CN103920455B - The preparation method of a kind of high activity and high-wearing feature microphere sulfur transfer agent - Google Patents
The preparation method of a kind of high activity and high-wearing feature microphere sulfur transfer agent Download PDFInfo
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Abstract
The invention discloses the preparation method of the microphere sulfur transfer agent of a kind of high activity and high-wearing feature, inorganic binder is put into phosphoric acid or ammonium phosphate salt solution floods, after taking-up, obtain the modified binder being coated with continuous aluminophosphates layer after drying; Then mix after adding prepared modified binder in the final step preparing microphere sulfur transfer agent, after drying, roasting, obtain sulfur transfer additive.Continuous print aluminophosphates clad can improve the active component content in sulfur transfer additive, obtains the sulfur transfer additive of high adsorption activity; And aluminophosphates is converted into phosphorus pentoxide by final calcination steps, the wear resistence of sulfur transfer additive is improved.This microphere sulfur transfer agent is mainly applicable in catalytic cracking FCC apparatus, to match incompatible catalytic cracking mink cell focus component with catalyst, the oxygen sulfur compound generated in the adsorbable cracking process of this microphere sulfur transfer agent, to reduce the harm of oxygen sulfur compound to equipment, environmental and human health impacts.
Description
Technical field
The present invention relates to a kind of preparation method having the microphere sulfur transfer agent of high activity and high-wearing feature concurrently, belong to catalyst preparation technical field.
Background technology
Along with the increase of yield, the petroleum reserves of China is constantly reducing and in oil, the ratio of mink cell focus, also in continuous increase, because mink cell focus can not directly use, therefore needs to carry out catalytic cracking to obtain available light oil composition to mink cell focus.
The FCC apparatus that mink cell focus catalytic cracking uses is made up of riser and regenerator usually, during production, first by catalyst mink cell focus, pyrolytic cracking occurs in riser to react, mink cell focus is transformed into light oil in cracking process, simultaneously catalyst also coking and deactivation; Afterwards, the catalyst of inactivation enters in regenerator and carries out high temperature regeneration; Because the petroleum sulfur of China's exploitation is very high, containing a large amount of sulphur compounds in the coking layer of thus inactivation rear catalyst, when the catalyst after inactivation enter regenerate in regenerator time, sulphur compound at high temperature can generate a large amount of oxygen sulfur compounds, comprises sulfur dioxide and sulfur trioxide.The oxygen sulfur compound one side meeting generated be reacted with the water in regeneration product and be formed acid, produces corrosion to equipment, can pass through on the other hand to discharge the harm caused environment and human health, so need the oxygen sulfur compound to generating to process.
At present, usually by allocating a small amount of sulfur transfer additive in catalyst into, oxygen sulfur compound is processed.In regenerator, Sulphur Dioxide can be sulfur trioxide and sulfur trioxide be adsorbed on its surface to form metal sulfate by sulfur transfer additive, area load has the sulfur transfer additive of metal sulfate together to enter in riser again carry out catalytic cracking reaction with the catalyst of regeneration afterwards, after reaction, the metal sulfate on sulfur transfer additive surface can be reduced to hydrogen sulfide, sulfur transfer additive have also been obtained regeneration simultaneously, the hydrogen sulfide produced can be discharged with crackate and recycle in retracting device through separated and collected, thus decreases the harm that oxygen sulfur compound causes.
Sulfur transfer additive mainly comprises solid and liquid two kinds of forms, low and be conducive to the performance and the form that keep catalyst because the regeneration of solid sulfur transfer agent is convenient, to matching requirements, thus uses more.In recent years, researcher finds that the spinel composition of alkaline-earth metal and aluminium has excellent adsorption and desorption performance for sulphur, therefore have developed the sulfur transfer additive of a large amount of spinelles or spinel-like system.But in use, above-mentioned sulfur transfer additive easily weares and teares because of the collision between sulfur transfer additive particle or between sulfur transfer additive particle and the wall of equipment, causes the problem that the total amount of sulfur transfer additive reduces, sulphur transfer effect is not good.
In order to solve the problems of the technologies described above, Chinese periodical " nonmetallic ore " volume the 4th phase 19-21 page July the 25th in 2002 discloses one using the kaolin of acidification as catalytic cracking and desulfurizing additive base Quality Research, after kaolin mixes with phosphoric acid by by a certain percentage, 14h is processed under the acidulated condition of pH=1-3, then by the sample drying after process, roasting 30-90min at 600-800 DEG C again, obtain the activity of metakaolin auxiliary agent containing B acid and L acid, above-mentioned coagent being added to basic proportioning is 10%Ce/MgAl
1.8fe
0.2o
4prepare sulfur transfer additive in the spinelle of MgO, improve the wear resistence of sulfur transfer additive.Coagent Surface coating prepared by above-mentioned technology has P
2o
5, thus improve the wear resistence of coagent, the coagent with wear resistence is joined in spinelle and prepares sulfur transfer additive, make the wear resistence of sulfur transfer additive have also been obtained raising.But, in the process preparing coagent, although the activity of metakaolin auxiliary agent surface obtained after roasting is sour containing some B and the active sites of L acid, but the activity being added with the sulfur transfer additive of this coagent is still very low, in use effectively cannot adsorb and remove the oxygen sulfur compound in FCC apparatus, and for the problem that above-mentioned technology sulfur transfer additive active is low, those skilled in the art fail to find suitable solution always.
Summary of the invention
Although the sulfur transfer additive that technical problem to be solved by this invention is prior art to be prepared has high-wearing feature, and its coagent has certain activity, but the activity of this sulfur transfer additive is still very low, cannot effectively remove the oxygen sulfur compound produced in cracking process; And then the preparation method of microphere sulfur transfer agent of a kind of high activity and high-wearing feature is proposed.
For solving the problems of the technologies described above, the invention provides the preparation method of the microphere sulfur transfer agent of a kind of high activity and high-wearing feature, comprising
(1) inorganic binder is put into phosphoric acid or ammonium phosphate salt solution floods, after taking-up, obtain modified binder after drying;
(2) in boehmite suspension, add acid to carry out being mixed to get gel, the suspension adding heavy-burned magnesia in above-mentioned gel mixes, and obtains mixed liquor;
(3) mix after adding cerium salt, vanadic salts and complex acid solution successively in above-mentioned mixed liquor, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, namely slurry dried, roasting are obtained the sulfur transfer additive of high activity and high-wearing feature.
The mass ratio of described inorganic binder and phosphoric acid or ammonium phosphate salt is (4.5-5): 1.
The concentration of described phosphoric acid or ammonium phosphate salt solution is 4-10wt%, and dip time is 12-14h.
Baking temperature in step (1) is 100-150 DEG C.
Described inorganic binder is one or more in kaolin, the sweet soil of sheep, bentonite and rod soil.
Described phosphate is one or more in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and diammonium hydrogen phosphate.
The mol ratio of described boehmite and acid is (0.43-0.45): 1, and the concentration of described boehmite suspension is 10-12wt%, and the concentration of described acid is 30-36wt%, and described acid is one or more in hydrochloric acid, nitric acid and glacial acetic acid.
The addition of described heavy-burned magnesia is the 0.62-0.64wt% of described boehmite addition, and the turbid liquid concentration of described heavy-burned magnesia is 10-12wt%.
With molar amount, described cerium salt addition is the 7-8% of described boehmite addition, and described vanadic salts addition is the 4-5% of described boehmite addition, and described complex acid addition is the 19-20% of described boehmite addition; The concentration of described complex acid solution is 33-35wt%.
Described modified binder addition is the 36-37wt% of described boehmite addition.
Baking temperature in step (4) is 400-500 DEG C, and sintering temperature is 600-700 DEG C.
Described cerium salt is one or more in cerous nitrate, cerous sulfate and cerium chloride, and described vanadic salts is ammonium metavanadate or ammonium poly-vanadate, and described complex acid is oxalic acid or citric acid.
The present invention has following beneficial effect compared with prior art:
(1) preparation method of the microphere sulfur transfer agent of high activity of the present invention and high-wearing feature, comprises and inorganic binder is put into phosphoric acid or ammonium phosphate salt solution floods, obtain modified binder after drying after taking-up; Add mixing after the modified binder prepared, dry, roasting in the final step preparing sulfur transfer additive, obtain the microphere sulfur transfer agent with high activity and high-wearing feature.
The applicant of the application finds in inorganic binder after deliberation usually containing aluminium oxide and silica, when preparing sulfur transfer additive, because inorganic binder directly can contact with other raw materials of sulfur transfer additive, silica in inorganic binder easily reacts with the raw material and magnesia that form spinelle, thus easily cause minimizing, the minimizing of activated adoption centric quantity of spinelle and MgO activity component in final sulfur transfer additive, the activity of sulfur transfer additive is reduced.Inorganic binder is first immersed in phosphoric acid or ammonium phosphate salt solution by the present invention, drying can obtain the inorganic binder that outer surface is coated with one deck aluminophosphates material again, because the dry run of low temperature is little for the destructiveness of this clad, thus the defect of aluminophosphates clad is less, this aluminophosphates clad can reduce silica in inorganic binder and spinel charge and magnesian contact probability effectively, thus the probability that silica and spinel charge and magnesia reacts can be reduced, make the content of spinelle and MgO activity component in the sulfur transfer additive finally obtained very high, aluminophosphates clad is made to change P into finally by roasting
2o
5, and then obtain the sulfur transfer additive with high activity and high-wearing feature.
In prior art, although the kaolin outer surface after high-temperature roasting is coated with P
2o
5wear resistence material, but high-temperature calcination process heavy damage P
2o
5the continuity of clad, makes P
2o
5defect on clad is a lot, and a large amount of stripping of Alumina from Kaolin after high-temperature roasting, and the content of silica is very high, and the silica of high-load is easily via P
2o
5the defect stripping of clad and the raw material of spinelle and magnesia react, and because this reducing the content of active component in sulfur transfer additive, the activity of sulfur transfer additive are reduced.Although kaolin has certain activity after changing metakaolin in prior art, the activity of metakaolin is compared active component and is wanted much weak, cannot play Main Function for the raising of sulfur transfer additive active.Therefore, the preparation method of microphere sulfur transfer agent of the present invention avoids above-mentioned defect of the prior art, finally can obtain the sulfur transfer additive of high activity and high-wearing feature.
(2) preparation method of the microphere sulfur transfer agent of high activity of the present invention and high-wearing feature, the mass ratio of described inorganic binder and phosphoric acid or ammonium phosphate salt is (4.5-5): 1.The concentration of described phosphoric acid or ammonium phosphate salt solution is 4-10wt%, and dip time is 12-14h.Inorganic binder and phosphoric acid or ammonium phosphate salt is kept to mix with certain part by weight, and inorganic binder is immersed in certain density phosphoric acid or ammonium phosphate salt solution keep a period of time, the coated with uniform of inorganic binder can be made to have there is certain thickness aluminophosphates layer, thus improve its buffer action, the silica in inorganic binder and spinel charge and magnesia is avoided to react, finally obtain the sulfur transfer additive that active component content is high, and the calcination steps in step (4) can obtain the sulfur transfer additive of high-wearing feature.
(3) preparation method of the microphere sulfur transfer agent of high activity of the present invention and high-wearing feature, described modified binder addition is the 36-37wt% of described boehmite addition.Keep the addition of modified binder and boehmite within the scope of certain proportion, while boehmite and other raw materials and modified binder strong bonded can be made, make the surface uniform of prepared sulfur transfer additive have wear resistence.
Detailed description of the invention
Embodiment 1
(1) phosphoric acid 45g kaolin being put into 250g, 4wt% floods 12h, obtains modified binder after taking-up after 100 DEG C of dry 5h;
(2) hydrochloric acid adding 486g, 30wt% in the boehmite suspension of 1223g, 10wt% carries out being mixed to get gel, the heavy-burned magnesia suspension adding 7.6g, 10wt% in above-mentioned gel mixes, obtain mixed liquor, the magnesia containing 80wt% in the heavy-burned magnesia added;
(3) mix add the oxalic acid solution of the cerous nitrate of 52g, 8g ammonium metavanadate and 89g, 33wt% successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in step described in 44g (1) obtained modified binder mix and obtain slurries, by slurries at 400 DEG C of dry 5h, again at 600 DEG C of roasting 5h, namely obtain the sulfur transfer additive 1 of high activity and high-wearing feature.
Embodiment 2
(1) ammonium phosphate that sweet for 50g sheep soil puts into 100g, 10wt% is flooded 14h, after taking-up, after 150 DEG C of dry 4h, obtain modified binder;
(2) nitric acid adding 700g, 36wt% in the boehmite suspension of 1067g, 12wt% carries out being mixed to get gel, the heavy-burned magnesia suspension adding 6.8g, 12wt% in above-mentioned gel mixes, obtain mixed liquor, the magnesia containing 90wt% in the heavy-burned magnesia added;
(3) mix add the citric acid solution of the cerous sulfate of 58g, 54g ammonium poly-vanadate and 197g, 35wt% successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in step described in 47g (1) obtained modified binder mix and obtain slurries, by slurries at 500 DEG C of dry 4h, again at 700 DEG C of roasting 4h, namely obtain the sulfur transfer additive 2 of high activity and high-wearing feature.
Embodiment 3
(1) ammonium hydrogen phosphate 47g bentonite being put into 125g, 8wt% floods 13h, obtains modified binder after taking-up after 120 DEG C of dry 5h;
(2) glacial acetic acid adding 750g, 32wt% in the boehmite suspension of 1138g, 11wt% carries out being mixed to get gel, the heavy-burned magnesia suspension adding 7.2g, 11wt% in above-mentioned gel mixes, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the citric acid solution of the cerium chloride of 32g, 47g ammonium poly-vanadate and 193g, 34wt% successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in step described in 45g (1) obtained modified binder mix and obtain slurries, by slurries at 450 DEG C of dry 4h, again at 650 DEG C of roasting 4h, namely obtain the sulfur transfer additive 3 of high activity and high-wearing feature.
Embodiment 4
(1) diammonium hydrogen phosphate 40g rod soil being put into 50g, 20wt% floods 10h, obtains modified binder after taking-up after 100 DEG C of dry 5h;
(2) glacial acetic acid adding 700g, 30wt% in the boehmite suspension of 1000g, 10wt% carries out being mixed to get gel, in above-mentioned gel, add 8, the heavy-burned magnesia suspension of 10wt% mixes, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the citric acid solution of the cerium chloride of 30g, 45g ammonium poly-vanadate and 150g, 40wt% successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in step described in 38g (1) obtained modified binder mix and obtain slurries, by slurries at 500 DEG C of dry 4h, again at 650 DEG C of roasting 4h, namely obtain the sulfur transfer additive 4 of high activity and high-wearing feature.
Embodiment 5
(1) mixed solution sweet for 10g sheep soil and 20g bentonite being put into the ammonium dibasic phosphate solution of 15g, 10wt% and the phosphoric acid solution of 15g, 10wt% floods 14h, obtains modified binder after taking-up after 150 DEG C of dry 1h;
(2) nitric acid of the hydrochloric acid and 10ml, 10wt% that add 10ml, 10wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the cerous nitrate of 39.6g, 6.4g ammonium metavanadate, the oxalic acid of 13.6g and the distilled water of 160g successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains the sulfur transfer additive 5 of high activity and high-wearing feature.
Embodiment 6
(1) phosphoric acid solution 26.8g rod soil being put into 27g, 10wt% floods 14h, obtains modified binder after taking-up after 150 DEG C of dry 1h;
(2) hydrochloric acid adding 10ml, 20wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the distilled water of the cerous nitrate of 19.6g, the cerous sulfate of 21g, 5.4g ammonium metavanadate, the ammonium poly-vanadate of 5g, the oxalic acid of 13.6g and 160g successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains the sulfur transfer additive 6 of high activity and high-wearing feature.
Embodiment 7
(1) phosphoric acid solution 20g bentonite being put into 31g, 15wt% floods 14h, obtains modified binder after taking-up after 150 DEG C of dry 1h;
(2) hydrochloric acid adding 10ml, 20wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the cerous nitrate of 39.6g, 6.4g ammonium metavanadate and the oxalic acid of 13.6g and the distilled water of 160g successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains the sulfur transfer additive 7 of high activity and high-wearing feature.
Embodiment 8
(1) phosphoric acid solution 26.8g kaolin being put into 54g, 20wt% floods 14h, obtains modified binder after taking-up after 150 DEG C of dry 1h;
(2) hydrochloric acid adding 10ml, 20wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the cerous nitrate of 39.6g, 6.4g ammonium metavanadate and the oxalic acid of 13.6g and the distilled water of 160g successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains the sulfur transfer additive 8 of high activity and high-wearing feature.
Comparative example 1
(1) hydrochloric acid adding 10ml, 20wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(2) mix add the cerous nitrate of 39.6g, 6.4g ammonium metavanadate and the oxalic acid of 13.6g and the distilled water of 160g successively in above-mentioned mixed liquor after, obtain mixture;
(3) kaolin adding 26.8g in said mixture mixes and obtains slurries, and slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains sulfur transfer additive I.
Comparative example 2
(1) phosphoric acid solution 26.8g kaolin being put into 54g, 20wt% floods 14h, after taking-up after 150 DEG C of dry 1h, then obtains wear-resistant binding agent after roasting 60min at 700 DEG C;
(2) hydrochloric acid adding 10ml, 20wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the cerous nitrate of 39.6g, 6.4g ammonium metavanadate and the oxalic acid of 13.6g and the distilled water of 160g successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in described step (1) obtained wear-resistant binding agent mix and obtain slurries, slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains sulfur transfer additive II.
Comparative example 3
(1) phosphoric acid solution 26.8g kaolin being put into 54g, 20wt% floods 14h, after taking-up after 150 DEG C of dry 1h, after grinding, obtains modified binder;
(2) hydrochloric acid adding 10ml, 20wt% in the boehmite suspension of 612g, 10wt% carries out being mixed to get the gel that pH value is 2, the distilled water adding 49.2g heavy-burned magnesia and 360g in above-mentioned gel carries out stirring 2h, obtain mixed liquor, the magnesia containing 85wt% in the heavy-burned magnesia added;
(3) mix add the cerous nitrate of 39.6g, 6.4g ammonium metavanadate and the oxalic acid of 13.6g and the distilled water of 160g successively in above-mentioned mixed liquor after, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, slurries are carried out spraying dry at 500 DEG C, then in 650 DEG C of roasting 4h, screening, namely obtains sulfur transfer additive III.
Test case
(1) abrasion index of microphere sulfur transfer agent measures:
Be positioned over respectively in abrasion index tester by microphere sulfur transfer agent prepared by embodiment 1-8 and comparative example 1-3 and test, the measurement result of abrasion index sees the following form.
It should be noted that, the abrasion index tester used is the MS-D type instrument that Shenyang Memec instrument and meter Manufacturing Co., Ltd produces, and any commercially available abrasion index determinator of every equipment requirement manufacture required for RIPP29-90 microballoon Cracking catalyst abrasion index determination method is equally applicable to this test.
(2) adsorption and desorption of microphere sulfur transfer agent measures:
Microphere sulfur transfer agent prepared by embodiment 1-8 and comparative example 1-3 is tested as sample.Get the crucible that thermal analyses balance put into by 5mg sample, pass into nitrogen with the speed of 40ml/min to sample surfaces, be simultaneously warming up to 700 DEG C with the speed of 20 DEG C/min and after constant temperature 30min, recording quality m
0; Then 5v%SO is passed into the speed of 40ml/min to sample surfaces
2, 50v%O
2and 45v%N
2mist adsorb, and after keeping 700 DEG C of constant temperature 1h, record m
1; Finally pass into 30v%H with the speed of 40ml/min to sample surfaces
2and 70v%N
2mist carry out reduction desorption, and after keeping 700 DEG C of constant temperature 1h, record m
2.According to following formulae discovery sample adsorption rate and sample desorption rate, the results are shown in following table.
| Microphere sulfur transfer agent | Abrasion index (%/h) | Sample adsorption rate | Sample desorption rate |
| Sulfur transfer additive 1 | 2.10 | 63% | 99.0% |
| Sulfur transfer additive 2 | 2.32 | 65% | 98.5% |
| Sulfur transfer additive 3 | 2.09 | 61% | 99.2% |
| Sulfur transfer additive 4 | 2.18 | 58% | 99.1% |
| Sulfur transfer additive 5 | 2.34 | 60% | 99.6% |
| Sulfur transfer additive 6 | 2.65 | 59% | 99.8% |
| Sulfur transfer additive 7 | 2.78 | 67% | 98.7% |
| Sulfur transfer additive 8 | 2.57 | 62% | 99.7% |
| Sulfur transfer additive I | 9.17 | 37% | 79.1% |
| Sulfur transfer additive II | 2.97 | 41% | 83.7% |
| Sulfur transfer additive III | 2.86 | 50% | 92.4% |
Sulfur transfer additive 1-8 is known compared with the test result of sulfur transfer additive I, and sulfur transfer additive 1-8 compares sulfur transfer additive I and has higher wearability, illustrates in sulfur transfer additive 1-8 containing wear resistence Substance P
2o
5sulfur transfer additive 1-8 has higher adsorptivity and desorption than sulfur transfer additive I simultaneously, illustrate that sulfur transfer additive 1-8 is in preparation process, the aluminophosphates material on inorganic binder surface can effectively stop silica to consume spinel charge and magnesia, thus making the active component content in final sulfur transfer additive 1-8 high, the adsorption activity of sulfur transfer additive is strong.
Sulfur transfer additive 1-8 is known compared with the test result of sulfur transfer additive II, and the wear resistence of sulfur transfer additive 1-8 and sulfur transfer additive II is close, and this illustrates wherein all containing wear resistence material; Simultaneously the adsorptivity of sulfur transfer additive 1-8, desorption are all higher than sulfur transfer additive II, illustrate that the aluminophosphates on sulfur transfer additive 1-8 inorganic binder surface can improve the content of wherein active component, and then improve the adsorption activity of sulfur transfer additive, and the active sites that this effect is greater than in sulfur transfer additive II on metakaolin improves role for sulfur transfer additive adsorption activity.
Sulfur transfer additive 1-8 is known compared with the test result of sulfur transfer additive III, adhesive surface continuous print aluminophosphates clad can be destroyed after being ground by dried inorganic binder, thus the buffer action of this clad is weakened, the activity of sulfur transfer additive reduces, and this inorganic binder also having confirmed sulfur transfer additive 1-8 is coated with continuous print aluminophosphates layer.
Contrast separately known by sulfur transfer additive I, II test result, sulfur transfer additive II is higher than the wear resistence of sulfur transfer additive I, and this is owing to containing wear resistence Substance P in sulfur transfer additive II
2o
5; Simultaneously the adsorptivity of sulfur transfer additive II, desorption are all a little more than sulfur transfer additive I, the metakaolin be transformed into has a certain amount of active sites, improve the activity of sulfur transfer additive after which illustrating the kaolin roasting in sulfur transfer additive II.
Sulfur transfer additive II, III test result is contrasted separately known, the adsorptivity of sulfur transfer additive III and desorption are all a little more than transfer agent II, even if illustrate that aluminophosphates clad produces a small amount of defect under certain milling action, it is also better than the P after roasting to silica and spinel charge, magnesian buffer action
2o
5clad, thus P is described
2o
5the defect of clad under roasting effect is more, the easier stripping of the silica of high-load in its inorganic binder.
In a word, can be shown that by above test result the sulfur transfer additive adopting the preparation method of microphere sulfur transfer agent of the present invention to obtain is while the abrasion index that maintenance is very low, sulfur transfer additive I-III pair of oxygen sulfur compound compared in ratio 1-3 has higher adsorptivity and desorption, thus the existing very high wear resistence of sulfur transfer additive that obtains of preparation method of the present invention, has again higher activity.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.
Claims (11)
1. a preparation method for high activity and high-wearing feature microphere sulfur transfer agent, comprises
(1) inorganic binder is put into phosphoric acid or ammonium phosphate salt solution floods, after taking-up, obtain modified binder after drying; Wherein, described inorganic binder is one or more in kaolin, the sweet soil of sheep, bentonite and rod soil;
(2) in boehmite suspension, add acid to carry out being mixed to get gel, the suspension adding heavy-burned magnesia in above-mentioned gel mixes, and obtains mixed liquor; (3) mix after adding cerium salt, vanadic salts and complex acid solution successively in above-mentioned mixed liquor, obtain mixture;
(4) in said mixture, to add in described step (1) obtained modified binder mix and obtain slurries, namely slurry dried, roasting are obtained the sulfur transfer additive of high activity and high-wearing feature.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described inorganic binder and phosphoric acid or ammonium phosphate salt is (4.5-5): 1.
3. preparation method according to claim 1 and 2, is characterized in that, the concentration of described phosphoric acid or ammonium phosphate salt solution is 4-10wt%, and dip time is 12-14h.
4. preparation method according to claim 1, is characterized in that, the baking temperature in step (1) is 100-150 DEG C.
5. preparation method according to claim 1 and 2, is characterized in that, described ammonium phosphate salt is one or more in ammonium phosphate, ammonium dihydrogen phosphate (ADP) and diammonium hydrogen phosphate.
6. preparation method according to claim 1, it is characterized in that, in step (2), the mol ratio of described boehmite and acid is (0.43-0.45): 1, the concentration of described boehmite suspension is 10-12wt%, the concentration of described acid is 30-36wt%, and described acid is one or more in hydrochloric acid, nitric acid and glacial acetic acid.
7. the preparation method according to claim 1 or 6, is characterized in that, the addition of described heavy-burned magnesia is the 0.62-0.64wt% of described boehmite addition, and the turbid liquid concentration of described heavy-burned magnesia is 10-12wt%.
8. the preparation method according to claim 1 or 6, it is characterized in that, with molar amount, described cerium salt addition is the 7-8% of described boehmite addition, described vanadic salts addition is the 4-5% of described boehmite addition, and described complex acid addition is the 19-20% of described boehmite addition; The concentration of described complex acid solution is 33-35wt%.
9. the preparation method according to claim 1 or 6, is characterized in that, described modified binder addition is the 36-37wt% of described boehmite addition.
10. preparation method according to claim 1, is characterized in that, the baking temperature in step (4) is 400-500 DEG C, and sintering temperature is 600-700 DEG C.
11. preparation methods according to claim 8, is characterized in that, described cerium salt is one or more in cerous nitrate, cerous sulfate and cerium chloride, and described vanadic salts is ammonium metavanadate or ammonium poly-vanadate, and described complex acid is oxalic acid or citric acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295877A (en) * | 1999-11-12 | 2001-05-23 | 中国石油化工集团公司 | Process for preparation of sulfur transfer catalyst |
| CN1334316A (en) * | 2000-07-13 | 2002-02-06 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and its preparing process |
| CN1485132A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and and the preparation thereof |
| CN101190416A (en) * | 2006-12-01 | 2008-06-04 | 石大卓越科技股份有限公司 | Catalytic cracking catalyst and its preparation method |
| CN102861568A (en) * | 2012-09-28 | 2013-01-09 | 山东齐鲁华信高科有限公司 | Preparation method of catalytic cracking flue gas desulfurization auxiliary agent |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295877A (en) * | 1999-11-12 | 2001-05-23 | 中国石油化工集团公司 | Process for preparation of sulfur transfer catalyst |
| CN1334316A (en) * | 2000-07-13 | 2002-02-06 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and its preparing process |
| CN1485132A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and and the preparation thereof |
| CN101190416A (en) * | 2006-12-01 | 2008-06-04 | 石大卓越科技股份有限公司 | Catalytic cracking catalyst and its preparation method |
| CN102861568A (en) * | 2012-09-28 | 2013-01-09 | 山东齐鲁华信高科有限公司 | Preparation method of catalytic cracking flue gas desulfurization auxiliary agent |
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