CN104209085A - Adsorbent for removing thiophenic sulfides from coked gasoline and preparation method of adsorbent - Google Patents

Abstract

The invention discloses an adsorbent for removing thiophenic sulfides from coked gasoline. The adsorbent is mainly prepared from a carrier, an active component main agent, an active component auxiliary agent, a surface active agent, a template agent and a reducing agent, and is characterized in that every 100 grams of the adsorbent for removing the thiophenic sulfides from the coked gasoline comprises the following components in percentage by weight: 90-96 percent of the carrier, 1-5 percent of the active component main agent and 1-5 percent of the active component auxiliary agent; the carrier is Al2O3 with a large pore volume and a large aperture; the active component main agent is a palladium element, and the active component auxiliary agent is a copper element; the surface active agent is a non-ion amphoteric surface active agent, namely polyisobutylene succinic acid diethanolamine ester; the template agent is 100MVI lubricating oil basic oil; the reducing agent is sodium tetraborate with the concentration being 0.1-1mol/L. The adsorbent for removing the thiophenic sulfides from the coked gasoline has the characteristics of high desulfurizing depth, high sulfur capability and the like.

Description

A kind ofly remove adsorbent of thiophene-type sulfide in coker gasoline and preparation method thereof

Technical field

The present invention relates to a kind of support type desulfuration adsorbent, particularly relate to a kind of to adsorbent removing thiophene-type sulfide in coker gasoline and preparation method thereof.

Background technology

Coker gasoline is the light-end products that heavy oil residue is produced through delay coking process.Owing to containing a large amount of non-hydrocarbon compounds containing N, O, S element in heavy oil residue, these non-hydrocarbon compounds also enter in different fraction oil with the difference of boiling point.Coker gasoline is often containing a large amount of non-hydrocarbon compound, and octane number is lower, does not often use as vehicle fuel, but as preparing the cracking stock of ethene.Due to the sour crude that a large amount of import of China is external, it is higher that this just causes sulfur content in the product of crude oil after processing, and the sulfur content especially in coker gasoline is higher.Coker gasoline must carry out desulfurization before using as cracking stock, and sulfur content is reduced to certain level.The method of desulfurization depends on kind and the character of institute's sulfur-containing compound in coker gasoline.Sulfur-containing compound in coker gasoline can be divided into heterocyclic and non-heterocyclic sulfur-containing compound, non-heterocycle compound mainly comprises mercaptan, thioether and disulphide, its boiling point is lower, the lone pair electrons Midst density of sulphur atom is larger, C-S key is more weak, therefore, hydrodesulfurizationprocess process is adopted just easily to remove.Heterocyclic sulfide mainly comprises the substituent of thiophene and alkyl or phenyl thereof, such as, and benzothiophene, dibenzothiophenes, methyldibenzothiophene and 4,6-dimethyl benzothiophene etc.For the compound of thiophene-based, substituted radical is more, and structure is more complicated, and owing to forming stable conjugated structure between the lone pair electrons on sulphur atom and the pi-electron in thiphene ring, hydrogenation activity is very low, its catalytic hydrogenation sterically hindered also larger.So catalytic hydrogenation is difficult to polysubstituted benzothiophene to remove.

Up to the present, the desulfur technology of industrial comparative maturity is hydrodesulfurization (HDS), this technology can remove non-heterocycle compound in coker gasoline effectively, sulfur content is made to be reduced to certain level, but it is very difficult to removing of the heterocyclic thiophenes sulfides in coker gasoline, very low level is reduced to make the sulfur content in coker gasoline, the cost that hydrogen consumption then in hydrogenation process, equipment investment and operating cost are brought sharply rises, and which also limits further developing of hydrodesulfurization.Therefore, be difficult to for hydrodesulfurization the research focus that green technology-adsorption desulfurize method that the thiophene-type sulfide that removes and derivative thereof carry out deep desulfuration becomes numerous researcher.Adsorption desulfurize method is a kind of effective ways removing organic sulfur compound in liquid phase, and the method, by there is strong interaction between the sulphur atom in adsorbent and sulfur-containing compound, is fixed sulfide on the sorbent, reached the object of desulfurization.The process of adsorption desulfurize can be carried out at ambient temperature and pressure, have operating condition gentleness, plant investment few, simple to operate, to advantages such as the characteristics influence of oil product are little.And if the hydrodesulfurization technology run at present is connected, and mutually supplements, very likely obtains more wide industrial prospect.

Pd/Al ₂o ₃it has been known method that adsorbent removes the organic sulfurs such as thiophene, in order to increase the adsorption capacity (Sulfur capacity) of the thiophene-type sulfide of adsorbent, not only to improve the content of Pd on adsorbent, also will consider that the pore volume of adsorbing agent carrier and the distribution situation in aperture are to increase the Sulfur capacity of adsorbent.Existing Pd/Al ₂o ₃sorbent preparation method is infusion process mainly, and be the known use of chemical industry, although the adsorbent utilizing infusion process to prepare has good adsorption desulfurize rate, but Sulfur capacity is less and can not regenerate, cause adsorbent in use to be changed comparatively frequent, cost is higher.

Super solubilising reverse micelle method is a kind of method that preparation has large pore volume and aperture catalyst.Compare with the infusion process that distributes with traditional uniform wet infusion process, the pore volume of the adsorbent that the method is prepared and aperture are comparatively large, and between mesoporous and macropore, the adsorbent activity composite distribution prepared is concentrated, decentralization high.Therefore obviously can increase the activated adoption position of adsorbent, the large pore volume of carrier and aperture add effective Sulfur capacity of adsorbent, extend the absorption life-span.

Summary of the invention

Object of the present invention, is to provide a kind of adsorbent removing thiophene-type sulfide in coker gasoline, the features such as it is high that this adsorbent has desulfurization depth, and Sulfur capacity is large.

Another object of the present invention, is to provide a kind of preparation method removing the adsorbent of thiophene-type sulfide in coker gasoline.

The technical scheme adopted is:

Remove an adsorbent for thiophene-type sulfide in coker gasoline, it is characterized in that:

Every 100g removes in the adsorbent of thiophenes sulfides in coking oil, by percentage to the quality containing carrier 90-96%, active constituent host 1-5%, active constituent auxiliary agent 1-5%:

Described carrier is pore volume 1.011-2.512cm ³the Al of/g and aperture 12.0-55.7nm ₂o ₃, active constituent host is palladium element, active constituent auxiliary agent is copper.

Remove a preparation method for the adsorbent of thiophene-type sulfide in coker gasoline, it is characterized in that comprising the steps:

1., by ester acid palladium 2-4g, stannous chloride 1-4g, nine water aluminum nitrate 690-720g and urea 120-500g mix, be under agitation heated to 120 DEG C of fusings, form eutectic, for subsequent use;

2., by the polyisobutylene succinic acid triethanolamine ester 30-200mL of 0.02-0.1mol/L and the mixing of 0.1-0.25mol/L 100MVI lubricating oil 10-200mL base oil, be heated to 120 DEG C under agitation, form homogeneous oil phase, for subsequent use;

3. the eutectic, by step 1. obtained is added in the oil phase that 2. step prepared, and is uniformly mixed under 120 DEG C of conditions, forms titania nanoparticle, for subsequent use;

4. ethanol solution of sodium borohydride 150-500mL is dripped in the titania nanoparticle, by step 3. prepared, reduction palladium and copper;

5., by step 4. in super hydrotrope after reduction palladium and copper load in autoclave, 2-5hr is reacted at 150 DEG C of temperature, wash, centrifugation (2000-5000r/min), dry (100-120 DEG C, 12-24hr) mix with the dust technology 30-80mL of adhesive 0.05-0.1mol/L afterwards, adopt extrusion method to be processed into stripe shape, obtain sorbent precursor body;

6. the sorbent precursor body, by step 5. obtained adds in Muffle furnace, and under nitrogen atmosphere protection, 500-650 DEG C is carried out roasting, and roasting 5-6hr, to obtain final product.

Advantage of the present invention is:

The present invention is for the preparation of a kind of adsorbent removing thiophene-type sulfide in coker gasoline, adsorbent prepared by the method can remove most of thiophene-type sulfide in coker gasoline effectively by chemisorbed, and the thiophene-type sulfide content of the coker gasoline after adsorption treatment significantly declines.Adsorbent adopts super solubilising reversed phase micelle, after being dissolved in low temperature organic molten salt forming common melt body by palladium, stannous chloride, aluminum nitrate, add non-ionic surface active agent and template, under the reducing condition of borane reducing agent sodium hydride, make the sorbent precursor body of the thiophene-type sulfide of support type, then make to wash with water, centrifugation, drying, the method such as shaping processes, last active constituent of can preparing after roasting in nitrogen atmosphere distributes concentrated, the adsorbent that high, the effective Sulfur capacity of decentralization is large.

Detailed description of the invention

Embodiment 1

With containing the palladium (Pd (CH being equivalent to 2g Pd ₃cOO) ₂), be equivalent to 1g Cu stannous chloride (CuCl) and be equivalent to nine water aluminum nitrates of 97 grams of aluminium oxide and urea 150g and be heated to 120 DEG C and be uniformly mixed formation eutectic, above-mentioned eutectic is joined containing 0.05mol/L non-ionic surface active agent polyisobutylene succinic acid triethanolamine ester 40mL and 0.1mol/L 100MVI lube base oil 20mL, be uniformly mixed in the homogeneous oil phase of formation, rapid stirring 1hr, dropwise drips the NaBH of 0.5mol/L ₄ethanolic solution 300mL, is added dropwise to complete rear continuation and stirs 4hr.To surpass hydrotrope after stirring loads in autoclave, at 150 DEG C of reaction 2-5hr.Reaction terminates afterproduct and obtains sorbent precursor body through washing 3 times, centrifugation (2800r/min), dry (10 DEG C, 12hr) and bonding (0.05mol/L, 50mL) extruded moulding.Finally by presoma nitrogen atmosphere protect under in Muffle furnace with 10 DEG C/min ramp to 550 DEG C, maintain this temperature 6hr, finished product adsorbent can be obtained.

Performance of the adsorbent is evaluated

Fixed bed reactors enter adsorption desulfurize performance evaluation to adsorbent of the present invention.Under normal temperature and pressure conditions, it is 200mm that the thiophene-type sulfide adsorbent of preparation is filled into length, internal diameter is in the adsorption column of 15mm, double plunger measuring pump is used to make it flow through adsorption bed from bottom to top the coker gasoline pressurization after process, in reactor, adsorptive pressure is 0.5MPa, adsorption temp is 100-150 DEG C, and air speed is 2.0 h ^-1, timing collects efflux in exit, uses the content of thiophene-type sulfide in gas chromatographic analysis sample, and calculate the removal efficiency of thiophene-type sulfide, adsorption assessment is in table 1.

Embodiment 2

The host of adsorbent uses containing the palladium (Pd (CH being equivalent to 2g Pd ₃cOO) ₂), auxiliary agent is equivalent to the nine water aluminum nitrates that the stannous chloride (CuCl) of 2g Cu and carrier are equivalent to 96g aluminium oxide, the preparation process of adsorbent is with example 1, and last sintering temperature is 600 DEG C.

This adsorbent such as method of testing in embodiment 1 is evaluated and tested, and its evaluation result is in table 1.

Embodiment 3

The host of adsorbent uses containing the palladium (Pd (CH being equivalent to 5gPd ₃cOO) ₂), auxiliary agent is equivalent to the nine water aluminum nitrates that the stannous chloride (CuCl) of 1g Cu and carrier are equivalent to 94g aluminium oxide, the preparation process of adsorbent is with example 1.

This adsorbent such as method of testing in embodiment 1 is evaluated and tested, and its evaluation result is in table 1.

Embodiment 4

The host of adsorbent uses containing the palladium (Pd (CH being equivalent to 2gPd ₃cOO) ₂), auxiliary agent is equivalent to the nine water aluminum nitrates that the stannous chloride (CuCl) of 4g Cu and carrier are equivalent to 94g aluminium oxide, the preparation process of adsorbent is with example 1, and last sintering temperature is 600 DEG C.

This adsorbent such as method of testing in embodiment 1 is evaluated and tested, and its evaluation result is in table 1.

Table 1 desulfurized effect table

Project	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Sulfide removal efficiency (%)	89	85	92	80
Effective Sulfur capacity (g/kg adsorbent)	2.06	1.74	2.27	1.35

Claims (2)

1. remove an adsorbent for thiophene-type sulfide in coker gasoline, it is characterized in that:

Every 100g removes in the adsorbent of thiophenes sulfides in coking oil, by percentage to the quality containing carrier 90-96%, active constituent host 1-5%, active constituent auxiliary agent 1-5%;

Described carrier is pore volume 1.011-2.512cm ³the Al of/g and aperture 12.0-55.7nm ₂o ₃, active constituent host is palladium element, active constituent auxiliary agent is copper.

2. remove a preparation method for the adsorbent of thiophene-type sulfide in coker gasoline, it is characterized in that comprising the steps:

1., by ester acid palladium 2-4g, stannous chloride 1-4g, nine water aluminum nitrate 690-720g and urea 190-500g mix, be under agitation heated to 120 DEG C of fusings, form eutectic, for subsequent use;

2., by 0.02-0.1mol/L polyisobutylene succinic acid triethanolamine ester 30-200mL and 0.1-0.25mol/L 100MVI lube base oil 10-200mL mix, be heated to 120 DEG C under agitation, form homogeneous oil phase, for subsequent use;

3. the eutectic, by step 1. obtained is added in the oil phase that 2. step prepared, and is uniformly mixed under 120 DEG C of conditions, forms titania nanoparticle, for subsequent use;

4. ethanol solution of sodium borohydride 150-500mL is dripped in the titania nanoparticle, by step 3. prepared, reduction palladium and copper;

5., by step 4. in super hydrotrope after reduction palladium and copper load in autoclave, 2-5hr is reacted at 150 DEG C of temperature, wash, centrifugation, centrifuge revolution is 2000-5000r/min, at 100-120 DEG C, mixes after dry 12-24hr with the dust technology 30-80mL of adhesive 0.05-0.1mol/L, adopt extrusion method to be processed into stripe shape, obtain sorbent precursor body;

6. the sorbent precursor body, by step 5. obtained adds in Muffle furnace, and under nitrogen atmosphere protection, 500-650 DEG C is carried out roasting, and roasting 5-6hr, to obtain final product.