CN1393527A - Catalyst for hydrorefining wax and its preparing process - Google Patents
Catalyst for hydrorefining wax and its preparing process Download PDFInfo
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- CN1393527A CN1393527A CN 01114183 CN01114183A CN1393527A CN 1393527 A CN1393527 A CN 1393527A CN 01114183 CN01114183 CN 01114183 CN 01114183 A CN01114183 A CN 01114183A CN 1393527 A CN1393527 A CN 1393527A
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Abstract
A catalyst for hydrorefining wax material contains weakly acidic SO2-P2O5-Al2O3 as carrier with high pore volume and specific surface area, and Ni and W as active components in mole ratio of 0.3-0.8. Its advantages are higher activity and higher selectivity.
Description
The invention belongs to the Wax hydrofining catalyst field, relate to a kind of pore distribution high concentration, large pore volume, weakly acidic Wax hydrofining catalyst and preparation method thereof specifically, particularly relate to the P of a kind of pore distribution high concentration, high dispersive, large pore volume and bigger serface
2O
5-SiO
2-Al
2O
3Carrier and preparation method thereof.
The main component of wax material is a normal paraffin, and normal temperature is solid down.Wax material purified main method is to adopt the hydrofining method, and this is a chemical reaction process, promptly is in the deep refining process that has under catalyzer existence and the certain processing condition.Purpose is intended to keep the essentially consist of normal paraffin, removes with 3, and the 4-benzopyrene is sulphur, nitrogen and the oxygen of carcinogenic substances such as the condensed-nuclei aromatics of representative and non-hydrocarbons.In order to make the wax material molecule fully carry out chemical reaction in catalyst active center, catalyzer must have big specific surface and large pore volume and unimpeded duct, for reactant and product molecule provide ideal reacting environment.In addition, the hydrorefining paraffin wax process is the very strong reaction process of selectivity, and it is saturated to make unsaturated components such as impurity removals such as sulphur, nitrogen and oxygen in the paraffin and condensed-nuclei aromatics be able to hydrogenation.Theoretically, this process does not allow to take place cracking reaction, otherwise will cause the increase of wax material oleaginousness and penetration degree.For this reason, catalyzer should have the few solid acid and based on slightly acidic of trying one's best.
At present, most Wax hydrofining catalyst still adopts Mo-Ni/Al
2O
3Form.It is generally acknowledged that the ideal Wax hydrofining catalyst should have following characteristics: bigger specific surface, pore volume and mean pore size, more weak acidity and concentrated pore distribution and higher physical strength.Therefore.People constantly improve Wax hydrofining catalyst towards this direction at present.
US4186078 has narrated a kind of Wax hydrofining catalyst, be characterized in that (1) adds the alkaline components of 0.2m%～5.0m% on carrier, to regulate the acid matter of catalyzer,, prevent that acid from measuring and strength of acid is excessive and the wax material overcracking generates oil so that be fit to the Wax hydrofining process.(2) to account for bore dia at the pore volume integration rate of (6～15) nm be more than 80% at the pore volume integration rate of (0～15) nm to bore dia, and bore dia accounts for 20%～30% of (0～60) nm pore volume at the pore volume integration rate of (6～15) nm, and the pore distribution that this patent catalyzer is described is than disperse.
CN 1032408C narration be to be active ingredient with Mo, Ni, with P
2O
5-SiO
2-Al
2O
3Be support of the catalyst, when the wet gel peptization, introduce phosphoric acid in the support of the catalyst preparation process, with strong acid center and the minimizing total acid content of eliminating carrier; In the preparing carriers process, silicon-aluminium colloidal sol becomes the glue after-filtration, is 23～27 ℃ with control washing temperature in the deionized water wash process, and washing times is 2～4 times.The pore volume integration rate of the bore dia of gained catalyzer in (4～15) nm scope accounts for pore volume integration rate 90% or more of bore dia in (0～60) nm scope, though pore distribution is very concentrated, but also has the leeway of further improving, and it is 70%～80% that the pore volume integration rate in the optimum bore dia of wax material catalyzer material hydrogenation catalyst (5～10) the nm scope accounts for the pore volume integration rate of bore dia in (0～60) nm scope, and the pore distribution in this scope is not very concentrated.
CN1210882A relates to a kind of nickelic tungsten type catalyst for hydrogenation refining of Vaseline, and its Ni/W (mole) value is 0.90～1.10, and the metal content of catalyzer is WO by weight
326～32%, NiO 8～12%, its WO
3The content height helps the aromatic hydrocarbons saturated reaction.But its NiO content is higher, and method for preparing catalyst also is at P
2O
5-SiO
2-Al
2O
3Or Al
2O
3Dipping W-Ni solution on the carrier, the Ni compound is the Ni (NO of favorable solubility
3)
2Or NiCl
2Deng, like this, in Catalyst Production, can cause the variation of catalyst pores structure and the pollution of environment in dipping or the roasting process, also can cause the raising of catalyzer cost.
The purpose of this invention is to provide a kind of pore distribution high concentration and weakly acidic SiO
2-P
2O
5-Al
2O
3Support of the catalyst and preparation method thereof, another object of the present invention provide a kind of have good hydrofining and aromatic hydrocarbons saturability Wax hydrofining catalyst and preparation method thereof.
SiO of the present invention
2-P
2O
5-Al
2O
3Contain SiO in the carrier by weight
25%～12%, contain P
2O
52%～6%, Al
2O
3Surplus, the pore volume of carrier are 0.75～1.10cm
3/ g, specific surface area is 300～400m
2It is 80%～90% that/g, the bore dia pore volume integration rate in 5～15nm scope accounts for the pore volume integration rate of bore dia in 0～100nm scope, and the pore volume integration rate of its median pore diameter in 6～10nm scope is 65%～80%.
Wax hydrofining catalyst of the present invention is an active ingredient with VIII family and vib metal element, with the SiO of above-mentioned large pore volume
2-P
2O
5-Al
2O
3Be carrier, catalyzer pore volume 0.42～0.55cm
3/ g, specific surface area is 200～260m
2It is 95%～99% that/g, the bore dia pore volume integration rate in 4～15nm scope accounts for the pore volume integration rate of bore dia in 0～100nm scope, and the pore volume integration rate of its median pore diameter in 5～10nm scope is 85%～90%.The above-mentioned preferred Ni of VIII family metallic element, the preferred W of vib metal element, WO by weight
3Be 22.0%～35.0%, NiO is 3.0%～8.0%, preferred WO
3Be 26.0%～32.0%, NiO is 4.0%～7.0%.
The preparation method of support of the catalyst of the present invention is:
(1) contains the AlCl of Si
3Solution and ammoniacal liquor are carried out to the glue reaction.
(2) silicon that (1) is obtained-aluminium colloidal sol washs, and temperature is controlled at 10～20 ℃, preferably is controlled between 15～18 ℃, and washing time is 0.5～2.0 hour, and washing times is 3～5 times.
(3) silicon-aluminium colloidal sol after the washing carries out peptization, adds the nitric acid-phosphoric acid solution of calculated amount, stirs simultaneously.
(4) carry out balling-up, drying, roasting behind the peptization and obtain support of the catalyst.
The concrete preparation process of support of the catalyst of the present invention is as follows:
(1) become the raw materials used preparation of glue:
AlCl
3The preparation of solution: general aluminum oxide and hydrochloric acid are reacted under 90～130 ℃, with gac deferrization method, feasible Fe/Al by weight
2O
3Value makes smart AlCl less than 0.005%
3Solution dilutes again, and concentration is 10～60g Al
2O
3Working fluid when/l just can be used as into glue.
The preparation of acidified sodium silicate: water glass is diluted to contains SiO
2It is the dilute solution of 50～100g/l, concentrated nitric acid is diluted to the salpeter solution that concentration is 30m%～40m%, under stirring fast, slowly water glass is being joined in the nitric acid, during acidifying temperature be controlled at＜40 ℃, control acidified sodium silicate PH＜3.0, solution is limpid, transparent sustain is more than 24 hours.
The preparation of ammoniacal liquor: liquefied ammonia joined be dissolved into ammoniacal liquor in the hydrostatic, be made into and contain NH
3Be the ammoniacal liquor of 60～150g/l.
The preparation of sial mixing solutions: under agitation acidified sodium silicate is joined AlCl
3In the solution, obtain as clear as crystal sial mixing solutions, control PH＜4.0.
(2) become glue: the sial mixing solutions is joined in the glue jar with certain flow velocity with ammoniacal liquor simultaneously, and stir, two kinds of solution hybrid reactions 8～12 minutes, be controlled to 10～20 ℃ of glue temperature, be preferably 14～18 ℃, control PH is 7～8 behind the one-tenth glue, and slurries wear out then, temperature temperature when becoming glue is identical, and digestion time is controlled at 20～90min.
(3) filter, wash: the slurries that will wear out filter, and mother liquor is separated, and the filter cake that obtains washs with deionized water, and controlled temperature is 15～18 ℃ during pulp, and washing times is 3～5 times, and total washing time is 0.5～2.0 hour.
(4) filter cake peptization: the filter cake that will wash carries out peptization with the mixing solutions of rare nitric acid and phosphoric acid, must stir in peptization course, and the mixing solutions of rare nitric acid and phosphoric acid divides 2～5 addings.Peptization time was controlled at 1.5～4.0 hours.
(5) carrier moulding: the slurries behind the peptization splash into the wet rubber ball that oil ammonia column under the room temperature becomes certain degree of hardness through water dropper.
(6) carrier drying, roasting
The carrier drying temperature is 100～200 ℃, and be 5～12 hours time of drying.Maturing temperature is 550～700 ℃, and constant temperature time is 2～6 hours.
Preparation of catalysts method of the present invention is as follows:
SiO with above-mentioned preparation
2-P
2O
5-Al
2O
3Be carrier, the W-Ni solution of the high density of preparation stable in properties is with the saturated dipping of vacuum or method load W, Ni active ingredient conventional saturated or the supersaturation dipping.Under 80～150 ℃ of temperature dry 2～12 hours then, 400～550 ℃ of roasting temperatures 2～5 hours.
W-Ni solution preparation: determine WO in the steeping liq according to the water-intake rate of carrier and the content of reactive metal on catalyzer of the load of wanting
3And the concentration of NiO, WO
3And the concentration of NiO is respectively 470～560g/l and 65～85g/l.The used raw material of preparation W-Ni solution is: tungsten salt is ammonium metawolframate, and nickel salt is soluble substances such as nickelous nitrate, nickelous chloride and nickel acetate, and the present invention is preferably nickelous nitrate.
Main character in order to the carrier of top method preparation and catalyzer is as shown in table 1.
The main character project support of the catalyst WO of table 1 carrier of the present invention and catalyzer
3/ m% 22～35/NiO/m% 3.0～8.0/SiO
2/ m% 3.0～7.0 5.0～12.0P
2O
5/ m% 1.0～3.0 2.0～6.0 pore volumes/mlg
-10.42～0.55 0.75～1.10 specific surface/m
2G
-1200～260 300～400 mean pore sizes/nm 7.0～9.0 9.0～12.0 tap densities/gml
-10.80～0.95 0.45～0.65 physical strength/N grain
-1〉=40.0 〉=40.0 pore distributions/%4.0nm 0.5～3.0 2.0～5.0,4.0～the 15.0nm of (＜5.0nm) 95.0～99.0 80.0～90.0, (5.0～15.0nm) 5.0～10.0nm 85.0～90.0 65.0～80.0, (6.0～10.0nm)＞15.0nm 0.5～2.0 8.0～15.0
In the preparation process of support of the catalyst of the present invention, solution temperature and slurries aging temperature are controlled between 10～18 ℃ when becoming glue, make carrier have bigger pore volume, when being higher than 18 ℃, the pore volume of carrier can reduce rapidly, if be lower than 10 ℃, then be unfavorable for into the glue successful reaction and carry out.Water washing process also is into the continuation weathering process behind the glue, and the washing condition has the influence of can not ignore to the character of product, adopts washing condition of the present invention to improving pore distribution concentration degree and pore volume tangible effect to be arranged.Peptization acid adds in batches and helps P at Al
2O
3The high dispersing on surface with the P content of trying one's best low, plays the purpose that increases carrier pore volume and reduction carrier strength of acid and acid amount, and P content is low simultaneously, and it is more concentrated that carrier hole is distributed.Add peptization acid in addition in batches, help abundant peptization, be convenient to phosphoric acid and slurries thorough mixing, avoid simultaneously once adding and make slurries viscosity increase in for some time very fast, and can not fully stir.Because the influence of these factors makes that the aperture of support of the catalyst of the present invention is more concentrated, with the catalyzer of this preparing carriers, has the pore distribution of high concentration.By table 1 as seen, catalyzer of the present invention has the pore distribution of high concentration, 95%～99% hole concentrates in the scope of 4.0～15.0nm, in addition, the pore volume of catalyzer of the present invention, specific surface are all bigger, also has higher physical strength, all these good physico-chemical properties have determined catalyzer to have good use properties, and the optimum activity atoms metal ratio that particularly cooperates the present invention to determine makes this catalyzer have higher activity and selectivity when being used for Wax hydrofining.Catalyzer of the present invention has also suitably reduced the consumption of reactive metal, has reduced production cost.
Catalyzer of the present invention can be used for the hydrofining of petroleum products, be specially adapted to the hydrofining of wax material, to remove carcinogenic substances such as impurity such as S, N in the paraffin class, O and condensed-nuclei aromatics, produce high-quality food packing wax, food wax and medical or used for cosmetic Vaseline etc.
When catalyzer of the present invention was used for the hydrofining of wax class, appropriate processing condition was: temperature of reaction is 240～310 ℃, and the hydrogen dividing potential drop is 5.0～15.0MPa, and hydrogen wax ratio is 100～300 (v/v), and volume space velocity is 0.5～2.0h
-1
Below describe the present invention in detail with embodiment.
Embodiment 1
(1) SiO
2-P
2O
5-Al
2O
3The preparation of carrier
1. the preparation of silicon-aluminium colloidal sol
The preparation of acidified sodium silicate: water glass is diluted to contains SiO
2Be the dilute solution of 7.5g/100ml, concentrated nitric acid is diluted to the salpeter solution that concentration is 35m%, under agitation water glass is joined in the nitric acid, temperature is controlled at 35 ℃ during acidifying, and control acidified sodium silicate PH is 2.0, and it is limpid, transparent more than 24 hours to keep solution.
With the concentration for preparing for containing Al
2O
33.0g/100ml aluminum trichloride solution (, make Fe/Al by weight with gac deferrization method
2O
3Value is less than 0.005%) 20l with contain SiO
26.0g/100ml acidified sodium silicate 2.5l mix, regulate the pH value to 2.4 of mixing solutions, start refrigerator and keep 13 ℃ of solution temperatures, left standstill 3 hours.
2. become glue: 13 ℃ of silicon-aluminum sol that will 1. prepare and temperature, concentration is that 7.0% ammonia soln joins in the glue jar by certain flow simultaneously, and constantly stir, it is 7.5 that whole process is kept pH value, temperature since in make into heat release that temperature is controlled at 17 ℃ in the glue jar, making two kinds of solution reaction duration of contact is 10min, stirs aging 50min.
3. filter and wash
Pump press filtration, use the deionized water wash filter cake, temperature is 15 ℃ during the control washing, and total washing time is 1 hour, washs 4 times.
4. wet colloidal sol peptization: the butt of the wet colloidal sol of control is 10.0%, rare nitric acid of 200ml 35% will be carried out peptization with the wet colloidal sol that joins 10kg after the phosphoric acid of 60g 56% mixes, peptization course stirs simultaneously, and the mixing solutions of rare nitric acid and phosphoric acid divides 3 addings, and total peptization time is 3 hours.
5. will be dripped by water dropper by the 4. colloidal sol of gained, by the oil ammonia column balling-up under the room temperature, the wet rubber ball that comes out from oil ammonia column soaks sclerosis in 2 hours 6.0% ammoniacal liquor.
6. drying and roasting: by the wet bulb of 5. gained 120 ℃ of dryings 5 hours, then 620 ℃ of following roastings 3 hours.
(2) Preparation of Catalyst
1. W-Ni dipping solution preparation: according to the water-intake rate preparation W-Ni dipping solution of carrier, WO
3Concentration be 510.0g/l, the concentration of NiO is 80.0g/l.Tungsten salt is ammonium metawolframate, and nickel salt is a nickelous nitrate.
2. impregnated carrier: take by weighing by the 6. carrier 1000g of gained, place the used commentaries on classics pot of dipping, start and change pot, saturated impregnated carrier, when beginning to flood, the solution spouting velocity is controlled at 10～15ml/min, after bed temperature dropped to 40 ℃, the speed that can strengthen dipping was 20～30ml/min.After solution impregnation finishes, continue to start the commentaries on classics pot, homogenize 20～40min.
3. drying and roasting: the ball of inhaling full solution 120 ℃ down dry 4 hours 500 ℃ of following roastings 3 hours, i.e. cost example.
Embodiment 2
With Al in the silicon-aluminum sol among the embodiment 1 (1)
2O
3Concentration change 10.0g/100ml into, SiO in the acidified sodium silicate
2Concentration change 9.0g/100ml into; Become the glue temperature to be controlled at 14 ℃, digestion time is 30min, and wash temperature is 15 ℃, and total washing time is 40min, washs 3 times.All the other are all identical with embodiment 1, i.e. the cost example.
Embodiment 3
With Al in the silicon-aluminum sol among the embodiment 1 (1)
2O
3Concentration change 7.0g/100ml into, SiO in the acidified sodium silicate
2Concentration change 4.0g/100ml into; Become the glue temperature to be controlled at 19 ℃, become glue after scouring temperature to be controlled at 18 ℃, all the other are all identical with embodiment 1, i.e. the cost example.
Embodiment 4
Change embodiment 1 (1) consumption with phosphoric acid into 100g, the mixing liquid of phosphoric acid and nitric acid divides adding, i.e. cost example 2 times.
Embodiment 5
With WO among the embodiment 1 (2)
3Concentration change 480.0g/l into, the concentration of NiO is 95.0g/, maturing temperature changes 550 ℃ of roastings, i.e. cost example into.
Embodiment 6
Press embodiment 1 method, in peptization course, required peptization acid is once added, i.e. the cost example.
Comparative example 1
In (1) of embodiment 1, filter with washing step in, washing temperature is adjusted to 27 ℃, all the other are all in identical with embodiment 1, i.e. the cost example.
Embodiment 7
This example is the main physical and chemical and the activity rating result of above each routine catalyzer.
The physico-chemical property of each routine catalyzer of table 2
| Catalyzer | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| ?WO 3/m％ | ???29.8 | ???30.5 | ???28.9 | ???30.2 | ???33.9 | ???30.0 | ???29.9 |
| ?NiO/m％ | ????5.0 | ????5.4 | ????4.5 | ????5.1 | ????6.5 | ????4.6 | ???4.52 |
| ?SiO 2/m％ | ????4.5 | ????5.0 | ????4.4 | ????4.6 | ????4.0 | ????4.1 | ????3.9 |
| ?P 2O 5/m％ | ????1.5 | ????2.0 | ????1.9 | ????4.0 | ????2.1 | ????1.6 | ????2.3 |
| Pore volume/mlg -1 | ???0.450 | ???0.473 | ???0.431 | ???0.462 | ???0.426 | ???0.421 | ???0.403 |
| Specific surface/m 2·g -1 | ????221 | ????216 | ????245 | ????215 | ????211 | ????205 | ????241 |
| Mean pore size/nm | ????8.1 | ????8.8 | ????7.0 | ????8.6 | ????8.1 | ????8.2 | ????6.9 |
| Tap density/gml -1 | ???0.90 | ???0.89 | ???0.95 | ???0.90 | ???0.96 | ???0.97 | ???0.96 |
| Physical strength/N grain -1 | ????52 | ????50 | ????60 | ????58 | ????61 | ????60 | ????62 |
| Pore distribution/% | |||||||
| ??＜4.0nm | ????1.0 | ????1.3 | ????4.0 | ????2.6 | ????3.4 | ????8.3 | ???13.4 |
| ??4.0～15.0nm | ????97 | ????95.5 | ????95 | ????95 | ????96 | ???90.5 | ???84.5 |
| ??5.0～10.0nm | ????87 | ????86 | ????85 | ????85 | ????87 | ???82.4 | ???76.8 |
| ??＞15.0nm | ????2.0 | ????3.2 | ????1.0 | ????2.4 | ????0.6 | ???1.2 | ???2.1 |
By table 2 as seen, compare with comparative example, catalyzer of the present invention has the pore distribution of high concentration, bigger pore volume and mean pore size.
During evaluate catalysts, raw materials used wax is No. 59 ketone benzin system waxes.Processing condition are: hydrogen dividing potential drop 6.0MPa, temperature is 260 ℃, volume space velocity 1.5h
-1, hydrogen wax than 120 (v)
Each routine catalyst activity evaluation result of table 3
| Project | Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Fusing point/℃ | ???59.2 | ??59.2 | ???59.3 | ???59.1 | ???25.2 | ???58.4 | ???59.3 | ???58.1 |
| Oleaginousness/% (m/m) | ???0.21 | ??0.22 | ???0.22 | ???0.23 | ???0.21 | ???0.21 | ???0.23 | ???0.24 |
| Color/(Sai Shi) number | ???+19 | ??+30 | ???+30 | ???+30 | ???+30 | ???+30 | ???+29 | ???+30 |
| Light stability/number | ???5～6 | ??2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???3～4 | ???3～4 |
| Heat-resistant quality/(Sai Shi) | ???+5 | ??+29 | ???+29 | ???+29 | ???+29 | ???+29 | ???+29 | ???+28 |
| Readily carbonizable substance | Do not pass through | By | By | By | By | By | By | By |
| Condensed-nuclei aromatics (simplified method) ultraviolet absorptivity | ||||||||
| ??280nm | ???0.383 | ??0.015 | ???0.014 | ???0.015 | ???0.015 | ???0.013 | ???0.016 | ??0.018 |
| ??290nm | ???0.290 | ??0.007 | ???0.008 | ???0.007 | ???0.008 | ???0.006 | ???0.009 | ??0.010 |
As seen from Table 3, catalyzer of the present invention has good hydrorefining paraffin wax performance, catalyzer is at low temperature, low pressure low hydrogen wax when has good activity under the high-speed condition, make hydrogenation paraffin reach slab wax standard (GB7189-94) fully, the stability of comparative example purified product is high No. one, and the ultraviolet absorptivity value also shows also higherly than embodiment, illustrates that catalyzer of the present invention has good hydrorefining paraffin wax effect.
Claims (10)
1, a kind of SiO
2-P
2O
5-Al
2O
3Support of the catalyst contains SiO by weight
25%～12%, contain P
2O
52%～6%, pore volume is 0.75～1.10cm
3/ g, specific surface area is 300～400m
2It is 80%～90% that/g, the bore dia pore volume integration rate in 5～15nm scope accounts for the pore volume integration rate of bore dia in 0～100nm scope, and the pore volume integration rate of bore dia in 6～10nm scope is 65%～80%.
2, a kind of Wax hydrofining catalyst is with the described SiO of claim 1
2-P
2O
5-Al
2O
3Carrier is a carrier, is active ingredient with VIII family and vib metal element, and the pore volume of catalyzer is 0.40～0.55cm
3/ g, specific surface area is 200～26m
2It is 95%～99% that/g, the bore dia pore volume integration rate in 4～15nm scope accounts for the pore volume integration rate of bore dia in 0～100nm scope, and the pore volume integration rate of bore dia in 5～10nm scope is 85%～90%.
3, according to the described catalyzer of claim 2, it is characterized in that described VIII family metallic element is Ni, the vib metal element is W.
4,, it is characterized in that described W is with WO according to the described catalyzer of claim 3
3Weight counts 22.0%～35.0%, and Ni counts 3.0%～8.0% with NiO weight.
5, the preparation method of the described support of the catalyst of a kind of claim 1 may further comprise the steps:
(1) contains the AlCl of Si
3Solution and ammoniacal liquor are carried out to the glue reaction;
(2) silicon that (1) is obtained-aluminium colloidal sol washs, and wash temperature is 10～20 ℃, and washing time is 0.5～2.0 hour, and washing times is 3～5 times;
(3) silicon-aluminium colloidal sol after the washing carries out peptization;
(4) carry out moulding, drying, roasting behind the peptization and obtain support of the catalyst.
6, in accordance with the method for claim 5, the AlCl that it is characterized in that the described Si of containing
3The preparation process of solution is:
(1) AlCl
3The preparation of solution: aluminum oxide and hydrochloric acid are reacted under 90～130 ℃, generate AlCl
3Solution filters, the gac deferrization, makes Fe/Al by weight
2O
3Value is less than 0.005%, dilute for concentration be 10～60g Al
2O
3The one-tenth glue working fluid of/l;
(2) preparation of acidified sodium silicate: water glass is diluted to contains SiO
2Be the dilute solution of 50～100g/l, concentrated nitric acid be diluted to the salpeter solution that concentration is 30～40m%, under agitation water glass is joined in the nitric acid, during acidifying temperature be controlled at＜40 ℃, control acidified sodium silicate PH＜3.0;
(3) preparation of sial mixing solutions: under agitation acidified sodium silicate is joined AlCl
3In the solution, obtain as clear as crystal sial mixing solutions, control PH＜4.0.
7, in accordance with the method for claim 5, it is characterized in that described one-tenth glue reaction conditions is: sial mixing solutions and ammoniacal liquor are joined in the glue jar simultaneously, two kinds of solution hybrid reactions are 8～12 minutes under agitation condition, be controlled to 10～20 ℃ of glue temperature, control PH is 7～8 behind the one-tenth glue, slurries wear out then, and temperature temperature when becoming glue is identical, and digestion time is controlled at 20～90min.
8, ask 7 described methods according to right, the concentration that it is characterized in that described ammoniacal liquor is for containing NH
3Be the ammoniacal liquor of 60～150g/l, becoming the glue temperature is 14～18 ℃.
9, in accordance with the method for claim 5, it is characterized in that described wash temperature is 15～18 ℃.
10, in accordance with the method for claim 5, it is characterized in that described peptization is: the filter cake that will wash carries out peptization with the mixing solutions of rare nitric acid and phosphoric acid, in peptization course, carry out under the whipped state, the mixing solutions of rare nitric acid and phosphoric acid divides 2～5 addings, and peptization time was controlled at 1.5～4.0 hours; Described carrier drying, roasting condition are: drying temperature is 100～200 ℃, and be 5～12 hours time of drying, and maturing temperature is 550～700 ℃, and constant temperature time is 2～6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011141832A CN1162521C (en) | 2001-07-02 | 2001-07-02 | Catalyst for hydrorefining wax and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011141832A CN1162521C (en) | 2001-07-02 | 2001-07-02 | Catalyst for hydrorefining wax and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1393527A true CN1393527A (en) | 2003-01-29 |
| CN1162521C CN1162521C (en) | 2004-08-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011141832A Expired - Lifetime CN1162521C (en) | 2001-07-02 | 2001-07-02 | Catalyst for hydrorefining wax and its preparing process |
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| Country | Link |
|---|---|
| CN (1) | CN1162521C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485847A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Method for hydrorefining petroleum wax |
| CN102039148B (en) * | 2009-10-22 | 2012-08-08 | 中国石油天然气股份有限公司 | Preparation method of petroleum wax hydrofining catalyst |
-
2001
- 2001-07-02 CN CNB011141832A patent/CN1162521C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039148B (en) * | 2009-10-22 | 2012-08-08 | 中国石油天然气股份有限公司 | Preparation method of petroleum wax hydrofining catalyst |
| CN102485847A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Method for hydrorefining petroleum wax |
| CN102485847B (en) * | 2010-12-03 | 2014-06-04 | 中国石油天然气股份有限公司 | Method for hydrorefining petroleum wax |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1162521C (en) | 2004-08-18 |
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