural formation, layer structure is similar to shepardite, when the part magnesium ion of shepardite is by aluminium ion isomorphous substitution, lamella is just with residue positive charge, carbonate anion balance between nationality sheet forms hydrotalcite, and the chemical formula of natural hydrotalcite is Mg 6al 2(OH) 16cO 34H 2o.When the magnesium of hydrotalcite or aluminium are replaced by other divalence or trivalent metal ion, or just define houghite when the carbanion between synusia is replaced by other anion.
Due to geological environment and biological chemistry action, at most of oil product, as all contained mercaptan in kerosene, gasoline, diesel oil, naphtha, liquefied gas etc.Mercaptan is a kind of odorant, has stronger corrosivity, has larger harm to environmental and human health impacts, and mercaptan is a kind of radical initiator simultaneously, and can promote unstable component oxidation in oil product, polymerization generates colloid, has a strong impact on quality and the stability of oil product.Therefore, the mercaptan in product must be removed in Petroleum Production.
At present, the method removing mercaptan in oil product has extraction process, catalytic oxidation, absorption method, microbial method and extracting-oxidizing process, various method has its characteristics and available field, from the applicability of method, economy and removal of mercaptans effect, uses more catalytic oxidation.Catalytic oxidation is to be polymerized titanium mountain valley with clumps of trees and bamboo cobalt or sulfonation titanium mountain valley with clumps of trees and bamboo cobalt for catalyst, mix with the oil product containing mercaptan in strong basicity (10% NaOH) solution, in oil product, first mercaptan be extracted into aqueous phase, tasteless disulphide is oxidized in aqueous phase, disulphide is extracted in oil phase again, and then sloughs mercaptan.Adopt said method to carry out oil product deodorization process, need to use a large amount of alkali lye, this not only causes production equipment to corrode, and causes secondary pollution, and adds the complexity of production technology, and operation controls difficulty and increases.In order to overcome the problems referred to above, someone utilizes solid base character, polymerization titanium mountain valley with clumps of trees and bamboo cobalt or sulfonation titanium mountain valley with clumps of trees and bamboo cobalt are combined on solid base, make solid catalysis oxidant, eliminate the various problems using alkali lye to cause, substantially increase speed of production and economic benefit, but regeneration difficulty after this catalysqt deactivation.
Summary of the invention
The technical problem that the present invention solves is to provide the houghite based on Pb-Al as the purposes of mercaptan-eliminating catalyst and using method.
Houghite based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Al for activity unit, each elemental mole ratios n (Pb): n (Al)=5 ~ 20:5.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Al)=5 ~ 15:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=8 ~ 12:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=10:5.
Further, houghite of the present invention is also containing X, namely the houghite based on Pb-Al of the present invention is as the purposes of mercaptan-eliminating catalyst, and described houghite is with the composite metal oxide of Pb/X/Al for activity unit, and described X is at least one in Mg, Cu, Mn and Zn.
Further, preferred described X is Cu, namely the houghite based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, the houghite based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Cu/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Cu): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Cu) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=14:2.5:5.
Further, preferred described X is Mg, the houghite namely based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Mg/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mg): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mg) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=14:2.5:5.
In houghite of the present invention, X is Mn, the houghite namely based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Mn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=14:2.5:5.
Houghite X of the present invention is Mn, and described houghite is also containing metal N, namely the houghite based on Pb-Al of the present invention is as the purposes of mercaptan-eliminating catalyst, described houghite is with the composite metal oxide of Pb/Mn/N/Al for activity unit, and described N is Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn or Mg.
Further, in order to reach better removal of mercaptans effect, preferred described N is Co, Ti, Ni, Zn, Cu or Mg.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu or Ni.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=13:1:1:5.
In houghite of the present invention, X is Zn, the houghite namely based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Zn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=14:2.5:5.
In houghite of the present invention, X is Zn, and described houghite is also containing transition metal M, namely the houghite based on Pb-Al of the present invention is as the purposes of mercaptan-eliminating catalyst, described houghite is with the composite metal oxide of Pb/Zn/M/Al for activity unit, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, preferred described M is Co, Ti, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=13:1:1:5.
The present invention, containing mercaptan mineral oil product deodour method, comprises the following steps: get containing mercaptan oil product x milliliter, add above-mentioned houghite y gram, pass into oxidizing gas, duration of ventilation t >=10min, stops ventilation, leaves standstill, and filters, obtains the refined oil after removing mercaptan; Wherein, y >=4%x; Preferred described y >=6%x; More preferably described y=6 ~ 15%x; More preferably described y=6%x.
The reason passing into oxidizing gas in said method is for liquid agitation and catalytic oxidation.
Mineral oil product deodorization removes the mercaptan in mineral oil product.
Further, in order to better removal of mercaptans effect can be reached, preferred described y >=6%x.
Further, the removal of mercaptans effect that the amount due to catalyst can reach 6%, tend towards stability, add more catalyst, removal of mercaptans effect is almost unchanged, in order to cost-saving, more preferably y=6 ~ 15%x.
Further, in order to cost-saving, preferred described y=6%x.
Further, in order to reach better removal of mercaptans effect, preferred described oxidizing gas is air or oxygen; Preferred described oxidizing gas is air.
Further, can requirement be reached owing to often rising when oil product draft speed is 40L/min during ventilation, so preferably described ventilation body, gas flow rate >=40L/(minL); Namely often liter is greater than 40L/min containing the flow velocity of ventilating in mercaptan oil product.
Further, when the speed of often liter of oil product ventilation is more than 100L/min, even if improve the speed same period, the effect of removal of mercaptans also can not improve, so preferably described ventilation body, gas flow rate is 40 ~ 100L/(minL); Namely often liter is 40 ~ 100L/min containing the flow velocity of ventilating in mercaptan oil product.
Further, when the speed of often liter of oil product ventilation is 56L/min, removal of mercaptans effect reaches best substantially, so preferably described gas flow rate is 56L/(minL); Namely often liter is 56L/min containing the flow velocity of ventilating in mercaptan oil product.
Further, because duration of ventilation is more than 20min, the effect of removal of mercaptans almost improves without further, so in order to cost-saving, and preferred described duration of ventilation t=10 ~ 20min.
Further, in order to cost-saving, preferred described duration of ventilation t=15min.
The present invention containing above-mentioned houghite, i.e. aforesaid houghite in mercaptan mineral oil product deodour method, described houghite with the composite metal oxide of Pb/Al for activity unit, each elemental mole ratios n (Pb): n (Al)=5 ~ 20:5.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Al)=5 ~ 15:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=8 ~ 12:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=10:5.
Further, described houghite is also containing X, and namely described houghite is with the composite metal oxide of Pb/X/Al for activity unit, and described X is at least one in Mg, Cu, Mn and Zn.
Further, preferred described X is Cu, namely described houghite with the composite metal oxide of Pb/Cu/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Cu): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Cu) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=14:2.5:5.
Further, preferred described X is Mg, namely described houghite with the composite metal oxide of Pb/Mg/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mg): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mg) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=14:2.5:5.
In described houghite, X is Mn, namely described houghite with the composite metal oxide of Pb/Mn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=14:2.5:5.
Described houghite X is Mn, and described houghite is also containing metal N, and namely described houghite is with the composite metal oxide of Pb/Mn/N/Al for activity unit, and described N is Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn or Mg.
Further, in order to reach better removal of mercaptans effect, preferred described N is Co, Ti, Ni, Zn, Cu or Mg.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu or Ni.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=13:1:1:5.
In described houghite, X is Zn, namely described houghite with the composite metal oxide of Pb/Zn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=14:2.5:5.
In described houghite, X is Zn, and described houghite is also containing transition metal M, and namely described houghite is with the composite metal oxide of Pb/Zn/M/Al for activity unit, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, preferred described M is Co, Ti, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=13:1:1:5.
During houghite based on Pb-Al of the present invention, the magnesium in Mg/Al hydrotalcite is replaced and is obtained by Pb, or on the basis of replacing, add the polynary houghites such as the obtained ternary of new metallic element or quaternary again.
The preparation method of described Pb/Al houghite catalytic oxidant can be the preparation method of houghite routine, as adopted low saturated coprecipitation, mixed solution co-precipitation metal salt solution being added carbonate containing and alkali obtains houghite compound, take houghite compound as presoma, carry out calcining and obtain described houghite catalyst, or can hydrothermal synthesis method be adopted.Enumerate the preparation method of several houghite of the present invention below:
Pb/Al houghite catalytic oxidant preparation method of the present invention, comprises the following steps:
According to the structure of hydrotalcite, according to n (Pb 2+): n (Al 3+) ratio be 3:1; Take the Pb (NO of 21.86g 3) 2; Get the Al (NO of 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
In 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 12, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Al houghite catalyst.
The preparation method of Pb/Mg/Al houghite catalyst of the present invention is as follows:
(I) according to the structure of hydrotalcite, according to n (Pb 2+): n (Mg 2+): n (Al 3+) ratio be 13:2:5; Take 18.95gPb (NO 3) 2; Get the Mg (NO of 1.3g 3) 2; Al (the NO of 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Mg 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Mg 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 13, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Mg/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Mg/Al houghite catalyst.
The preparation method of Pb/Mn/Cu/Al houghite catalyst of the present invention is as follows:
(I) according to the structure of hydrotalcite, according to n(Pb 2+): n (Mn 2+): n(Cu 2+): n (Al 3+) ratio be 13:1:1:5.Measure 1.02mL, the Mn (NO of 50wt% 3) 2solution, takes 18.94g Pb (NO 3) 2, 1.29g Cu (NO 3) 2﹒ 3H 2al (the NO of O, 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Mn 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Mn 2+)+c (Cu 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 13, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Mn/Cu/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Mn/Cu/Al houghite catalyst.
The present invention various types of hydrotalcite preparation method described in other and upper with, total class, the proportioning difference of nitrate in A liquid, different nitrate can be selected as required to obtain solution A, the amount of NaOH calculates according to c (the NaOH)/substance withdrawl syndrome sum of metal ion [in the A liquid]=2.25, and the amount of sodium carbonate is according to c (Na 2cO 3the substance withdrawl syndrome sum of metal ion in)/[A liquid]=0.67 to calculate.
The present invention has following beneficial effect:
1, mineral Light Oil Deodorization Method of the present invention is adopted, good deodorization effect.
2, adopt mineral Light Oil Deodorization Method of the present invention, the houghite catalyst after filtration can circulate and repeatedly use, and has saved cost.
3, mineral Light Oil Deodorization Method of the present invention, raw material sources are simple, simple to operate, consuming time short.
Accompanying drawing explanation
Fig. 1 be add catalyst consumption to the influential effect curve of mineral mercaptan oxidation;
Fig. 2 is the influential effect curve of duration of ventilation to mineral mercaptan oxidation;
Fig. 3 is the influential effect curve of venting flow rate to mineral mercaptan oxidation;
Fig. 4 is that the molar content of Pb element in Pb/Al class neatly is to the influence curve of the removal of mercaptans effect of houghite;
Fig. 5 is that the molar content of Pb element in Pb/Mg/Al class neatly is to the influence curve of the removal of mercaptans effect of houghite;
Fig. 6 is that the molar content of Mg element in Pb/Mg/Al class neatly is to the influence curve of the removal of mercaptans effect of houghite;
Fig. 7 is that the molar content of Pb element in Pb/Mn/Ni/Al class neatly is to the influence curve of the removal of mercaptans effect of houghite;
Fig. 8 is that the molar content of Mn element in Pb/Mn/Ni/Al class neatly is to the influence curve of the removal of mercaptans effect of houghite;
Fig. 9 is that the molar content of Ni element in Pb/Mn/Ni/Al class neatly is to the influence curve of the removal of mercaptans effect of houghite;
Detailed description of the invention
The technical problem that the present invention solves is to provide the houghite based on Pb-Al as the purposes of mercaptan-eliminating catalyst and using method.
Houghite based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Al for activity unit, each elemental mole ratios n (Pb): n (Al)=5 ~ 20:5.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Al)=5 ~ 15:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=8 ~ 12:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=10:5.
Further, houghite of the present invention is also containing X, namely the houghite based on Pb-Al of the present invention is as the purposes of mercaptan-eliminating catalyst, and described houghite is with the composite metal oxide of Pb/X/Al for activity unit, and described X is at least one in Mg, Cu, Mn and Zn.
Further, preferred described X is Cu, namely the houghite based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, the houghite based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Cu/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Cu): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Cu) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=14:2.5:5.
Further, preferred described X is Mg, the houghite namely based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Mg/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mg): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mg) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=14:2.5:5.
In houghite of the present invention, X is Mn, the houghite namely based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Mn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=14:2.5:5.
Houghite X of the present invention is Mn, and described houghite is also containing metal N, namely the houghite based on Pb-Al of the present invention is as the purposes of mercaptan-eliminating catalyst, described houghite is with the composite metal oxide of Pb/Mn/N/Al for activity unit, and described N is Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn or Mg.
Further, in order to reach better removal of mercaptans effect, preferred described N is Co, Ti, Ni, Zn, Cu or Mg.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu or Ni.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=13:1:1:5.
In houghite of the present invention, X is Zn, the houghite namely based on Pb-Al of the present invention as the purposes of mercaptan-eliminating catalyst, described houghite with the composite metal oxide of Pb/Zn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=14:2.5:5.
In houghite of the present invention, X is Zn, and described houghite is also containing transition metal M, namely the houghite based on Pb-Al of the present invention is as the purposes of mercaptan-eliminating catalyst, described houghite is with the composite metal oxide of Pb/Zn/M/Al for activity unit, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, preferred described M is Co, Ti, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=13:1:1:5.
The present invention, containing mercaptan mineral oil product deodour method, comprises the following steps: get containing mercaptan oil product x milliliter, add above-mentioned houghite y gram, pass into oxidizing gas, duration of ventilation t >=10min, stops ventilation, leaves standstill, and filters, obtains the refined oil after removing mercaptan; Wherein, y >=4%x; Preferred described y >=6%x; More preferably described y=6 ~ 15%x; More preferably described y=6%x.
The reason passing into oxidizing gas in said method is for liquid agitation and catalytic oxidation.
Mineral oil product deodorization removes the mercaptan in mineral oil product.
Further, in order to better removal of mercaptans effect can be reached, preferred described y >=6%x.
Further, the removal of mercaptans effect that the amount due to catalyst can reach 6%, tend towards stability, add more catalyst, removal of mercaptans effect is almost unchanged, in order to cost-saving, more preferably y=6 ~ 15%x.
Further, in order to cost-saving, preferred described y=6%x.
Further, in order to reach better removal of mercaptans effect, preferred described oxidizing gas is air or oxygen; Preferred described oxidizing gas is air.
Further, can requirement be reached owing to often rising when oil product draft speed is 40L/min during ventilation, so preferably described ventilation body, gas flow rate >=40L/(minL); Namely often liter is greater than 40L/min containing the flow velocity of ventilating in mercaptan oil product.
Further, when the speed of often liter of oil product ventilation is more than 100L/min, even if improve the speed same period, the effect of removal of mercaptans also can not improve, so preferably described ventilation body, gas flow rate is 40 ~ 100L/(minL); Namely often liter is 40 ~ 100L/min containing the flow velocity of ventilating in mercaptan oil product.
Further, when the speed of often liter of oil product ventilation is 56L/min, removal of mercaptans effect reaches best substantially, so preferably described gas flow rate is 56L/(minL); Namely often liter is 56L/min containing the flow velocity of ventilating in mercaptan oil product.
Further, because duration of ventilation is more than 20min, the effect of removal of mercaptans almost improves without further, so in order to cost-saving, and preferred described duration of ventilation t=10 ~ 20min.
Further, in order to cost-saving, preferred described duration of ventilation t=15min.
The present invention containing above-mentioned houghite, i.e. aforesaid houghite in mercaptan mineral oil product deodour method, described houghite with the composite metal oxide of Pb/Al for activity unit, each elemental mole ratios n (Pb): n (Al)=5 ~ 20:5.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Al)=5 ~ 15:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=8 ~ 12:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Al)=10:5.
Further, described houghite is also containing X, and namely described houghite is with the composite metal oxide of Pb/X/Al for activity unit, and described X is at least one in Mg, Cu, Mn and Zn.
Further, preferred described X is Cu, namely described houghite with the composite metal oxide of Pb/Cu/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Cu): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Cu) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Cu): n (Al)=14:2.5:5.
Further, preferred described X is Mg, namely described houghite with the composite metal oxide of Pb/Mg/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mg): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mg) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:0 ~ 6:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mg): n (Al)=14:2.5:5.
In described houghite, X is Mn, namely described houghite with the composite metal oxide of Pb/Mn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Mn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=14:2.5:5.
Described houghite X is Mn, and described houghite is also containing metal N, and namely described houghite is with the composite metal oxide of Pb/Mn/N/Al for activity unit, and described N is Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn or Mg.
Further, in order to reach better removal of mercaptans effect, preferred described N is Co, Ti, Ni, Zn, Cu or Mg.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu or Ni.
Further, in order to reach better removal of mercaptans effect, more preferably described N is Cu.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=13:1:1:5.
In described houghite, X is Zn, namely described houghite with the composite metal oxide of Pb/Zn/Al for activity unit.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:0 ~ 6:5, wherein n (Zn) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:1 ~ 4:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=14:2.5:5.
In described houghite, X is Zn, and described houghite is also containing transition metal M, and namely described houghite is with the composite metal oxide of Pb/Zn/M/Al for activity unit, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, preferred described M is Co, Ti, Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni or Cu.
Further, in order to reach better removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach better removal of mercaptans effect, preferred each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, preferred described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5, wherein, n (X) ≠ 0, n (M) ≠ 0.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5.
Further, in order to reach better removal of mercaptans effect, more preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=13:1:1:5.
During houghite based on Pb-Al of the present invention, the magnesium in Mg/Al hydrotalcite is replaced and is obtained by Pb, or on the basis of replacing, add the polynary houghites such as the obtained ternary of new metallic element or quaternary again.
The preparation method of described Pb/Al houghite catalytic oxidant can be the preparation method of houghite routine, as adopted low saturated coprecipitation, mixed solution co-precipitation metal salt solution being added carbonate containing and alkali obtains houghite compound, take houghite compound as presoma, carry out calcining and obtain described houghite catalyst, or can hydrothermal synthesis method be adopted.Enumerate the preparation method of several houghite of the present invention below:
Pb/Al houghite catalytic oxidant preparation method of the present invention, comprises the following steps:
According to the structure of hydrotalcite, according to n (Pb 2+): n (Al 3+) ratio be 3:1; Take the Pb (NO of 21.86g 3) 2; Get the Al (NO of 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
In 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 12, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Al houghite catalyst.
The preparation method of Pb/Mg/Al houghite catalyst of the present invention is as follows:
(I) according to the structure of hydrotalcite, according to n (Pb 2+): n (Mg 2+): n (Al 3+) ratio be 13:2:5; Take 18.95gPb (NO 3) 2; Get the Mg (NO of 1.3g 3) 2; Al (the NO of 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Mg 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Mg 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 13, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Mg/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Mg/Al houghite catalyst.
The preparation method of Pb/Mn/Cu/Al houghite catalyst of the present invention is as follows:
(I) according to the structure of hydrotalcite, according to n(Pb 2+): n (Mn 2+): n(Cu 2+): n (Al 3+) ratio be 13:1:1:5.Measure 1.02mL, the Mn (NO of 50wt% 3) 2solution, takes 18.94g Pb (NO 3) 2, 1.29g Cu (NO 3) 2﹒ 3H 2al (the NO of O, 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Mn 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Mn 2+)+c (Cu 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 13, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Mn/Cu/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Mn/Cu/Al houghite catalyst.
The present invention various types of hydrotalcite preparation method described in other and upper with, total class, the proportioning difference of nitrate in A liquid, different nitrate can be selected as required to obtain solution A, the amount of NaOH calculates according to c (the NaOH)/substance withdrawl syndrome sum of metal ion [in the A liquid]=2.25, and the amount of sodium carbonate is according to c (Na 2cO 3the substance withdrawl syndrome sum of metal ion in)/[A liquid]=0.67 to calculate.
As follows to the research reusing number of times containing the consumption of catalyst in mercaptan Light Oil Deodorization Method, duration of ventilation, gas flow rate and catalyst:
The Pb/Al houghite adopted the research institute of these parameters is prepared from as follows:
(I) according to the structure of hydrotalcite, according to n (Pb 2+): n (Al 3+) ratio be 3:1; Take the Pb (NO of 21.86g 3) 2; Get the Al (NO of 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 12, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Al houghite catalyst.
1, the consumption of catalyst is on the test experiments of the impact of oil product deodorization effect
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, adds Pb/Al houghite, passes into air, and air velocity is 2.8L/min, and ventilation 15min, stops reaction, and leave standstill, Filtration of catalyst, obtains refined oil.
Carry out catalyst amount test experiments according to the method described above: result is as shown in table 1:
The consumption of table 1 catalyst is on the impact experiment table of deodorising effect
Experiment numbers 1 2 3 4 5 6 7
Catalyst amount (%) 0 1.00 2.00 3.00 4.00 5.00 6.00
The content (wt%) of mercaptan sulfur after removal of mercaptans 0.16 0.11 0.07 0.04 0.03 0.03 0.02
Catalyst amount to the curve map of oil product deodorization influential effect as shown in Figure 1.Catalyst amount percentage is the grams/containing the percentage of the volume of mercaptan oil product of catalyst.
From accompanying drawing 1 and table 1, catalyst action successful, adds 1% catalyst, and odorless can be smelt, and doctor is up to the standards; Quantitative analytical data shows, adds 4% catalyst and sulfur content in oil product can be made to drop to less than 0.03%, reach national derv fuel standard.
2, duration of ventilation is on the test experiments of the impact of oil product deodorization effect
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, adds Pb/Al houghite 2g, passes into air, and air velocity is 2.8L/min, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Carry out the test experiments of duration of ventilation on the impact of deodorising effect according to the method described above: result is as shown in table 2:
Table 2 duration of ventilation is on the impact experiment table of deodorising effect
Test number 1 2 3 4 5 6
Duration of ventilation (min) 0 5 10 15 20 25
The content (wt%) of mercaptan sulfur after removal of mercaptans 0.16 0.06 0.04 0.03 0.03 0.02
Duration of ventilation to the curve map of oil product deodorization influential effect as shown in Figure 2.
From accompanying drawing 2 and table 2, oxygen is the necessary condition of mercaptan oxidation reaction, so must pass into enough air in reaction, but after passing into 15min, reaction reaches balance, then adds to no effect.So best duration of ventilation is fixed on 15min in technique.
3, venting flow rate is on the test experiments of the impact of oil product deodorization effect
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, adds Pb/Al houghite 2g, passes into air, duration of ventilation 15min, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Carry out the test experiments of venting flow rate on the impact of deodorising effect according to the method described above: result is as shown in table 3:
Table 3 venting flow rate is on the impact experiment table of deodorising effect
Experiment numbers 1 2 3 4 5
Air velocity (L/min) 0 2.5 5 7.5 10
The content (wt%) of mercaptan sulfur after removal of mercaptans 0.16 0.02 0.03 0.03 0.03
Venting flow rate to the curve map of oil product deodorization influential effect as shown in Figure 3.
From table 3, Fig. 3, in oil product, the oxidation reaction of mercaptan is very fast, under the air mass flow of 2.5L/min, mercaptan sulfur is substantially oxidized (≤0.02%), continue below to increase air mass flow, mercaptan sulfur content slightly rises (≤0.03%) on the contrary, but it is constant to maintain this level.Consider the stability of technique, it is 5.0L/min that subsequent experimental all controls air mass flow.
4, the number of times of reusing of catalyst is tested
Catalyst reuse the service life that number of times determines catalyst, directly affect use cost and the utilization and extention of this catalyst.Containing mercaptan oil volume in control is 50mL, and catalyst is Pb/Al houghite 2g, duration of ventilation 15min, under the experiment condition of air mass flow 2.5L/min, by same catalyst Reusability 8 times, with there being odorless to judge deodorising effect, experimental result is as shown in table 4.
The experimental result table of 8 times reused by table 4 catalyst
Table 4 repeating test proves, this catalytic oxidant can be used for repeatedly deodorizing in oil product, first three best results, and catalyst is without significantly sacrificing, after reusing three times, solid catalyst particle diameter attenuates, rapid precipitation can not be separated, Filter paper filtering ability quantitative recovery catalyst after 6 times, must be adopted.Phenomenon shows the reactions such as catalyst does not in use dissolve, decomposition thus, just catalyst dispersion in use occurs, as long as energy quantitative recovery catalyst, this catalyst can Long-Time Service.
In catalyst, the mol ratio of each element is tested the impact of removal of mercaptans effect
Now the preparation method of citing Pb/Al houghite is as follows:
Wherein, n (Pb 2+): n (Al 3+)=3:1.
(I) Pb (NO of 21.86g is taken 3) 2; Get the Al (NO of 8.25g 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 12, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Al houghite catalyst.
In catalyst, the mol ratio of each element is all with reference to above-mentioned Pb/Al houghite n (Pb on the preparation method of other houghites in the impact test of removal of mercaptans effect 2+): n (Al 3+the preparation method of)=3:1 is prepared from, the kind, the proportioning that are only metallic element are different, different nitrate can be selected as required to obtain solution A, the amount of NaOH calculates according to c (the NaOH)/substance withdrawl syndrome sum of metal ion [in the A liquid]=2.25, and the amount of sodium carbonate is according to c (Na 2cO 3the substance withdrawl syndrome sum of metal ion in)/[A liquid]=0.67 to calculate.
1 tests the impact of the effect of removal of mercaptans for the content of Pb element in Pb/Al houghite
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, add Pb/Al houghite 2g, in Pb/Al houghite, n (Pb): n (Al)=1:1, passes into air, duration of ventilation 15min,, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
N (Pb): n (Al)=2:1, n (Pb): n (Al)=3:1, n (Pb): n (Al)=4:1 tri-kinds Pb/Al houghite is adopted to carry out removal of mercaptans process according to the method described above respectively.
In final oil product mercaptan sulfur mass content with the change of the molar content of Pb element curve map as shown in Figure 4.
2 test the impact of the effect of removal of mercaptans for the content of Pb element in Pb/Mg/Al houghite
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, add Pb/Mg/Al houghite 2g, in Pb/Mg/Al houghite, n (Pb): n (Mg): n (Al)=11:1:5, passes into air, duration of ventilation 15min,, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Adopt respectively according to the method described above n (Pb): n (Mg): n (Al)=12:1:5, n (Pb): n (Mg): n (Al)=13:1:5, n (Pb): n (Mg): n (Al)=15:1:5, n (Pb): n (Mg): n (Al)=17:1:5 tetra-kinds of Pb/Mg/Al houghites carry out removal of mercaptans process.
In final oil product mercaptan sulfur mass content with the change of the molar content of Pb element curve map as shown in Figure 5.
3 test the impact of the effect of removal of mercaptans for the content of Mg element in Pb/Mg/Al houghite
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, add Pb/Mg/Al houghite 2g, in Pb/Mg/Al houghite, n (Pb): n (Mg): n (Al)=13:0:5, passes into air, duration of ventilation 15min,, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Adopt respectively according to the method described above n (Pb): n (Mg): n (Al)=13:1:5n (Pb): n (Mg): n (Al)=13:4:5, n (Pb): n (Mg): n (Al)=13:7:5 tri-kinds of Pb/Mg/Al houghites carry out removal of mercaptans process.
In final oil product mercaptan sulfur mass content with the change of the molar content of Mg element curve map as shown in Figure 6.
4 test the impact of the effect of removal of mercaptans for the content of Pb element in Pb/Mn/Ni/Al houghite
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, add Pb/Mn/Ni/Al houghite 2g, in Pb/Mn/Ni/Al houghite, n (Pb): n (Mn): n (Ni): n (Al)=11:1:1:5, passes into air, duration of ventilation 15min,, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Adopt respectively according to the method described above n (Pb): n (Mn): n (Ni): n (Al)=12:1:1:5n (Pb): n (Mn): n (Ni): n (Al)=13:1:1:5, n (Pb): n (Mn): n (Ni): n (Al)=15:1:1:5 tri-kinds Pb/Mn/Ni/Al houghite carries out removal of mercaptans process.
In final oil product mercaptan sulfur mass content with the change of the molar content of Pb element curve map as shown in Figure 7.
5 test the impact of the effect of removal of mercaptans for the content of Mn element in Pb/Mn/Ni/Al houghite
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, add Pb/Mn/Ni/Al houghite 2g, in Pb/Mn/Ni/Al houghite, n (Pb): n (Mn): n (Ni): n (Al)=13:0:1:5, passes into air, duration of ventilation 15min,, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Adopt respectively according to the method described above n (Pb): n (Mn): n (Ni): n (Al)=13:1:1:5, n (Pb): n (Mn): n (Ni): n (Al)=13:2:1:5, n (Pb): n (Mn): n (Ni): n (Al)=13:3:1:5 tri-kinds Pb/Mn/Ni/Al houghite carries out removal of mercaptans process.
In final oil product mercaptan sulfur mass content with the change of the molar content of Mn element curve map as shown in Figure 8.
6 test the impact of the effect of removal of mercaptans for the content of Ni element in Pb/Mn/Ni/Al houghite
Get containing thiol starting material oil product 50mL, in raw material oil product, mercaptans content is 0.15%, add Pb/Mn/Ni/Al houghite 2g, in Pb/Mn/Ni/Al houghite, n (Pb): n (Mn): n (Ni): n (Al)=13:1:0:5, passes into air, duration of ventilation 15min,, stop reaction, leave standstill, Filtration of catalyst, obtains refined oil.
Adopt respectively according to the method described above n (Pb): n (Mn): n (Ni): n (Al)=13:1:1:5, n (Pb): n (Mn): n (Ni): n (Al)=13:1:2:5, n (Pb): n (Mn): n (Ni): n (Al)=13:1:3:5 tri-kinds Pb/Mn/Ni/Al houghite carries out removal of mercaptans process.
In final oil product mercaptan sulfur mass content with the change of the molar content of Ni element curve map as shown in Figure 9.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1 mineral oil product deodorization
The preparation method of Pb/Mg/Al houghite is as follows:
(I) according to the structure of hydrotalcite, according to n (Pb 2+): n (Mg 2+): n (Al 3+) ratio be 13:2:5; Take 18.95gPb (NO 3) 2, get the Mg (NO of 1.3g 3) 2, 8.25g Al (NO 3) 3﹒ 9H 2o, is made into 30mL solution by deionized water, and this liquid is A liquid; Again according to c(NaOH)/[c (Pb 2+)+c (Mg 2+)+c (Al 3+)]=2.25, c (Na 2cO 3)/[c (Pb 2+)+c (Mg 2+)+c (Al 3+)]=ratio of 0.67, take NaOH7.92g respectively, anhydrous Na 2cO 36.25g, is made into 30mL solution by deionized water, and this liquid is B liquid;
(II) in 250mL beaker, add about 5 ~ 10mL deionized water, heating water bath is to 65 DEG C.Then drip methods just A, B two liquid with two, be added drop-wise in this beaker with the speed of 10mL/min, constant pH is about 13, about raised temperature to 75 DEG C, with preservative film and adhesive plaster sealed beaker mouth, keeps the static crystallization 20h of constant temperature.Then, cyclic washing is to neutral, and by product dry 24h at 80 DEG C, ground 200 mesh sieves, obtain product P b/Mg/Al hydrotalcite.Hydrotalcite product to be moved in Muffle furnace in 300 DEG C of roasting 2h, obtain end product Pb/Mg/Al houghite catalyst;
Get containing thiol starting material oil product 100mL, in raw material oil product, mercaptans content is 0.15wt%, adds the Pb/Mg/Al houghite 4g of above-mentioned preparation, passes into air, air velocity is 5L/min, and ventilation 15min, stops reaction, leave standstill, Filtration of catalyst, obtains refined oil.
After testing: the content 0.00307wt% of mercaptan sulfur in the refined oil that the present embodiment obtains.
Embodiment 2 ~ 23 mineral oil product deodorization
According to the deodour method of embodiment 1, each parameter of embodiment 2 ~ 23 is as shown in table 5 below:
The parameters table of table 5 embodiment 2 ~ 23
In table 5, the oil product of non-removal of mercaptans is containing mercaptan 0.15wt%.
The preparation method of the houghite catalyst of above-described embodiment 2 ~ 23 is with reference to embodiment 1.
Comparative example 1 ~ 3 mineral oil product deodorization
According to the deodour method of embodiment 1, each parameter of comparative example 1 ~ 3 is in table 6:
The parameters of table 6 comparative example 1 ~ 3
In table 6, the oil product of non-removal of mercaptans is containing mercaptan 0.15wt%.
In comparative example 1 ~ 3, the preparation method of houghite is with reference to embodiment 1.
In above-described embodiment, the method for inspection of mercaptan completes with reference to GB/T1792-1988 " in distillate fuel mercaptan sulfur determination method (potentiometric titration) ".

Claims (16)

  1. Houghite based on 1.Pb-Al, as the purposes of mercaptan-eliminating catalyst, is characterized in that: described houghite with the composite metal oxide of Pb/Al for activity unit, each elemental mole ratios n (Pb): n (Al)=5 ~ 20:5.
  2. 2. the houghite based on Pb-Al according to claim 1, as the purposes of mercaptan-eliminating catalyst, is characterized in that: described each elemental mole ratios n (Pb): n (Al)=5 ~ 15:5;
    Preferred described each elemental mole ratios n (Pb): n (Al)=8 ~ 12:5;
    More preferably described each elemental mole ratios n (Pb): n (Al)=10:5.
  3. 3. the houghite based on Pb-Al according to claim 1, as the purposes of mercaptan-eliminating catalyst, is characterized in that: it is at least one in Mg, Cu, Mn and Zn that described houghite also contains X, described X.
  4. 4. the houghite based on Pb-Al according to claim 3, as the purposes of mercaptan-eliminating catalyst, is characterized in that: described X is Cu or Mg; Preferred described X is Mg.
  5. 5. the houghite based on Pb-Al according to claim 4 is as the purposes of mercaptan-eliminating catalyst, it is characterized in that: each elemental mole ratios n (Pb): n (X): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (X) ≠ 0;
    Preferred described each elemental mole ratios n (Pb): n (X): n (Al)=13 ~ 15:0 ~ 6:5;
    More preferably described each elemental mole ratios n (Pb): n (X): n (Al)=13 ~ 15:1 ~ 4:5;
    More preferably described each elemental mole ratios n (Pb): n (X): n (Al)=14:2.5:5.
  6. 6. the houghite based on Pb-Al according to claim 3, as the purposes of mercaptan-eliminating catalyst, is characterized in that: described X is Mn.
  7. 7. the houghite based on Pb-Al according to claim 6 is as the purposes of mercaptan-eliminating catalyst, it is characterized in that: each elemental mole ratios n (Pb): n (Mn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Mn) ≠ 0;
    Preferred described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:0 ~ 6:5;
    More preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=13 ~ 15:1 ~ 4:5;
    More preferably described each elemental mole ratios n (Pb): n (Mn): n (Al)=14:2.5:5.
  8. 8. the houghite based on Pb-Al according to claim 6, as the purposes of mercaptan-eliminating catalyst, is characterized in that: it is Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn or Mg that described houghite also contains metal N, described N;
    Preferred described N is Co, Ti, Ni, Zn, Cu or Mg;
    More preferably described N is Cu or Ni;
    More preferably described N is Cu.
  9. 9. the houghite based on Pb-Al according to claim 8 is as the purposes of mercaptan-eliminating catalyst, it is characterized in that: each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (Mn) ≠ 0, n (N) ≠ 0;
    Preferred described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5;
    More preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5;
    More preferably described each elemental mole ratios n (Pb): n (Mn): n (N): n (Al)=13:1:1:5.
  10. 10. the houghite based on Pb-Al according to claim 3, as the purposes of mercaptan-eliminating catalyst, is characterized in that: described X is Zn.
  11. Houghite based on 11. Pb-Al according to claim 10 is as the purposes of mercaptan-eliminating catalyst, it is characterized in that: each elemental mole ratios n (Pb): n (Zn): n (Al)=10 ~ 20:0 ~ 6:5, wherein n (Zn) ≠ 0;
    Preferred described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:0 ~ 6:5;
    More preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=13 ~ 15:1 ~ 4:5;
    More preferably described each elemental mole ratios n (Pb): n (Zn): n (Al)=14:2.5:5.
  12. Houghite based on 12. Pb-Al according to claim 10, as the purposes of mercaptan-eliminating catalyst, is characterized in that: described houghite is also containing transition metal M, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu;
    Preferred described M is Co, Ti, Ni or Cu;
    More preferably described M is Ni or Cu;
    More preferably described M is Ni.
  13. Houghite based on 13. Pb-Al according to claim 12 is as the purposes of mercaptan-eliminating catalyst, it is characterized in that: each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 20:0 ~ 5:0 ~ 5:5, wherein, n (X) ≠ 0, n (M) ≠ 0;
    Preferred described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0 ~ 2:0 ~ 2:5;
    More preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=10 ~ 16:0.5 ~ 1.5:0.5 ~ 1.5:5;
    More preferably described each elemental mole ratios n (Pb): n (Zn): n (M): n (Al)=13:1:1:5.
  14. 14., containing mercaptan mineral oil product deodour method, is characterized in that: get containing mercaptan oil product x milliliter, add houghite y gram described in any one of claim 1 ~ 13, pass into oxidizing gas, duration of ventilation t >=10min, stop ventilation, leave standstill, filter, obtain the refined oil after removing mercaptan; Wherein, y >=4%x; Preferred described y >=6%x; More preferably described y=6 ~ 15%x; More preferably described y=6%x.
  15. 15. mineral Light Oil Deodorization Methods according to claim 14, is characterized in that: described oxidizing gas is air or oxygen; Preferred described oxidizing gas is air.
  16. 16. mineral Light Oil Deodorization Methods according to claims 14 or 15, is characterized in that: described in pass into oxidizing gas, gas flow rate >=40L/(minL);
    Pass into oxidizing gas preferably, gas flow rate is 40 ~ 100L/(minL);
    More preferably pass into oxidizing gas described in, gas flow rate is 56L/(minL);
    Described duration of ventilation t=10 ~ 20min; Preferred described duration of ventilation t=15min.
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AIMIN CHEN ET AL.: "M-Mn-Al Hydrotalcite-like Compounds as Precursors for Methyl Benzoate Hydrogenation Catalysts", 《IND. ENG. CHEM. RES.》 *
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