CN104711011B - Uses of hydrotalcite-like compound as mercaptan removing catalyst, and use method of hydrotalcite-like compound - Google Patents
Uses of hydrotalcite-like compound as mercaptan removing catalyst, and use method of hydrotalcite-like compound Download PDFInfo
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Abstract
The present invention provides uses of a hydrotalcite-likecompound as a mercaptan removing catalyst, and belongs to the field of chemical industry. The technical problem solved by the present invention is to provide the uses of the hydrotalcite-like compound as the mercaptan removing catalyst, and the use method of the hydrotalcite-like compound. According to the present invention, the hydrotalcite-like compound is adopted as the mercaptan catalysis oxidation catalyst and adopts the Mg/X/Al composite metal oxide as the active unit, the molar ratio of n (Mg) to n (X) to n (Al) is 10-20:0-6:5, X is at least one selected from Mn, Pb and Zn, n (X) is not equal to 0, and the transition metal element such as M or N is added on the basis so as to form the new multi-component hydrotalcite-like compound. The present invention further provides a mercaptan removing method. The hydrotalcite-like compound of the present invention has the prominent mercaptan removing effect, and the hydrotalcite-like compound catalyst can be recycled so as to reduce the cost.
Description
Technical field
The present invention relates to houghite, as the purposes of mercaptan-eliminating catalyst and using method, belongs to chemical field.
Background technology
What brucite was originally naturally occurring has the anionic clay ore deposit of layer structure, and layer structure is similar to shepardite,
When the part magnesium ion of shepardite is by aluminium ion isomorphous substitution, lamella just carries remaining positive charge, the carbonate between nationality piece
Anion balance forms brucite, and the chemical formula of natural hydrotalcite is Mg6Al2(OH)16CO3·4H2O.Magnesium or aluminum when brucite
Replaced by other bivalence or trivalent metal ion, or be the formation of class when the carbanion between synusia is replaced by other aniones
Brucite.
Due to geological environment and biological chemistry action, in most of oil products, such as kerosene, gasoline, diesel oil, Petroleum,
Mercaptan is all contained in liquefied gas etc..Mercaptan is a kind of odorant, has stronger corrosivity, environmental and human health impacts are had relatively
Big harm, mercaptan is a kind of radical initiator simultaneously, can promote unstable component oxidation in oil product, and polymerization generates colloid, sternly
Ghost image rings 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-oxygen
Change method, various methods have its characteristics and available field, from the point of view of the suitability of method, economy and removal of mercaptans effect, use
More catalytic oxidation.Catalytic oxidation 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 as catalyst, in strong basicity（10% hydrogen-oxygen
Change sodium）Mix with the oil product containing mercaptan in solution, in oil product, mercaptan is extracted into aqueous phase first, be oxidized to tasteless in aqueous phase
Disulphide, disulphide is extracted in oil phase again, and then sloughs mercaptan.Oil product deodorization process is carried out using said method, needs
To use substantial amounts of alkali liquor, this not only causes production equipment to corrode, and causes secondary pollution, and increased the complexity of production technology
Property, operational control difficulty increases.In order to overcome the problems referred to above, someone utilizes solid base property, will be polymerized titanium mountain valley with clumps of trees and bamboo cobalt or sulfonation titanium
Mountain valley with clumps of trees and bamboo cobalt combines on solid base, makes solid catalysis oxidant, eliminates the various problems causing using alkali liquor, substantially increases
Speed of production and economic benefit, but after this catalyst inactivation, regeneration is difficult.
Content of the invention
Present invention solves the technical problem that being houghite as the purposes of mercaptan-eliminating catalyst and using method.
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the composition metal of Mg/X/Al for houghite of the present invention
Oxide is activity unit, each element mol ratio n (Mg):n(X):N (Al)=10～20:0～6:5, wherein, X is Mn, Pb and Zn
In at least one, n (X) ≠ 0.
Further, it is preferable to described X is Zn, that is, houghite of the present invention is as the purposes of mercaptan-eliminating catalyst, described class
Brucite is with the metal composite oxide of Mg/Zn/Al as activity unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=12～16:0～4:5, wherein, n (Zn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=14:3:5.
Further, in houghite of the present invention, X is Zn, and described houghite also contains transition metal M, that is,
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the metal composite oxide of Mg/Zn/M/Al for houghite of the present invention
For activity unit, described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach more preferable removal of mercaptans effect, preferably described M is Co, Ni or Ti.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Zn):n(M):n
(Al)=10～20:0～3:0～3:5, wherein, n (Zn) ≠ 0, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(M):n(Al)=13:1:1:5.
In houghite of the present invention, X is Pb, and that is, houghite of the present invention is as the purposes of mercaptan-eliminating catalyst, described
Houghite is with the metal composite oxide of Mg/Pb/Al as activity unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=12～16:0～4:5, wherein, n (Pb) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=14:3:5.
In houghite of the present invention, X is also to contain transition metal N in Pb, and described houghite, i.e. the present invention
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the metal composite oxide of Mg/Pb/N/Al as activity for houghite
Unit, described N is Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described N is Zn, Co, Mn, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn or Zn.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Pb):n(N):n
(Al)=10～20:0～3:0～3:5, wherein, n (Pb) ≠ 0, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):n(Al)=13:1:1:5.
In houghite of the present invention, X is Mn, and that is, houghite of the present invention is as the purposes of mercaptan-eliminating catalyst, described
Houghite is with the metal composite oxide of Mg/Mn/Al as activity unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=12～16:0～4:5, wherein, n (Mn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13:3:5.
In houghite of the present invention, X is also to contain transition metal Y in Mn, and described houghite, i.e. the present invention
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the metal composite oxide of Mg/Mn/Y/Al as activity for houghite
Unit, described Y is Sc, Ti, V, Cr, Fe, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described Y is Zn, Co, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described Y is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～20:0～3:0～3:5, wherein, n (Mn) ≠ 0, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Y):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Y):N (Al)=10～15:0.5～2:0.5～2:5.
One step ground, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Y):n(Al)=13:1:1:5.
Houghite of the present invention is based on Mg/Al houghite, adds new metallic element on its basis
The houghite being formed.
Mg/Mn/Al houghite, because manganese has bivalence, tetravalence, sexavalence and the multiple valence state of septivalency, it is as in activity
The heart, projects compared to the houghite catalytic oxidation effect that other transition metal are formed, but inventor sends out further
The catalytic oxidation effect of existing Mg/Pb/Al houghite is more preferable, far beyond the catalytic oxidation effect of Mg/Mn/Al houghite.
Houghite after present invention calcining is as mercaptan-eliminating catalyst.
Present invention mineral oil containing mercaptan product deodour method, comprises the steps：Take the x milliliter of oil product containing mercaptan, add above-mentioned
Y gram of houghite, is passed through oxidizing gas, duration of ventilation t >=10min, stops ventilation, standing, filters, after obtaining removing mercaptan
Refined oil；Wherein, y >=4%x.
The reason be passed through gas in said method is for liquid agitation and catalysis oxidation.
Mineral oil product deodorization is the mercaptan in removing mineral oil product.
Further, in order to reach more preferable removal of mercaptans effect, preferably described y >=6%x.
Further, because the amount of catalyst is in the 6% removal of mercaptans effect that can reach, tend towards stability, add more
Catalyst, removal of mercaptans effect is almost unchanged, for cost-effective, more preferably y=6～15%x.
Further, for cost-effective, preferably described y=6%x.
Further, from cost-effective consideration, preferably described oxidizing gas are air or oxygen；More preferably described oxidation
Property gas be air.
Further, due to during ventilation every liter of oil product draft speed be to reach requirement during 40L/min, it is advantageous to institute
State and be passed through oxidizing gas, gas flow rate >=40L/（min·L）；I.e. in every liter of oil product containing mercaptan, the flow velocity of ventilation is more than 40L/
min.
Further, when the speed of every liter of oil product ventilation is more than 100L/min, even if improving same period speed, the effect of removal of mercaptans
Fruit also will not be improved, it is advantageous to described be passed through oxidizing gas, gas flow rate is 40～100L/（min·L）；I.e. every liter contains
In mercaptan oil product, the flow velocity of ventilation is 40～100L/min.
Further, when the speed of every liter of oil product ventilation is 56L/min, removal of mercaptans effect basically reach best, so
Preferably described be passed through oxidizing gas, gas flow rate be 56L/（min·L）；I.e. in every liter of oil product containing mercaptan, the flow velocity of ventilation is
56L/min.
Further, because duration of ventilation is more than 20min, the effect of removal of mercaptans improves almost without further, so being
Cost-effective, preferably described duration of ventilation t=10～20min.
Further, for cost-effective, preferably described duration of ventilation t=15min.
In present invention mineral oil containing mercaptan product deodour method, above-mentioned houghite is aforesaid houghite, described class neatly
Stone with the metal composite oxide of Mg/X/Al as activity unit, each element mol ratio n (Mg):n(X):N (Al)=10～20:0～
6:5, wherein, X is at least one in Mn, Pb and Zn, n (X) ≠ 0.
Further, it is preferable to described X is Zn, that is, described houghite is with the metal composite oxide of Mg/Zn/Al as activity
Unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=12～16:0～4:5, wherein, n (Zn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=14:3:5.
In described houghite, X is Zn, and described houghite also contains transition metal M, that is, described houghite with
The metal composite oxide of Mg/Zn/M/Al is activity unit, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach more preferable removal of mercaptans effect, preferably described M is Co, Ni or Ti.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Zn):n(M):n
(Al)=10～20:0～3:0～3:5, wherein, n (Zn) ≠ 0, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(M):n(Al)=13:1:1:5.
In described houghite, X is Pb, and that is, described houghite is single for activity with the metal composite oxide of Mg/Pb/Al
Unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=12～16:0～4:5, wherein, n (Pb) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=14:3:5.
In described houghite, X is also to contain transition metal N in Pb, and described houghite, i.e. described houghite
With the metal composite oxide of Mg/Pb/N/Al as activity unit, described N is Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described N is Zn, Co, Mn, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn or Zn.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Pb):n(N):n
(Al)=10～20:0～3:0～3:5, wherein, n (Pb) ≠ 0, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):n(Al)=13:1:1:5.
In described houghite, X is Mn, and that is, described houghite is single for activity with the metal composite oxide of Mg/Mn/Al
Unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=12～16:0～4:5, wherein, n (Mn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13:3:5.
In described houghite, X is also to contain transition metal Y in Mn, and described houghite, i.e. described houghite
With the metal composite oxide of Mg/Mn/Y/Al as activity unit, described Y is Sc, Ti, V, Cr, Fe, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described Y is Zn, Co, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described Y is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～20:0～3:0～3:5, wherein, n (Mn) ≠ 0, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～15:0.3～3:0～2.5:5, wherein, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=13:1:1:5.
Houghite of the present invention is to add new metallic element on the basis of Mg/Al brucite to form ternary or four
The polynary houghite such as unit.
The preparation method of described houghite catalytic oxidant can be the conventional preparation method of houghite, such as adopt
Coprecipitation, metal salt solution is added carbonate containing and the mixed solution co-precipitation of alkali to obtain houghite compound, with class
Hydrotalcite compound is presoma, carries out calcining the houghite catalyst described in obtaining；The tool of several houghites is presented herein below
Preparation：
The preparation method of Mg/Mn/Al houghite comprises the steps：
(I) structure according to brucite, according to n (Mg2+):n(Mn2+):n(Al3+) ratio be 13:2:5.Measure corresponding
Mn (the NO of 2.04mL, 50wt%3)2Solution, weighs 14.64g Mg (NO respectively3)26H28.25g Al (the NO of O sum3)39H2O's
Amount, deionized water is made into 30mL solution, and this liquid is A liquid；According still further to c（NaOH）/[c(Mn2+)+c(Mg2+)+c(Al3+)]=
2.25, c (Na2CO3)/[c(Mn2+)+c(Mg2+)+c(Al3+)]=0.67 ratio, weigh NaOH7.92g and anhydrous respectively
Na2CO36.25g, deionized water is made into 30mL solution, and this liquid is B liquid；
(II) 5～10mL deionized water, heating in water bath to 65 DEG C are added in 250mL beaker.Then double dripping method are used just
A, B two liquid, is added drop-wise in this beaker with the speed of 10mL/min, and constant pH is 13 about, rises high-temperature to 75 DEG C about, close
Envelope, keeps static crystallization 20h of constant temperature.Then, cyclic washing, to neutral, product is dried 24h at 80 DEG C, ground 200 mesh
Sieve, obtains final product product Mn/Mg/Al brucite.Hydrotalcite product is moved in Muffle furnace in 300 DEG C of roasting 2h, obtains final product final product
Mg/Mn/Al houghite catalyst.
The preparation method of Mg/Mn/Pb/Al houghite comprises the steps：
(I) structure according to brucite, according to n（Mg2+）:n(Mn2+):n（Pb2+）:n(Al3+) ratio be 13:1:1:5.
Measure 1.02mL, the Mn (NO of 50wt%3)2Solution, weighs 1.46g Pb (NO3)2, weigh 14.64g Mg (N03)26H2O weighs
Al (the NO of 8.25g3)39H2O, deionized water is made into 30mL solution, and this liquid is A liquid；According still further to c（NaOH）/[c(Mn2+)+
n（Pb2+）+n（Mg2+）+c(Al3+)]=2.25, c (Na2CO3)/[c(Mn2+)+n（Pb2+）+n（Mg2+）+c(Al3+)]=0.67 ratio
Example, weighs NaOH7.92g and anhydrous Na respectively2CO36.25g, deionized water is made into 30mL solution, and this liquid is B liquid；
(II) in 250mL beaker add 5～10mL about deionized water, heating in water bath to 65 DEG C.Then double dripping method are used
Just A, B two liquid, is added drop-wise in this beaker with the speed of 10mL/min, and constant pH is 13 about, rises high-temperature to 75 DEG C about,
With preservative film and adhesive plaster sealed beaker mouth, keep static crystallization 20h of constant temperature.Then, cyclic washing is extremely neutral, by product in 80 DEG C
Under 24h is dried, ground 200 mesh sieves, obtain final product product Mg/Mn/Pb/Al houghite.Hydrotalcite product is moved in Muffle furnace
In 300 DEG C of roasting 2h, obtain final product final product Mg/Mn/Pb/Al houghite catalyst.
Other described various houghite preparation methoies of the present invention are same with upper, and in A liquid, total class of nitrate, proportioning are different,
Can select different nitrate that solution A be obtained as needed, the amount of sodium hydroxide is according to c (NaOH)/[metal ion in A liquid
Substance withdrawl syndrome sum]=2.25 calculating, the amount of sodium carbonate is according to c (Na2CO3In)/[A liquid, the amount of the material of metal ion is dense
Degree sum]=0.67 calculating.
The invention has the advantages that：
1st, houghite removal of mercaptans effect of the present invention projects, particularly Mg/Mn/Pb/Al, Mg/Pb/Al houghite, and
And the removal of mercaptans effect of Mg/Pb/Al houghite is beyond the effect of Mg/Mn/Al houghite removal of mercaptans.
2nd, adopt mineral Light Oil Deodorization Method of the present invention, the houghite catalyst after filtration can circulate and be used for multiple times,
Save cost.
3rd, mineral Light Oil Deodorization Method of the present invention, raw material sources are simple, simple to operate, take short.
Brief description
Fig. 1 is the influential effect curve to mineral mercaptan oxidation for the consumption adding catalyst；
Fig. 2 is the influential effect curve to mineral mercaptan oxidation for the duration of ventilation；
Fig. 3 is the influential effect curve to mineral mercaptan oxidation for the venting flow rate；
Specific embodiment
Present invention solves the technical problem that being houghite as the purposes of mercaptan-eliminating catalyst and using method.
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the composition metal of Mg/X/Al for houghite of the present invention
Oxide is activity unit, each element mol ratio n (Mg):n(X):N (Al)=10～20:0～6:5, wherein, X is Mn, Pb and Zn
In at least one, n (X) ≠ 0.
Further, it is preferable to described X is Zn, that is, houghite of the present invention is as the purposes of mercaptan-eliminating catalyst, described class
Brucite is with the metal composite oxide of Mg/Zn/Al as activity unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=12～16:0～4:5, wherein, n (Zn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=14:3:5.
Further, in houghite of the present invention, X is Zn, and described houghite also contains transition metal M, that is,
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the metal composite oxide of Mg/Zn/M/Al for houghite of the present invention
For activity unit, described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach more preferable removal of mercaptans effect, preferably described M is Co, Ni or Ti.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Zn):n(M):n
(Al)=10～20:0～3:0～3:5, wherein, n (Zn) ≠ 0, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(M):n(Al)=13:1:1:5.
In houghite of the present invention, X is Pb, and that is, houghite of the present invention is as the purposes of mercaptan-eliminating catalyst, described
Houghite is with the metal composite oxide of Mg/Pb/Al as activity unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=12～16:0～4:5, wherein, n (Pb) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=14:3:5.
In houghite of the present invention, X is also to contain transition metal N in Pb, and described houghite, i.e. the present invention
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the metal composite oxide of Mg/Pb/N/Al as activity for houghite
Unit, described N is Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described N is Zn, Co, Mn, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn or Zn.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Pb):n(N):n
(Al)=10～20:0～3:0～3:5, wherein, n (Pb) ≠ 0, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):n(Al)=13:1:1:5.
In houghite of the present invention, X is Mn, and that is, houghite of the present invention is as the purposes of mercaptan-eliminating catalyst, described
Houghite is with the metal composite oxide of Mg/Mn/Al as activity unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=12～16:0～4:5, wherein, n (Mn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13:3:5.
In houghite of the present invention, X is also to contain transition metal Y in Mn, and described houghite, i.e. the present invention
, as the purposes of mercaptan-eliminating catalyst, described houghite is with the metal composite oxide of Mg/Mn/Y/Al as activity for houghite
Unit, described Y is Sc, Ti, V, Cr, Fe, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described Y is Zn, Co, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described Y is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～20:0～3:0～3:5, wherein, n (Mn) ≠ 0, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Y):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Y):N (Al)=10～15:0.5～2:0.5～2:5.
One step ground, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Y):n(Al)=13:1:1:5.
Houghite of the present invention is based on Mg/Al houghite, adds new metallic element on its basis
The houghite being formed.
Mg/Mn/Al houghite, because manganese has bivalence, tetravalence, sexavalence and the multiple valence state of septivalency, it is as in activity
The heart, projects compared to the houghite catalytic oxidation effect that other transition metal are formed, but inventor sends out further
The catalytic oxidation effect of existing Mg/Pb/Al houghite is more preferable, far beyond the catalytic oxidation effect of Mg/Mn/Al houghite.
Houghite after present invention calcining is as mercaptan-eliminating catalyst.
Present invention mineral oil containing mercaptan product deodour method, comprises the steps：Take the x milliliter of oil product containing mercaptan, add above-mentioned
Y gram of houghite, is passed through oxidizing gas, duration of ventilation t >=10min, stops ventilation, standing, filters, after obtaining removing mercaptan
Refined oil；Wherein, y >=4%x.
The reason be passed through gas in said method is for liquid agitation and catalysis oxidation.
Mineral oil product deodorization is the mercaptan in removing mineral oil product.
Further, in order to reach more preferable removal of mercaptans effect, preferably described y >=6%x.
Further, because the amount of catalyst is in the 6% removal of mercaptans effect that can reach, tend towards stability, add more
Catalyst, removal of mercaptans effect is almost unchanged, for cost-effective, more preferably y=6～15%x.
Further, for cost-effective, preferably described y=6%x.
Further, from cost-effective consideration, preferably described oxidizing gas are air or oxygen；More preferably described oxidation
Property gas be air.
Further, due to during ventilation every liter of oil product draft speed be to reach requirement during 40L/min, it is advantageous to institute
State and be passed through oxidizing gas, gas flow rate >=40L/（min·L）；I.e. in every liter of oil product containing mercaptan, the flow velocity of ventilation is more than 40L/
min.
Further, when the speed of every liter of oil product ventilation is more than 100L/min, even if improving same period speed, the effect of removal of mercaptans
Fruit also will not be improved, it is advantageous to described be passed through oxidizing gas, gas flow rate is 40～100L/（min·L）；I.e. every liter contains
In mercaptan oil product, the flow velocity of ventilation is 40～100L/min.
Further, when the speed of every liter of oil product ventilation is 56L/min, removal of mercaptans effect basically reach best, so
Preferably described be passed through oxidizing gas, gas flow rate be 56L/（min·L）；I.e. in every liter of oil product containing mercaptan, the flow velocity of ventilation is
56L/min.
Further, because duration of ventilation is more than 20min, the effect of removal of mercaptans improves almost without further, so being
Cost-effective, preferably described duration of ventilation t=10～20min.
Further, for cost-effective, preferably described duration of ventilation t=15min.
In present invention mineral oil containing mercaptan product deodour method, above-mentioned houghite is aforesaid houghite, described class neatly
Stone with the metal composite oxide of Mg/X/Al as activity unit, each element mol ratio n (Mg):n(X):N (Al)=10～20:0～
6:5, wherein, X is at least one in Mn, Pb and Zn, n (X) ≠ 0.
Further, it is preferable to described X is Zn, that is, described houghite is with the metal composite oxide of Mg/Zn/Al as activity
Unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=12～16:0～4:5, wherein, n (Zn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Zn):n
(Al)=14:3:5.
In described houghite, X is Zn, and described houghite also contains transition metal M, that is, described houghite with
The metal composite oxide of Mg/Zn/M/Al is activity unit, and described M is Sc, Ti, V, Cr, Fe, Co, Ni or Cu.
Further, in order to reach more preferable removal of mercaptans effect, preferably described M is Co, Ni or Ti.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described M is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Zn):n(M):n
(Al)=10～20:0～3:0～3:5, wherein, n (Zn) ≠ 0, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (M) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(M):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Zn):n
(M):n(Al)=13:1:1:5.
In described houghite, X is Pb, and that is, described houghite is single for activity with the metal composite oxide of Mg/Pb/Al
Unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=12～16:0～4:5, wherein, n (Pb) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Pb):n
(Al)=14:3:5.
In described houghite, X is also to contain transition metal N in Pb, and described houghite, i.e. described houghite
With the metal composite oxide of Mg/Pb/N/Al as activity unit, described N is Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described N is Zn, Co, Mn, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn or Zn.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described N is Mn.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Pb):n(N):n
(Al)=10～20:0～3:0～3:5, wherein, n (Pb) ≠ 0, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.3～3:0～2.5:5, wherein, n (N) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):N (Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Pb):n
(N):n(Al)=13:1:1:5.
In described houghite, X is Mn, and that is, described houghite is single for activity with the metal composite oxide of Mg/Mn/Al
Unit.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=12～16:0～4:5, wherein, n (Mn) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13～15:2～4:5.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described each element mol ratio n (Mg):n(Mn):n
(Al)=13:3:5.
In described houghite, X is also to contain transition metal Y in Mn, and described houghite, i.e. described houghite
With the metal composite oxide of Mg/Mn/Y/Al as activity unit, described Y is Sc, Ti, V, Cr, Fe, Co, Ni, Cu or Zn.
Further, in order to reach more preferable removal of mercaptans effect, preferably described Y is Zn, Co, Ti or Ni.
Further, in order to reach more preferable removal of mercaptans effect, more preferably described Y is Ni.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～20:0～3:0～3:5, wherein, n (Mn) ≠ 0, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～15:0.3～3:0～2.5:5, wherein, n (Y) ≠ 0.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=10～15:0.5～2:0.5～2:5.
Further, in order to reach more preferable removal of mercaptans effect, preferably each element mol ratio n (Mg):n(Mn):n(Y):n
(Al)=13:1:1:5.
Houghite of the present invention is to add new metallic element on the basis of Mg/Al brucite to form ternary or four
The polynary houghite such as unit.
The preparation method of described houghite catalytic oxidant can be the conventional preparation method of houghite, such as adopt
Coprecipitation, metal salt solution is added carbonate containing and the mixed solution co-precipitation of alkali to obtain houghite compound, with class
Hydrotalcite compound is presoma, carries out calcining the houghite catalyst described in obtaining；The tool of several houghites is presented herein below
Preparation：
The preparation method of Mg/Mn/Al houghite comprises the steps：
(I) structure according to brucite, according to n (Mg2+):n(Mn2+):n(Al3+) ratio be 13:2:5.Measure corresponding
Mn (the NO of 2.04mL, 50wt%3)2Solution, weighs 14.64g Mg (NO respectively3)26H28.25g Al (the NO of O sum3)39H2O's
Amount, deionized water is made into 30mL solution, and this liquid is A liquid；According still further to c（NaOH）/[c(Mn2+)+c(Mg2+)+c(Al3+)]=
2.25, c (Na2CO3)/[c(Mn2+)+c(Mg2+)+c(Al3+)]=0.67 ratio, weigh NaOH7.92g and anhydrous respectively
Na2CO36.25g, deionized water is made into 30mL solution, and this liquid is B liquid；
(II) 5～10mL deionized water, heating in water bath to 65 DEG C are added in 250mL beaker.Then double dripping method are used just
A, B two liquid, is added drop-wise in this beaker with the speed of 10mL/min, and constant pH is 13 about, rises high-temperature to 75 DEG C about, close
Envelope, keeps static crystallization 20h of constant temperature.Then, cyclic washing, to neutral, product is dried 24h at 80 DEG C, ground 200 mesh
Sieve, obtains final product product Mn/Mg/Al brucite.Hydrotalcite product is moved in Muffle furnace in 300 DEG C of roasting 2h, obtains final product final product
Mg/Mn/Al houghite catalyst.
The preparation method of Mg/Mn/Pb/Al houghite comprises the steps：
(I) structure according to brucite, according to n（Mg2+）:n(Mn2+):n（Pb2+）:n(Al3+) ratio be 13:1:1:5.
Measure 1.02mL, the Mn (NO of 50wt%3)2Solution, weighs 1.46g Pb (NO3)2, weigh 14.64g Mg (N03)26H2O weighs
Al (the NO of 8.25g3)39H2O, deionized water is made into 30mL solution, and this liquid is A liquid；According still further to c（NaOH）/[c(Mn2+)+
n（Pb2+）+n（Mg2+）+c(Al3+)]=2.25, c (Na2CO3)/[c(Mn2+)+n（Pb2+）+n（Mg2+）+c(Al3+)]=0.67 ratio
Example, weighs NaOH7.92g and anhydrous Na respectively2CO36.25g, deionized water is made into 30mL solution, and this liquid is B liquid；
(II) in 250mL beaker add 5～10mL about deionized water, heating in water bath to 65 DEG C.Then double dripping method are used
Just A, B two liquid, is added drop-wise in this beaker with the speed of 10mL/min, and constant pH is 13 about, rises high-temperature to 75 DEG C about,
With preservative film and adhesive plaster sealed beaker mouth, keep static crystallization 20h of constant temperature.Then, cyclic washing is extremely neutral, by product in 80 DEG C
Under 24h is dried, ground 200 mesh sieves, obtain final product product Mg/Mn/Pb/Al houghite.Hydrotalcite product is moved in Muffle furnace
In 300 DEG C of roasting 2h, obtain final product final product Mg/Mn/Pb/Al houghite catalyst.
Other described various houghite preparation methoies of the present invention are same with upper, and in A liquid, total class of nitrate, proportioning are different,
Can select different nitrate that solution A be obtained as needed, the amount of sodium hydroxide is according to c (NaOH)/[metal ion in A liquid
Substance withdrawl syndrome sum]=2.25 calculating, the amount of sodium carbonate is according to c (Na2CO3In)/[A liquid, the amount of the material of metal ion is dense
Degree sum]=0.67 calculating.
To in Light Oil Deodorization Method containing mercaptan the consumption of catalyst, duration of ventilation, gas flow rate and catalyst repeat make
Research with number of times is as follows：
The houghite that the institute of these parameters is adopted is Mg/Mn/Al houghite catalyst, and it is as follows
It is prepared from：
(I) structure according to brucite, according to n (Mg2+):n(Mn2+):n(Al3+) ratio be 13:2:5.Measure corresponding
Mn (the NO of 2.04mL, 50wt%3)2Solution, weighs 14.64g Mg (NO respectively3)26H28.25g Al (the NO of O sum3)39H2O's
Amount, deionized water is made into 30mL solution, and this liquid is A liquid；According still further to c（NaOH）/[c(Mn2+)+c(Mg2+)+c(Al3+)]=
2.25, c (Na2CO3)/[c(Mn2+)+c(Mg2+)+c(Al3+)]=0.67 ratio, weigh NaOH7.92g and anhydrous respectively
Na2CO36.25g, deionized water is made into 30mL solution, and this liquid is B liquid；
(II) 5～10mL deionized water, heating in water bath to 65 DEG C are added in 250mL beaker.Then double dripping method are used just
A, B two liquid, is added drop-wise in this beaker with the speed of 10mL/min, and constant pH is 13 about, rises high-temperature to 75 DEG C about, close
Envelope, keeps static crystallization 20h of constant temperature.Then, cyclic washing, to neutral, product is dried 24h at 80 DEG C, ground 200 mesh
Sieve, obtains final product product Mn/Mg/Al brucite.Hydrotalcite product is moved in Muffle furnace in 300 DEG C of roasting 2h, obtains final product final product
Mg/Mn/Al houghite catalyst.
1st, the test experiments of the impact to oil product deodorization effect for the consumption of catalyst
Take the 50mL of oil product containing thiol starting material, in raw material oil product, mercaptans content is 0.15%, add Mg/Mn/Al houghite to urge
Agent, is passed through air, and air velocity is 2.8L/min, and ventilate 15min, stopped reaction, standing, and 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 impact experiment table to deodorising effect for the consumption of table 1 catalyst
| 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 of mercaptan sulfur after removal of mercaptans（wt%） | 0.16 | 0.11 | 0.07 | 0.04 | 0.03 | 0.03 | 0.02 |
Catalyst amount is to the curve chart of oil product deodorization influential effect as shown in Figure 1.Catalyst amount percent is to urge
The grams of agent/containing mercaptan oil product volume percent.
From accompanying drawing 1 and table 1, catalyst action effect substantially, adds 1% catalyst, and odorless can be smelt, and wins
Scholar's inspection is qualified；Quantitative analytical data shows, adds 4% catalyst that sulfur content in oil product can be made to drop to less than 0.03%, reaches state
Family's derv fuel standard.
2nd, the test experiments of the impact to oil product deodorization effect for the duration of ventilation
Take the 50mL of oil product containing thiol starting material, in raw material oil product, mercaptans content is 0.15%, add Mg/Mn/Al houghite to urge
Agent 2g, is passed through air, and air velocity is 2.8L/min, stopped reaction, standing, Filtration of catalyst, obtain refined oil
Product.
Carry out the test experiments of the impact to deodorising effect for the duration of ventilation according to the method described above：Result is as shown in table 2：
The impact experiment table to deodorising effect for table 2 duration of ventilation
| Test number | 1 | 2 | 3 | 4 | 5 | 6 |
| Duration of ventilation（min） | 0 | 5 | 10 | 15 | 20 | 25 |
| The content of mercaptan sulfur after removal of mercaptans（wt%） | 0.16 | 0.06 | 0.04 | 0.03 | 0.03 | 0.02 |
Duration of ventilation is to the curve chart of oil product deodorization influential effect as shown in Figure 2.
From accompanying drawing 2 and table 2, oxygen is the essential condition of mercaptan oxidation reaction, so must be passed through enough in reaction
Air, but after being passed through 15min, reaction reaches balance, then adds to no effect.So, in technique, optimal duration of ventilation is fixed on
15min.
3rd, the test experiments of the impact to oil product deodorization effect for the venting flow rate
Take the 50mL of oil product containing thiol starting material, in raw material oil product, mercaptans content is 0.15%, add Mg/Mn/Al houghite to urge
Agent 2g, is passed through air, duration of ventilation 15min, stopped reaction, standing, Filtration of catalyst, obtain refined oil.
Carry out the test experiments of the impact to deodorising effect for the venting flow rate according to the method described above：Result is as shown in table 3：
The impact experiment table to deodorising effect for table 3 venting flow rate
| Experiment numbers | 1 | 2 | 3 | 4 | 5 |
| Air velocity（L/min） | 0 | 2.5 | 5 | 7.5 | 10 |
| The content of mercaptan sulfur after removal of mercaptans（wt%） | 0.16 | 0.02 | 0.03 | 0.03 | 0.03 |
Venting flow rate is to the curve chart 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, sulfur
Alcohol sulfur is substantially oxidized（≤0.02%）, after continue to increase air mass flow, mercaptan sulfur content slightly rises on the contrary（≤
0.03%）, but it is constant to maintain this level.In view of the stability of technique, it is 5.0L/ that subsequent experimental all controls air mass flow
min.
4th, the reuse number of times test of catalyst
The reuse number of times of catalyst determines the service life of catalyst, directly affects the use cost of this catalyst
And utilization and extention.Oil volume containing mercaptan is being controlled to be 50mL, catalyst is Mg/Mn/Al houghite catalyst, and catalyst is used
Amount 2g, duration of ventilation 15min, under the experiment condition of air mass flow 2.5L/min, by same catalyst Reusability 8 times, with having
Odorless judges to deodorising effect, and experimental result is as shown in table 4.
The experimental result table of 8 times reused by table 4 catalyst
Table 4 repeats test to be proved, this catalytic oxidant can be used for multiple deodorization in oil product, first three best results, and urges
Agent no significantly sacrificing, after reusing three times, solid catalyst particle diameter attenuates it is impossible to rapid precipitation separates, necessary after 6 times
Could quantitative recovery catalyst using filter paper filtering.Show that catalyst does not dissolve in use, decomposes by this phenomenon
, simply there is catalyst dispersion in reaction, as long as energy quantitative recovery catalyst, this catalyst can be with life-time service in use.
With reference to embodiment, the specific embodiment of the present invention is further described, therefore the present invention is not limited
System is among described scope of embodiments.
The preparation of embodiment 1 houghite and mineral oil product deodorization
The preparation of Mg/Pb/Al houghite：
（Ⅰ）According to the structure of brucite, according to n (Mg2+):n(Pb2+):n(Al3+) ratio be classified as 13:2:5.Weigh
2.93gPb(NO3)2；Take the Mg (NO of 14.64g3)26H2Al (the NO of O, 8.25g3)39H2O, it is molten that deionized water is made into 30mL
Liquid, this liquid is A liquid；According still further to c（NaOH）/[c(Pb2+)+c(Mg2+)+c(Al3+)]=2.25, c (Na2CO3)/[c(Pb2+)+c
(Mg2+)+c(Al3+)]=0.67 ratio, weigh NaOH7.92g, anhydrous Na respectively2CO36.25g, deionized water is made into 30mL
Solution, this liquid is B liquid；
（Ⅱ）In 250mL beaker add 5～10mL about deionized water, heating in water bath to 65 DEG C.Then double dripping method are used
Just A, B two liquid, is added drop-wise in this beaker with the speed of 10mL/min, and constant pH is 13 about, rises high-temperature to 75 DEG C about,
With preservative film and adhesive plaster sealed beaker mouth, keep static crystallization 20h of constant temperature.Then, cyclic washing is extremely neutral, by product in 80 DEG C
Under 24h is dried, ground 200 mesh sieves, obtain final product product Mg/Pb/Al brucite.Hydrotalcite product is moved in Muffle furnace in 300
DEG C roasting 2h, obtains final product final product Mg/Pb/Al houghite catalyst；
Take the 100mL of oil product containing thiol starting material, in raw material oil product, mercaptans content is 0.15wt%, adds the Mg/ of above-mentioned preparation
Pb/Al houghite 4g, is passed through air, and air velocity is 5L/min, and ventilate 15min, stopped reaction, and standing is filtered to remove class
Brucite, obtains refined oil.
After testing：Mercaptan mass content 0.0031% in the refined oil that the present embodiment obtains.
Embodiment 2～20 mineral oil product deodorization
According to the deodour method of embodiment 1, each parameter of embodiment 2～20 is as shown in table 5 below：
The parameters table of table 5 embodiment 2～20
In table 5, the oil product 0.15wt% containing mercaptan of non-removal of mercaptans.
The preparation method of the houghite catalyst described in embodiment 2～20 is with reference to the method for embodiment 1.
Comparative example 1,2 mineral oil product deodorizations
According to the deodour method of embodiment 1, comparative example 1,2 each parameters are as shown in table 6 below：
The parameters of table 6 comparative example 1,2
In table 6, the oil product 0.15wt% containing mercaptan of non-removal of mercaptans.
The preparation method of Mg/Cu/Al, Mg/Ni/Al houghite is with reference to embodiment 1.
In above-described embodiment, the method for inspection of mercaptan is with reference to GB/T1792-1988《Mercaptan sulfur algoscopy in distillate fuel
（Potentiometric titration）》Complete.
Claims (13)
1. houghite as mercaptan-eliminating catalyst purposes it is characterised in that：Described houghite answering with Mg/Mn/Pb/Al
Conjunction metal-oxide is activity unit, each element mol ratio n (Mg):n(Pb):n(Mn):N (Al)=10～20:0～3:0～3:
5, wherein, n (Pb) and n (Mn) is all ≠ 0.
2. houghite according to claim 1 as mercaptan-eliminating catalyst purposes it is characterised in that：Described each element
Mol ratio n (Mg):n(Pb):n(Mn):N (Al)=10～15:0.3～3:0～2.5:5.
3. houghite according to claim 1 as mercaptan-eliminating catalyst purposes it is characterised in that：Described each element
Mol ratio n (Mg):n(Pb):n(Mn):N (Al)=10～15:0.5～2:0.5～2:5.
4. houghite according to claim 1 as mercaptan-eliminating catalyst purposes it is characterised in that：Described each element
Mol ratio n (Mg):n(Pb):n(Mn):N (Al)=13:1:1:5.
5. the product deodour method of mineral oil containing mercaptan it is characterised in that：Take the x milliliter of oil product containing mercaptan, add Claims 1 to 4 to appoint
Y gram of houghite described in one, is passed through oxidizing gas, duration of ventilation t >=10min, stops ventilation, standing, filters, obtain
Refined oil after removing mercaptan；Wherein, y >=4%x.
6. mineral Light Oil Deodorization Method according to claim 5 it is characterised in that：Described y >=6%x.
7. mineral Light Oil Deodorization Method according to claim 5 it is characterised in that：Described y=6～15%x.
8. mineral Light Oil Deodorization Method according to claim 5 it is characterised in that：Described y=6%x.
9. the mineral Light Oil Deodorization Method according to any one of claim 5-8 it is characterised in that：Described oxidizing gas are
Air or oxygen.
10. mineral Light Oil Deodorization Method according to claim 9 it is characterised in that：Described oxidizing gas are air.
11. mineral Light Oil Deodorization Methods according to any one of claim 5-8 it is characterised in that：Described it is passed through oxidisability
Gas flow rate >=40L/ (min L) during gas, described duration of ventilation t=10～20min.
12. mineral Light Oil Deodorization Methods according to claim 11 it is characterised in that：Described it is passed through oxidizing gas seasonal epidemic pathogens
Rate of flow of fluid is 40～100L/ (min L).
13. mineral Light Oil Deodorization Methods according to claim 11 it is characterised in that：Described it is passed through oxidizing gas seasonal epidemic pathogens
Rate of flow of fluid is 56L/ (min L), duration of ventilation t=15min.
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| CN106179294A (en) * | 2016-07-11 | 2016-12-07 | 山东师范大学 | A kind of method that hydrotalcite catalyst economic benefits and social benefits catalyze and synthesize benzazolyl compounds |
| CN111068611B (en) * | 2018-10-18 | 2022-07-12 | 中国石油化工股份有限公司 | Low-carbon olefin desulfurizing agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6497811B1 (en) * | 1998-03-13 | 2002-12-24 | Den Norske Stat Oljeselskap A.S. | Reduction of sulphur content in FCC-naphtha |
| CN101072849A (en) * | 2003-12-05 | 2007-11-14 | 英特凯特公司 | Gasoline sulfur reduction using hydrotalcite like compounds |
| CN101544908A (en) * | 2008-03-26 | 2009-09-30 | 通用电气公司 | Oxidative desulfurization of fuel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6497811B1 (en) * | 1998-03-13 | 2002-12-24 | Den Norske Stat Oljeselskap A.S. | Reduction of sulphur content in FCC-naphtha |
| CN101072849A (en) * | 2003-12-05 | 2007-11-14 | 英特凯特公司 | Gasoline sulfur reduction using hydrotalcite like compounds |
| CN101544908A (en) * | 2008-03-26 | 2009-09-30 | 通用电气公司 | Oxidative desulfurization of fuel oil |
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