CN102744054A - Catalyst for catalytic conversion of mercaptan and preparation method thereof - Google Patents
Catalyst for catalytic conversion of mercaptan and preparation method thereof Download PDFInfo
- Publication number
- CN102744054A CN102744054A CN2012102507562A CN201210250756A CN102744054A CN 102744054 A CN102744054 A CN 102744054A CN 2012102507562 A CN2012102507562 A CN 2012102507562A CN 201210250756 A CN201210250756 A CN 201210250756A CN 102744054 A CN102744054 A CN 102744054A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mercaptan
- alkali metal
- metal hydroxide
- catalyzed conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a catalyst for the catalytic conversion of mercaptan, and the catalyst is made from the following raw materials: MgO, alkali metal hydroxide and a binder. The invention also provides a preparation method of the catalyst, and the preparation method comprises the following steps of: dissolving a certain amount of alkali metal hydroxide in water to prepare water solution of the alkali metal hydroxide; evenly mixing the water solution of the alkali metal hydroxide with MgO and the binder; and carrying out molding, drying and roasting to obtain the catalyst for the catalytic conversion of mercaptan. When the catalyst provided by the invention is used for carrying out catalytic oxidation on the mercaptan in light fraction of catalytically cracked gasoline or the macromolecule mercaptan in hydrogenated gasoline, test for 35 hours proves that the catalytic conversion rate for the macromolecule mercaptan is higher than 80% and the stability of the catalyst is superior to the stability of phthalocyanine cobalt catalysts. Moreover, the catalyst provided by the invention is low in raw material cost and simple in preparation process, so that the gasoline deodorization cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of catalyst that is used for the mercaptan catalyzed conversion, relate in particular to a kind of Catalysts and its preparation method that is used for the big molecule mercaptan of catalyzed conversion, belong to the refining of petroleum product manufacture field.
Background technology
Along with the continuous development of petroleum refining industry, catalytic cracking (FCC) becomes the important means of oil deep processing day by day, in petroleum refining industry, occupies critical role.FCC technology is with light materialization of heavy oil, and target product is liquefied gas and light-end products such as gasoline, diesel oil and kerosene.In order to satisfy market growing to the light-end products demand, the FCC technology has become the main pillar of the core technology and the petrochemical enterprise economic benefit of China petroleum refining industry.
But, with containing H usually in the light-end products of FCC explained hereafter
2Sulphur compound such as S and mercaptan.The existence of these sulphur compounds can cause oil quality to descend in the FCC light-end products, has a strong impact on its serviceability.Wherein mercaptan can make light-end products produce stench, and metal is also had stronger corrosivity.In order to reduce the content of sulphur compound in the light-end products; Especially the content of FCC sulfur in gasoline compound; Oil plant generally with FCC gasoline be cut into light, weigh two kinds of cuts; Wherein olefin(e) centent is high in the light gasoline fraction, mercaptans content is low and be main with the pure and mild mercaptan relatively simple for structure of little molecular sulfur, industry in mainly the traditional alkali refining method of employing mercaptan is converted into the disulphide form it is removed; Then adopt hydrogen addition technology to remove for institute's sulfur-containing compound in the heavy naphtha.For avoiding the loss of octane number of heavy naphtha in hydrodesulfurization bigger, hydroconversion condition generally comparatively relaxes, but under the hydrodesulfurizationconditions conditions that relaxes, can generate the big molecule mercaptan of secondary in the hydrodesulfurization again (generally is C
6Above mercaptan), though big molecule mercaptan content in the heavy naphtha of handling through hydrodesulfurization is not high, its stability is very high, is difficult to remove, and the quality of hydrogasoline is a greater impact.
In the prior art, existing a large amount of about removing the report of mercaptan in the light-end products.For example; Chinese patent document CN1952051A discloses a kind of catalytic gasoline fixed bed alkaline-free sweetening method; Be specially: will remove bubbling air after catalytically cracked gasoline and the activator mix of hydrogen sulfide; Again the mixture behind the bubbling air being carried out removal of mercaptans through the removal of mercaptans oxidizing tower that the solid mercaptan-eliminating catalyst is housed handles; Wherein said activator is the mixture that alcohols, guanidine class and Titanium cyanines mix by a certain percentage, and said solid mercaptan-eliminating catalyst is by weight percentage 0.01 ~ 1% Titanium cyanines or metal to be gathered the titanium cyanines to load on the active carbon and make.
In the above-mentioned technology, the guanidine class in the activator be easy to gasoline in the complexing of big molecule mercaptan, make that the mercaptan in the gasoline is removed by titanium cyanines class catalyst more easily, have that activation effect is good, the mercaptan in the catalytically cracked gasoline removes advantage completely.But the active component of catalyst system therefor is mainly the Titanium cyanines in the above-mentioned technology, and costing an arm and a leg of these materials causes adopting such catalyst that the cost that catalytically cracked gasoline carries out deodorization is increased greatly.
People such as the Pan Guangcheng of Research Institute of Petro-Chemical Engineering are difficult for the problem of conversion to the big molecule mercaptan in the hydrogasoline; Phthalocyanine cobalt class catalyst is improved; Developed ion pair type catalyst, and the FCC gasoline that has proposed to match with hydrogen addition technology is light, heavy distillat removal of mercaptans group technology, but its catalyst that uses still be phthalocyanine cobalt class catalyst; Cost an arm and a leg, the cost that causes adopting such catalyst to carry out the deodorization processing increases greatly.
In the prior art; The catalyst that is used for the mercaptan catalyzed conversion generally selects metal phthalocyanine as active component; And those skilled in the art think that the metal phthalocyanine active component costs an arm and a leg, and cause the cost of such catalyst to increase, and how to reduce to be used for mercaptan; The cost of the catalyst that transforms in particular for big molecular sulfur alcohol catalysis so just need be sought a kind of catalytic active substance that can replace metal phthalocyanine; At present, those skilled in the art fail to solve this technical problem always.
Summary of the invention
Technical problem to be solved by this invention is in the prior art to be that the catalyst cost of active component is high with the metal phthalocyanine, so provide a kind of with low cost, effectively the catalyzed conversion sulfur in gasoline is pure, the catalyst of especially big molecule mercaptan.
In order to solve the problems of the technologies described above, the invention provides a kind of catalyst that is used for the mercaptan catalyzed conversion, process by following raw material at least: MgO, alkali metal hydroxide.
The said catalyst that is used for the mercaptan catalyzed conversion, comprise the raw material of following parts by weight: said MgO is 60 ~ 87 parts, and said alkali metal hydroxide is 10 ~ 30 parts.
Further, the said catalyst that is used for the mercaptan catalyzed conversion, comprise the raw material of following parts by weight: said MgO is 67 ~ 80 parts, and said alkali metal hydroxide is 15 ~ 25 parts.
Said raw material also comprises binding agent, and said binding agent is kaolin, bentonite or attapulgite, and wherein, in parts by weight, said binding agent is 3 ~ 10 parts.
Further, in parts by weight, said binding agent is 5 ~ 8 parts.
Further, said alkali metal hydroxide is for being potassium hydroxide or NaOH.
The present invention also further provides the said Preparation of catalysts method that is used for the mercaptan catalyzed conversion, and it comprises the steps:
(1) alkali metal hydroxide of specified quantitative is soluble in water, prepare the aqueous solution of alkali metal hydroxide;
(2) aqueous solution of above-mentioned alkali metal hydroxide and MgO or MgO, binding agent are mixed after, moulding, drying, roasting obtains the catalyst that said mercaptan transforms.
Further, the catalyst of said moulding under 90 ~ 120 ℃ of conditions, dry 2 ~ 4h, under 350 ~ 800 ℃ of conditions, roasting 3 ~ 6h obtains the catalyst that said mercaptan transforms again.
The present invention compared with prior art has following advantage:
(1) catalyst that is used for the mercaptan catalyzed conversion according to the invention is prepared by MgO and alkali metal hydroxide at least, and this activity of such catalysts position is the strong basicity center.Discover through the inventor; Be used for the catalyst that big molecular sulfur alcohol catalysis transforms; The key point of its catalytic activity is the basic center active sites of catalyst, as long as make the basic center active sites of catalyst reach certain intensity and quantity, and can be under the condition that does not have Titanium cyanines class active component; Make big molecule mercaptan dissociate into the mercaptan anion, and then make big molecule mercaptan be converted into disulphide.Because the catalyst that is used for the mercaptan catalyzed conversion according to the invention has strong basicity center active sites; It can replace the present big molecule mercaptan of phthalocyanine cobalt class catalyst oxidation; Make it be converted into disulphide, and have the effect of the excellent big molecule mercaptan of catalytic oxidation.Adopt catalyst according to the invention, the pure and mild mercaptan relatively simple for structure of little molecular sulfur in not only can catalyzed conversion gasoline, the big molecule mercaptan in especially can the catalyzed conversion hydrogasoline.Can know by evaluation result; Through the test of 35h, its catalytic conversion to big molecule mercaptan is higher than 80%, and phthalocyanine cobalt class catalyst is after the 30h test; Its catalytic conversion to big molecule mercaptan is lower than 80%, explains that the stability of catalyst according to the invention is superior to phthalocyanine cobalt class catalyst.
(2) catalyst that is used for the mercaptan catalyzed conversion according to the invention; Further limit said MgO60 ~ 87 part; 10 ~ 30 parts of said alkali metal hydroxides; The catalyst that under this conditions of mixture ratios, prepares, the basic center active sites that it has can make big molecule mercaptan dissociate into the mercaptan anion better, and then are converted into disulphide; And ought further preferred said alkali metal hydroxide be NaOH; When said NaOH and MgO co-production obtain catalyst; It has best strong basicity center active sites, can be simultaneously the pure and mild mercaptan relatively simple for structure of little molecular sulfur in the catalyzed conversion gasoline and the big molecule mercaptan in the hydrogasoline efficiently.
(3) preparation method who is used for thiols conversion catalyst according to the invention, through raw material is mixed, moulding, drying and roasting prepare this catalyst.Under sintering temperature condition according to the invention; The interaction of MgO and alkali metal hydroxide can produce enough basic center active sites; Make the catalyst for preparing replace present phthalocyanine cobalt class catalyst, the big molecule mercaptan in mercaptan in the light fractions of FCC naphtha or the hydrogasoline is carried out deodorization, have excellent mercaptan changing effect; And it is simple to adopt Preparation of catalysts method according to the invention also to have preparation technology, the advantage that preparation cost is cheap.
Description of drawings
Fig. 1 is the embodiment of the invention 3 said XRD diffraction patterns that are used for the catalyst of mercaptan catalyzed conversion;
Fig. 2 is the mass spectrogram of product dioctyl disulphide in the test case.
The specific embodiment
Below in conjunction with embodiment, the present invention is made further specific descriptions, but be not limited to this.
Embodiment 1
(1) NaOH with 10g is dissolved in the water of 15ml, prepares sodium hydrate aqueous solution;
(2) above-mentioned sodium hydrate aqueous solution and 60gMgO are mixed after, mix and pinch, extruded moulding, dry 4h under 90 ℃ of conditions, again under 350 ℃ of conditions, roasting 6h obtains the catalyst A of said mercaptan catalyzed conversion.
Embodiment 2
(1) NaOH with 15g is dissolved in the water of 20ml, prepares sodium hydrate aqueous solution;
(2) above-mentioned sodium hydrate aqueous solution and 67gMgO, 3g kaolin are mixed after, mix and pinch, extruded moulding, dry 3h under 100 ℃ of conditions, again under 500 ℃ of conditions, roasting 5h obtains the catalyst B of said mercaptan catalyzed conversion.
Embodiment 3
(1) potassium hydroxide with 20g is dissolved in the water of 25ml, prepares potassium hydroxide aqueous solution;
(2) above-mentioned potassium hydroxide aqueous solution and 75gMgO, 5g kaolin are mixed after, mix and pinch, extruded moulding, dry 2h under 120 ℃ of conditions, again under 600 ℃ of conditions, roasting 4h obtains the catalyst C of said mercaptan catalyzed conversion.
Embodiment 4
(1) potassium hydroxide with 25g is dissolved in the water of 30ml, prepares potassium hydroxide aqueous solution;
(2) above-mentioned potassium hydroxide aqueous solution and 80gMgO, 8g attapulgite are mixed after, mix and pinch, extruded moulding, dry 2.5h under 110 ℃ of conditions, again under 700 ℃ of conditions, roasting 4h obtains the catalyst D of said mercaptan catalyzed conversion.
(1) potassium hydroxide with 30g is dissolved in the water of 40ml, prepares potassium hydroxide aqueous solution;
(2) above-mentioned potassium hydroxide aqueous solution and 87gMgO, 10g bentonite are mixed after, mix and pinch, extrusion, under 120 ℃ of conditions, dry 2h, again under 800 ℃ of conditions, roasting 3h obtains the catalyst E of said mercaptan catalyzed conversion.
Catalyst performance evaluation embodiment
The phthalocyanine cobalt thiols conversion catalyst that catalyst that embodiment 1 ~ 5 is prepared and commercially available model are M-28 carries out the test evaluation of big molecular sulfur alcohol catalysis conversion performance, and test condition and test result are following:
Test condition: the n-hexane to contain the 1-spicy thioalcohol is a raw material, during beginning in the raw material mercaptan sulfur content be 871.3 μ g/g, change into when running to 11h and contain the higher n-hexane raw material of 1-spicy thioalcohol concentration, its mercaptan sulfur content is 1757 μ g/g; The fixed bed reactors internal diameter is 1.2cm; Dress dosage 6ml; Catalyst grain size 40-60 order; Volume space velocity is 3h
-1Normal pressure; Reaction temperature is 40 ℃; Air is an oxidant; Raw material and air mixed through a static mixer before getting into reactor.The mercaptan conversion ratio is lower than at 80% o'clock and stops evaluation test, and test result is as shown in table 1:
Table 1 catalyst performance evaluation test result
Can know by above-mentioned test result; The catalyst that is used for big molecular sulfur alcohol catalysis conversion according to the invention carries out catalyzed conversion to the n-hexane that contains the 1-spicy thioalcohol; After the test of 35h, its catalytic conversion to the 1-spicy thioalcohol still is higher than 80%, and commercially available M-28 phthalocyanine cobalt catalyst is after the 30h test; Its catalytic conversion to the 1-spicy thioalcohol has been lower than 80%, explains that the stability that is used for the catalyst of big molecular sulfur alcohol catalysis conversion according to the invention is superior to the M-28 catalyst.
Product in the test case is carried out application of gas chromatorgraphy/mass (GC-MS) analysis; Its mass spectrogram is as shown in Figure 2; Can know that by Fig. 2 this product is identical with the dioctyl disulfide structure, explain that the 1-spicy thioalcohol is converted into dioctyl disulphide through after the catalyst conversion according to the invention.
Obviously, the foregoing description only be for explanation clearly done for example, and be not qualification to embodiment.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here need not also can't give to all embodiments exhaustive, and the conspicuous variation of being extended out thus or the change still be among the protection domain of the invention claim.
Claims (8)
1. a catalyst that is used for the mercaptan catalyzed conversion is characterized in that, is processed by following raw material at least: MgO, alkali metal hydroxide.
2. according to the said catalyst that is used for the mercaptan catalyzed conversion of claim 1, it is characterized in that, comprise the raw material of following parts by weight: said MgO is 60 ~ 87 parts, and said alkali metal hydroxide is 10 ~ 30 parts.
3. according to the said catalyst that is used for the mercaptan catalyzed conversion of claim 2, it is characterized in that, comprise the raw material of following parts by weight: said MgO is 67 ~ 80 parts, and said alkali metal hydroxide is 15 ~ 25 parts.
4. according to claim 1 or the 2 or 3 said catalyst that are used for the mercaptan catalyzed conversion, it is characterized in that said raw material also comprises binding agent, said binding agent is kaolin, bentonite or attapulgite, and wherein, in parts by weight, said binding agent is 3 ~ 10 parts.
5. according to the said catalyst that is used for the mercaptan catalyzed conversion of claim 4, it is characterized in that in parts by weight, said binding agent is 5 ~ 8 parts.
6. according to the arbitrary said catalyst that is used for the mercaptan catalyzed conversion of claim 1 ~ 5, it is characterized in that said alkali metal hydroxide is potassium hydroxide or NaOH.
7. the arbitrary said Preparation of catalysts method that is used for the mercaptan catalyzed conversion of claim 1 ~ 6, it comprises the steps:
(1) alkali metal hydroxide of specified quantitative is soluble in water, prepare the aqueous solution of alkali metal hydroxide;
(2) aqueous solution of above-mentioned alkali metal hydroxide and MgO or MgO, binding agent are mixed after, moulding, drying, roasting obtains the catalyst of said mercaptan catalyzed conversion.
8. according to the said Preparation of catalysts method that is used for the mercaptan catalyzed conversion of claim 7, it is characterized in that, to the catalyst of moulding under 90 ~ 120 ℃ of conditions, dry 2 ~ 4h, again under 350 ~ 800 ℃ of conditions, roasting 3 ~ 6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210250756.2A CN102744054B (en) | 2012-07-19 | 2012-07-19 | A kind of catalyst for catalytic conversion of mercaptan and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210250756.2A CN102744054B (en) | 2012-07-19 | 2012-07-19 | A kind of catalyst for catalytic conversion of mercaptan and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102744054A true CN102744054A (en) | 2012-10-24 |
| CN102744054B CN102744054B (en) | 2018-02-06 |
Family
ID=47024751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210250756.2A Active CN102744054B (en) | 2012-07-19 | 2012-07-19 | A kind of catalyst for catalytic conversion of mercaptan and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102744054B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049551A (en) * | 2006-04-07 | 2007-10-10 | 大连普瑞特化工科技有限公司 | Desulfurizer with high sulfur capacity for eliminating sulfur alcohol, sulphide and hydrogen sulfide through catalytic oxidation, and preparation |
| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
-
2012
- 2012-07-19 CN CN201210250756.2A patent/CN102744054B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049551A (en) * | 2006-04-07 | 2007-10-10 | 大连普瑞特化工科技有限公司 | Desulfurizer with high sulfur capacity for eliminating sulfur alcohol, sulphide and hydrogen sulfide through catalytic oxidation, and preparation |
| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
Non-Patent Citations (1)
| Title |
|---|
| MARÍA MANRÍQUEZ-RAMÍREZ ET AL.: "Advances in the transesterification of triglycerides to biodiesel using MgO–NaOH, MgO–KOH and MgO–CeO2 as solid basic catalysts", 《CATALYSIS TODAY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102744054B (en) | 2018-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5552063B2 (en) | Desulfurization substance | |
| JP5392979B2 (en) | Selective hydrogenation process using sulfurization catalyst. | |
| CN102125846B (en) | Mercaptan etherification catalyst | |
| CN102430412B (en) | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection | |
| RU2402380C1 (en) | Catalyst for hydrofining hydrocarbon material, method of preparing said catalyst and hydrofining process | |
| US10005070B2 (en) | Bimetallic mercaptan conversion catalyst for sweetening liquefied petroleum gas at low temperature | |
| CN103055933A (en) | Hydrocracking catalyst as well as preparation method and application thereof | |
| RU2629355C1 (en) | Production method of low sulfur diesel fuel | |
| CN100434170C (en) | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method | |
| CN102500403A (en) | Liquefied gas hydrogenating, olefin content decreasing and desulfurizing catalyst and preparation method thereof | |
| WO2022038514A1 (en) | Method of light oil desulfurization in the presence of methane containing gas environment and catalyst structure | |
| CN102039154B (en) | Hydrogenation sweetening catalyst, preparing method and application thereof | |
| WO2007132857A1 (en) | Hydrorefining process | |
| RU2626400C1 (en) | Method for producing low-sulfur catalytic cracking feedstock | |
| CN101322945B (en) | Method for preparing sulphur-containing condensate oil modifying catalyst and use | |
| CN104549345B (en) | Active hydrocracking proppant and preparation method thereof | |
| CN103122256B (en) | Application of W-Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil | |
| CN104511287A (en) | A preparing method of a mercaptan etherification catalyst | |
| JP5123635B2 (en) | Method for producing gasoline base material and gasoline | |
| CN103933927A (en) | Solid desulfurizing agent and preparation method thereof | |
| CN102744054A (en) | Catalyst for catalytic conversion of mercaptan and preparation method thereof | |
| CN101434856B (en) | Gasoline desulphurization technological process | |
| RU2708643C1 (en) | Catalytic cracking gasoline hydrotreating catalyst and a method for production thereof | |
| RU2534999C1 (en) | Method of hydrofining hydrocarbon material | |
| CN102614889A (en) | Hydrotreatment catalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100080, Beijing, Haidian District people's Congress Road 33, the big line foundation building 17 floor Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |
|
| CP03 | Change of name, title or address |