CN1072705C - Process for preparing residuum hydrogenation catalyst - Google Patents
Process for preparing residuum hydrogenation catalyst Download PDFInfo
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- CN1072705C CN1072705C CN98121076A CN98121076A CN1072705C CN 1072705 C CN1072705 C CN 1072705C CN 98121076 A CN98121076 A CN 98121076A CN 98121076 A CN98121076 A CN 98121076A CN 1072705 C CN1072705 C CN 1072705C
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Abstract
The present invention discloses a preparation method of hydrogenation processing catalysts, which overcomes the defect of high production cost of the existing congener hydrogenation processing catalysts, particularly residual oil hydrogenation catalysts. In the method of the present invention, the mixing kneading process of aluminum hydroxide monohydrate, metal salts, etc. is optimized for promoting the dispersion of metal; all of the materials are once mixed and kneaded into plastic bodies and are squeezed into strips, and are made into catalysts through steam-air high temperature activation. The catalysts prepared by the method of the present invention have high hydrogenation denitrification activity, hydrogenation carbon residue removing activity and deep hydrodesulfurization activity; simultaneously, the preparation cost of the catalysts is obviously reduced as compared with that of catalysts of the existing methods.
Description
The present invention relates to a kind of hydrogenization catalyst preparation method, particularly the residual hydrogenation denitrogenation especially residual hydrogenation carbon residue (HDCR) and residual oil deep hydrodesulfurizationof Preparation of catalysts method are fallen.
In the residual hydrocracking process, owing to contain a large amount of heavy metals such as nickel, vanadium in the residual oil, they are accumulated on the catalyzer, make the catalyzer behind the inactivation be difficult to regeneration.And owing to residual oil viscosity height, wherein contain impurity such as a large amount of S, N, thereby the air speed of residual hydrocracking process is very little, so catalyst consumption increases greatly than other oil refining process.So the very big factor of this process technology economic feasibility of decision is how to reduce the cost of catalyzer, makes the cost of whole hydrotreatment process more favourable on Technological Economy.Therefore, guaranteeing to reduce the catalyzer cost under the prerequisite that the every use properties of catalyzer does not descend, be long term studies problem in this area.
The catalyzer cost comprises two aspects, i.e. material cost and production cost.If raw materials variations is little, only on preparation technology, full kneading method has been save carrier roasting, dipping, dipping humectant drying and other steps than pickling process, thereby the former is more more economical, but because active metal component can not play one's part to the full, often the use properties of catalyzer is not good.Its chief reason is, the catalyst metal degree of scatter of full kneading method preparation is low than catalyst prepared, and metal easily generates the extremely strong inactive substance of interaction with carrier in the full kneading process; For making catalyzer reach certain activity, its terms of settlement is to strengthen the add-on of reactive metal, and this just makes the cost of catalyzer improve greatly.
US5089453 adopts full kneading method to prepare residual oil hydrocatalyst, uses a large amount of TiCl in its preparation process
4Make improvements agent, contain TiO in the catalyzer
2Amount reaches 4～6w%, because TiCl
4Hydrolytic process easily produces harmful fog, makes will use specific equipment in the production process, and the production technique more complicated, the production difficulty is big, and security is low, and cost is higher.CN1070418A adopts the catalyzer of full kneading method preparation, is improving agent with titanium, boron, and its acidity is stronger, NH
3-TPD acidity reaches 1.449mmol/g, and carbon deposit speed is fast, and catalyst deactivation is fast, the life-span is short.CN1098433A adopts and mix-to soak the bonded production technique, is still will advance impregnation steps mixed after pinching the part reactive metal, and Production Flow Chart is long.And above-mentioned catalyzer only has hydrodenitrogenationactivity activity and removal of ccr by hydrotreating activity preferably, and hydrodesulfurization activity is relatively poor, must be used with Hydrobon catalyst during use and could handle residual oil effectively.
The objective of the invention is to overcome the deficiency of above-mentioned preparation residual oil hydrocatalyst method, a kind of preparation method of residual oil hydrocatalyst is provided, on the basis that guarantees the various use propertieies of catalyzer, simplify the Preparation of Catalyst flow process, reduce production costs, prolong catalyst life, when reaching higher hydrodenitrification rate and removal of ccr by hydrotreating rate, reach higher hydrogenating desulfurization rate.
The process of the inventive method is: 1, all powder shape solid materials is evenly mixed by a certain percentage; 2, add the siliceous aqueous solution and carry out premix, and then add acidic solution and fully mixed pinching; 3, moulding, drying, under water vapor-air atmosphere, activate.
The detailed process of the inventive method is: aequum powdered one water-aluminum hydroxide, nickel compound, molybdenum compound are added premixed device mix evenly; Add the siliceous aqueous solution, premix 10～60 minutes adds acidic solution again, mixes and pinches 40～150 minutes; Gained plastic extruded moulding, the wet bar of gained is at 20～150 ℃ of drying 2～6h; At last the gained strip is carried out water vapor-air high-temperature activation, activation condition is water inlet weight space velocity 0.1～10.0h
-1, be preferably 1.0～3.0h
-1, air/catalyst volume ratio is 50～2000, is preferably 200～500, and activation temperature is 420～700 ℃, is preferably 500～600 ℃, and soak time is 2～12h, is preferably 2～5h.
Above-mentioned Powdered nickel compound is selected from least a in basic nickel carbonate, nickelous nitrate and the nickelous chloride, Powdered molybdenum compound is technical grade molybdenum oxide and/or technical grade ammonium molybdate, the siliceous aqueous solution is the neutral aqueous solution that contains silicon sol, acidic solution is selected from acetic acid solution, salpeter solution and hydrochloric acid soln, preferably contains titanous chloride in the described acid solution.
Adopt the catalyzer of the inventive method preparation to have following physico-chemical property: with final catalyst weight is benchmark, and catalyzer contains MoO
320～25%, NiO 7～10%, SiO
24～6%, TiO
21～2%, the catalyzer pore volume is 0.35～0.45ml/g, specific surface area 180～230m
2/ g, tap density 0.84～0.90g/mL.
The catalyzer that adopts the inventive method to prepare can be used for the hydrotreatment of distillate, is particularly useful for the hydrotreatment process of residual oil, has the ability of hydrodenitrification preferably, removal of ccr by hydrotreating and deep hydrodesulfurizationof.
For reducing the catalyzer cost, preparation method of the present invention adopts full kneading method.In premixed device all solids powder material thorough mixing; Add the siliceous aqueous solution again and carry out premix, can alleviate the strong interaction between metal and carrier, suppress too much inactive substance and generate, guarantee that most of metal all produces catalytic active center, improve activity of such catalysts; And then add acidic solution and carry out fully mixing pinching, its purpose is to promote metal to disperse, and improves the utilization ratio of metal, weakens the full detrimentally affect that the method for pinching is brought that mixes; At last the dry sample after the moulding is carried out water vapor-air high-temperature activation, in order to physico-chemical properties such as the acidity of regulating catalyzer, tap densities, catalyzer has certain acidity can improve activity of such catalysts, can accelerate carbon deposit speed but acidity is too high, shortened the work-ing life of catalyzer, suitable acidity is to make residual oil hydrocatalyst the have premium properties important factor in catalyzer work-ing life particularly, and suitable in addition parameters such as tap density also are the important service indexs of residual oil hydrocatalyst.
The advantage of method for preparing catalyst of the present invention is: 1, adopt full kneading method to shorten the production cycle, simplified preparation flow, reduce number of devices, correspondingly reduced production and managerial personnel, greatly improved productivity, greatly reduce production cost; 2, adopt silicon, titanium as structural promoter, improved the interaction strength between metal and carrier, suppressed the excessive generation of inactive substance, mixed to pinch combining with substep, helped metal and disperse, improved activity of such catalysts; 3, adopt water vapor-air associating high-temperature activation, make the physico-chemical properties such as acidity, tap density of catalyzer obtain favourable adjustment, guaranteed every service index of catalyzer, guarantee that particularly catalyzer has long work-ing life.What deserves to be explained is especially with the catalyzer of the inventive method preparation simultaneously tool with higher hydrodenitrification, removal of ccr by hydrotreating activity and hydrodesulfurization activity, broken through the restriction that to use Hydrobon catalyst and hydrodenitrogenation catalyst to be used simultaneously in the prior art, for producing and use provides convenience.
Below further specify the present invention with embodiment.
Embodiment 1
Take by weighing 500g and contain Al
2O
3The water-aluminum hydroxide powder of 67w%, the Powdered basic nickel carbonate of 100.0g (containing NiO 56.3w%) 144.0g technical grade molybdenum oxide (contains MoO
396w%) mix, add 81.0g and (contain SiO
230w%) the mixing solutions of silicon sol and 150g water, premix 50 minutes adds 42.5g again and (contains TiCl
37w%) TCl
3The mixing solutions of solution and 30g HAc and 150g water mixes and to pinch 50 minutes, and the gained plastic is extruded into the strip of Φ 0.82mm on banded extruder, and this strip is carried out water vapor-air-activated 3h at 80 ℃ of dry 3h down in stoving oven under 550 ℃.The water inlet weight space velocity is 1.50h
-1, air/catalyst volume ratio is 400.
Embodiment 2
Under the charging capacity of each material and all identical situation of other operational condition with embodiment (1), under 620 ℃, carry out water vapor-air-activated 2h, the water inlet weight space velocity is 0.50h
-1, air/catalyst volume ratio is 80, i.e. the cost example.
Embodiment 3
Under the charging capacity of each material and all identical situation of other operational condition with embodiment (1), under 490 ℃, carry out water vapor-air-activated 8h, the water inlet weight space velocity is 6.0h
-1, air/catalyst volume ratio is 1600, i.e. the cost example.
Comparative example 1
Press each material charging capacity and the preparation of its operational condition, i.e. the cost example of CN1098433A embodiment 1.
Comparative example 2
Press each material charging capacity and the preparation of its operational condition, i.e. the cost example of CN1070418A embodiment 1.
Comparative example 3
The charging capacity of each material is all identical with embodiment (1) with other operational condition, is that dried strip is 540 ℃ of following roasting 3h, i.e. cost examples.
Physico-chemical property and activity rating result that 4 examples of embodiment are above each routine catalyzer.
The physico-chemical property of each routine catalyzer sees Table 1.Estimate and see Table 2 with stock oil character.
During evaluate catalysts, from top to bottom by beds, through Hydrobon catalyst, pass through above each routine catalyzer more earlier after hydrogen and stock oil mix, take One-through design, Hydrobon catalyst is with batch Industrial products.The processing condition of estimating each routine catalyzer employing are all identical, are respectively: reaction pressure, 14.6MPa; Temperature of reaction, 400 ℃; Total liquid hourly space velocity, 0.33h
-1Hydrogen-oil ratio (v), 1000.Reactor volume is: φ 25mm * 2000mm.Loaded catalyst is respectively: Hydrobon catalyst, 120cm
3More than each routine catalyzer, 180cm
3Evaluation result sees Table 3.
By this example as can be known, acid amount, the acidity distribution of the catalyzer of employing the inventive method preparation are more suitable, have the ability of hydrodenitrification preferably, especially removal of ccr by hydrotreating and deep hydrodesulfurizationof.
5 examples of embodiment are the stability test evaluation result of embodiment 1 and comparative example 2 catalyzer.
Estimate and see Table 2 with stock oil character.
During evaluate catalysts; hydrogen and stock oil pass through beds from top to bottom after mixing; elder generation is through the protective material and the Hydrodemetalation catalyst of first reactor; again through the Hydrobon catalyst of second reactor; at last through above each routine catalyzer of the 3rd reactor; take One-through design, first reactor and second reactor catalyst are with batch Industrial products.The processing condition of estimating each routine catalyzer employing are all identical, are respectively: reaction pressure, 14.6MPa; Temperature of reaction, 400 ℃; Total liquid hourly space velocity, 0.22h
-1Hydrogen-oil ratio (v), 1000.Three reactor volumes are: φ 25mm * 2000mm.Loaded catalyst is respectively: protective material, 40cm
3Hydrodemetalation catalyst, 40cm
3Hydrobon catalyst, 115cm
3Embodiment 1 catalyzer or comparative example 2 catalyzer, 260cm
3Estimation of stability the results are shown in Table 4.
Above-mentioned used Hydrobon catalyst is that the trade mark that first fertilizer plant of Qilu Petrochemical company produces is the Hydrobon catalyst of ZTS-01, and protective material and Hydrodemetalation catalyst are that the trade mark that Fushun Petrochemical Research Institute produces is the protective material of CEN-4 and the Hydrodemetalation catalyst of CEN-6.
By this example as can be known, adopt the activity of such catalysts of the inventive method preparation to have good stability, deactivation rate is slow, cooperates the suitable temperature of reaction of adjusting can reach long running period, and has the ability of hydrodenitrification preferably, especially removal of ccr by hydrotreating and deep hydrodesulfurizationof.
The physico-chemical property of each catalyzer of table 1
Table 2 stock oil character
Table 3 evaluation result
The stability test result of table 4. catalyzer
Claims (9)
1, a kind of preparation method of residual oil hydrocatalyst may further comprise the steps:
(1) water-aluminum hydroxide and powdery nickel compound and powdery molybdenum compound are mixed;
(2) the adding acidic solution is mixed in the said mixture material pinches;
(3) (2) gained plastic is carried out extruded moulding, dry, active gained strip;
It is characterized in that mixture adds siliceous aqueous solution earlier before adding acidic solution in (2) step, the activation in (3) step is carried out under water vapor-air atmosphere.
2, method as claimed in claim 1 is characterized in that the aqueous solution that contains silicon in the step (2) is the aqueous solution of neutral silicon sol.
3, method as claimed in claim 1 is characterized in that the drying temperature in the step (3) is 20～150 ℃, and the time is 2～6h.
4, as the method for claim 1 or 2, it is characterized in that the activation temperature in the step (3) is 420～700 ℃, the time is 2～12h, water vapor adopts water inlet to add thermogenesis or directly feeds, water inlet weight space velocity 0.1～10.0h
-1, air/catalyst volume is than 50～2000.
5, method as claimed in claim 4 is characterized in that described activation temperature is 500～600 ℃, and the time is 2～5h, and the water inlet weight space velocity is 1.0～3.0h
-1, air/catalyst volume ratio is 200～500.
6, method as claimed in claim 1 is characterized in that Powdered nickel compound is selected from least a in basic nickel carbonate, nickelous nitrate and the nickelous chloride, and Powdered molybdenum compound is technical grade molybdenum oxide and/or technical grade ammonium molybdate.
7, method as claimed in claim 1 is characterized in that used acid solution is selected from acetic acid solution, salpeter solution and hydrochloric acid soln in the step (2).
8,, it is characterized in that used acid solution is the acid solution that contains titanous chloride in the step (2) as the method for claim 1 or 7.
9, method as claimed in claim 1 is characterized in that prepared catalyzer is a benchmark with final catalyst weight, contains following ingredients: MoO
320～25%, NiO 7～10%, SiO
24～6%, TiO
21～2%; The pore volume of catalyzer is 0.35～0.45cm
3/ g, specific surface area is 180～230m
2/ g, tap density is 0.84～0.90g/cm
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121076A CN1072705C (en) | 1998-12-16 | 1998-12-16 | Process for preparing residuum hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121076A CN1072705C (en) | 1998-12-16 | 1998-12-16 | Process for preparing residuum hydrogenation catalyst |
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|---|---|
| CN1257103A CN1257103A (en) | 2000-06-21 |
| CN1072705C true CN1072705C (en) | 2001-10-10 |
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|---|---|---|---|
| CN98121076A Expired - Lifetime CN1072705C (en) | 1998-12-16 | 1998-12-16 | Process for preparing residuum hydrogenation catalyst |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104646006B (en) * | 2013-11-22 | 2017-04-05 | 中国石油天然气股份有限公司 | Supported hydrodenitrogenation catalyst and preparation method thereof |
| CN111632627A (en) * | 2020-05-18 | 2020-09-08 | 上海国惠环保科技集团有限公司 | Preparation method of structural auxiliary for molding |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| CN1098433A (en) * | 1993-08-04 | 1995-02-08 | 中国石油化工总公司抚顺石油化工研究院 | The preparation method of Hydrobon catalyst |
| CN1181409A (en) * | 1996-10-28 | 1998-05-13 | 中国石油化工总公司 | Catalyzer for hydrotreating residuum and its prepn. method |
-
1998
- 1998-12-16 CN CN98121076A patent/CN1072705C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| CN1098433A (en) * | 1993-08-04 | 1995-02-08 | 中国石油化工总公司抚顺石油化工研究院 | The preparation method of Hydrobon catalyst |
| CN1181409A (en) * | 1996-10-28 | 1998-05-13 | 中国石油化工总公司 | Catalyzer for hydrotreating residuum and its prepn. method |
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