CN1243084C - Method for preparing adsorbent for paraffin refining from shale ashes - Google Patents
Method for preparing adsorbent for paraffin refining from shale ashes Download PDFInfo
- Publication number
- CN1243084C CN1243084C CN 200310104976 CN200310104976A CN1243084C CN 1243084 C CN1243084 C CN 1243084C CN 200310104976 CN200310104976 CN 200310104976 CN 200310104976 A CN200310104976 A CN 200310104976A CN 1243084 C CN1243084 C CN 1243084C
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- CN
- China
- Prior art keywords
- shale ashes
- shale
- ashes
- paraffin
- acid
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002956 ash Substances 0.000 title claims abstract description 66
- 235000002918 Fraxinus excelsior Nutrition 0.000 title claims abstract description 62
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003463 adsorbent Substances 0.000 title claims description 10
- 238000007670 refining Methods 0.000 title abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000037452 priming Effects 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000004058 oil shale Substances 0.000 claims description 5
- 239000002594 sorbent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 239000001993 wax Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a method for preparing a paraffin refining absorbant from shale ashes. The method comprises the steps that the shale ashes are crushed; then, the crushed shale ashes and mineral acid are proportionally added into a reactor and the mixed liquid is heated, activated, filtered, washed by water and dried to prepare the absorbant under the condition of stirring. By means of the waste shale ashes as raw materials to prepare the paraffin absorbant, the present invention has the advantages of simple preparation process, low cost, obvious economic benefit and low environmental pollution by the shale ashes. The activated shale ashes are used as the paraffin refining absorbant so that the quality of a paraffin product is improved, and paraffin which meets the quality standard is obtained.
Description
Technical field
The invention belongs to the preparing technical field of paraffin treating adsorbent, specifically relate to a kind of method for preparing the paraffin treating adsorbent by shale ashes.
Background technology
Resinous shale is a kind of solid combustible mineral, and texture in the form of sheets can be by the split layer flakiness.Resinous shale is made up of mineral substance and organism, and hydrogen richness is higher in the organism, after destructive distillation, can get the shale oil of the similar natural oil of ratio of carbon-hydrogen.The destructive distillation semicoke burns in oxygen-containing gas, makes full use of the fixed carbon in the semicoke, and the solid residue of formation is shale ashes.
" Liaoning urban and rural environment science and technology " the 22nd the 6th phase of volume exercise question of delivering of the 19th～21 page of Jiang Gao is for pointing out in " after the shale retorting solid waste utilize approach " literary composition, the production rate of the solid residue after the oil shale distillation is 60～80wt% of resinous shale content, and most of solid residue is rejected and can not effectively utilizes, when taking a large amount of arable lands, again surrounding environment is caused secondary pollution, also increased the traffic capacity and the trucking costs of enterprise simultaneously.This article has proposed a kind of method of utilizing the resinous shale solid residue to make the shale vitrified brick.
" clean coal technology " the 8th the 2nd phase of volume exercise question of delivering such as 44～47 pages of what red plums points out also that in " development and utilization of resinous shale " literary composition the mode of effectively utilizing of shale ashes mainly contains at present: mine filling, system cement, haydite, sial carbon black and produced sintering brick etc.
This shows that the problem that needs at present to solve is effectively to utilize shale ashes, reduces environmental pollution, increases economic efficiency.
Summary of the invention
Purpose of the present invention is exactly in order effectively to utilize the shale ashes after resinous shale is processed, to reduce environmental pollution, having proposed a kind of method that is prepared the paraffin treating adsorbent by shale ashes.
Method of the present invention is as follows: shale ashes are pulverized, and preferably being crushed to granularity is 0.1～3.0mm, is 1: 1～1: 6 with mineral acid with weight ratio then, be preferably 1: 1～1: 4, add in the reactor, under agitation condition, be warming up to 60～150 ℃ and carry out priming reaction, constant temperature 1～8 hour; After priming reaction is finished, after filtration, washing, drying make sorbent material.
The shale ashes that the present invention adopts are to be adopted conventional method destructive distillation and burnt the solid residue that obtains behind the carbon residue by oil shale.The concrete production process of shale ashes is as follows: oil shale is heated to 400～500 ℃ of temperature, organism in the shale decomposes, tell from shale with oil gas and hydrocarbon gas form, semicoke is in certain oxygen containing atmosphere, remaining charcoal in 600～800 ℃ of temperature burning-off solids, utilize carbon residue to provide heat for destructive distillation, the solid residue that obtains is shale ashes.The main component of shale ashes is SiO
2, Al
2O
3, Fe
2O
3, MgO, CaO, NaO, K
2O etc.
Shale ashes of the present invention and mineral acid carry out priming reaction, and temperature of reaction is preferably 80～120 ℃, the reaction times be 1～6 hour preferable, used mineral acid is one or more in sulfuric acid, hydrochloric acid, nitric acid and the phosphoric acid; Described washing be with the shale ashes after the activation directly wash with water to pH value be 5～7, or the shale ashes after the activation are first uses the diluted hydrochloric acid aqueous solution washed twice, being washed with water to the pH value again is 5～7, the weight concentration of aqueous hydrochloric acid is 5%～15%; Described oven dry is meant and is dried to the moisture 6～8wt% of product under 105～140 ℃.The resulting active shale ashes sorbent material of the present invention can be made particulate state, also can be made into Powdered.
Organism in resinous shale decomposes and burns in the process of carbon residue, and shale ashes are inner can to produce many holes, forms bigger internal surface area, has certain absorption property, but active low.Adopt the mineral acid activation treatment, by means of H
+Tradable positively charged ion in the displacement shale ashes lattice vacancy is as Fe
3+, Mg
2+, Al
3+, Ca
2+, Na
+, K
+After, make shale ashes on physical structure, present more hole again, and on electrochemistry, present activity, just after the mineral acid activation treatment, can improve the activity and the adsorptive power of shale ashes greatly.Shale ashes after the activation can improve the quality product of paraffin as the paraffin treating adsorbent, obtain meeting the paraffin of quality standard.Paraffin process for refining process can be suitable for continuous operation, also can be used for periodical operation.
The present invention utilizes the depleted shale ashes as feedstock production paraffin sorbent material, and preparation process is simple, and cost is low, and has utilized the depleted shale ashes fully, has reduced the shale ashes pollution on the environment, has remarkable social benefit and economic benefit.
Shale ashes sorbent material of the present invention except that be used for paraffin refining, also can be used for gasoline, kerosene, diesel oil and lubricant base refining.
Embodiment
Below in conjunction with embodiment, specify technical scheme of the present invention and effect.
The used shale ashes sample of embodiment is the waste residue of Fushun oil shale behind destructive distillation and burning carbon residue.The paraffin that refining with adsorbents is used is No. 58 fully refined wax material, and its character sees Table 1.
Embodiment 1
It is 1.0mm that block shale ashes are crushed to granularity, is that the sulfuric acid of 90wt% is to join in reactor at 1: 1.5 with weight ratio again with shale ashes and concentration, heating while stirring, and temperature is controlled at 80 ℃, keeps 5 hours reaction times.After reaction product was filtered, being washed with water to the pH value was 5, is dried to the moisture 7wt% of product at 105 ℃ then.Get active shale ashes 3wt% and paraffin and add in the refining reaction device, 110 ℃ of extraction temperatures, constant temperature time 40 minutes, the character and the product yield of products obtained therefrom wax see Table 1.
Embodiment 2
It is 1.0mm that block shale ashes are crushed to granularity, is to join reactor at 1: 4 with shale ashes and concentrated hydrochloric acid (weight concentration is 30wt%) with weight ratio again, heating while stirring, and 3 hours reaction times is kept in 95 ℃ of temperature controls.Reaction product is washed with water to the pH value 6 after filtering, and is dried to the moisture 6wt% of product at 110 ℃ then.Get active shale ashes 3.5wt% and paraffin and add in the refining reaction device, 115 ℃ of extraction temperatures, constant temperature time 1 hour, the character of products obtained therefrom wax and the yield of product see Table 1.
Embodiment 3
It is 1.0mm that block shale ashes are crushed to granularity, is 1: 5 adding reactor with shale ashes and nitric acid (weight concentration is 65wt%) with weight ratio again, heating while stirring, and temperature is controlled at 105 ℃, keeps 2 hours reaction times.Reaction product is washed with water to the pH value 6 after filtering, and is dried to the moisture 7wt% of product at 110 ℃ then.Get active shale ashes 2.5wt% and paraffin and add in the refining reaction device, 120 ℃ of extraction temperatures, constant temperature time 1 hour, the character and the product yield of products obtained therefrom wax see Table 1.
Embodiment 4
It is 1.0mm that block shale ashes are crushed to granularity, is 1: 1 adding reactor with shale ashes and sulfuric acid (weight concentration is 98wt%) with weight ratio again, heating while stirring, and temperature is controlled at 110 ℃, keeps 1 hour reaction times.After reaction product is filtered,, and then be washed with water to the pH value 7 with 10wt% aqueous hydrochloric acid washed twice; After the water washing of activating shale ash, be dried to the moisture 8wt% of product at 105 ℃.Get active shale ashes 2wt% and paraffin and add in the refining reaction device, 120 ℃ of extraction temperatures, constant temperature time 1 hour, the character and the product yield of products obtained therefrom wax see Table 1.
Embodiment 5
It is 1.0mm that block shale ashes are crushed to granularity, is 1: 2.5 adding reactor with shale ashes and phosphoric acid (weight concentration is 70wt%) with weight ratio again, heating while stirring, and temperature is controlled at 120 ℃, keeps 4 hours reaction times.After reaction product is filtered, and then to be washed with water to the pH value be 6; After the water washing of activating shale ash, be dried to the moisture 7wt% of product at 108 ℃.Get active shale ashes 4wt% and paraffin and add in the refining reaction device, 120 ℃ of extraction temperatures, constant temperature time 1 hour, the character and the product yield of products obtained therefrom wax see Table 1.
Embodiment 6
It is 2.5mm that block shale ashes are crushed to granularity, is 90wt% sulfuric acid with shale ashes and concentration again, is 1: 5 adding reactor with weight ratio, heating while stirring, and temperature is controlled at 70 ℃, keeps 7 hours reaction times.After reaction product was filtered, with 15wt% aqueous hydrochloric acid washing 2 times, and then to be washed with water to the pH value be 7; After the water washing of activating shale ash, be dried to the moisture 8wt% of product at 130 ℃.Get active shale ashes 3wt% and paraffin and add in the refining reaction device, 120 ℃ of extraction temperatures, constant temperature time 1 hour, the character and the product yield of products obtained therefrom wax see Table 1.
Embodiment 7
It is 0.5mm that block shale ashes are crushed to granularity, is the sulfuric acid of 95wt% with shale ashes and concentration again, is 1: 1 adding reactor with weight ratio, heating while stirring, and temperature is controlled at 140 ℃, keeps 1 hour reaction times.After reaction product is filtered,, and then be washed with water to the pH value 6 with 5wt% aqueous hydrochloric acid washed twice; After the water washing of activating shale ash, be dried to the moisture 8wt% of product at 115 ℃.Get active shale ashes 2wt% and paraffin and add in the refining reaction device, 120 ℃ of extraction temperatures, constant temperature time 1 hour, the character and the product yield of products obtained therefrom wax see Table 1.
The character of the product wax after table 1 paraffin and each the embodiment refining with adsorbents
| Character | Paraffin | Product wax | ||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | ||
| Oleaginousness, wt% | 0.20 | 0.23 | 0.21 | 0.20 | 0.20 | 0.22 | 0.21 | 0.2 |
| The Sai Shi colorimetric, number | +12 | +30 | +30 | +28 | +28 | +29 | +30 | +28 |
| Light stability, number | 6～7 | 3 | 3～4 | 4 | 4 | 3 | 3 | 4 |
| Penetration degree, 1/10mm | 14 | 14 | 14 | 14 | 14 | 14 | 14 | 13 |
| Fusing point, ℃ | 58.5 | 58.5 | 58.3 | 58.6 | 58.6 | 58.6 | 58.4 | 58.2 |
| Product wax yield, wt% | 96.5 | 96.2 | 97.1 | 97.6 | 96.1 | 95.9 | 95.8 | |
By table 1 as seen, adopt the prepared active shale ashes of the inventive method as the paraffin treating adsorbent, the yield height of the wax product after making with extra care meets target level of product quality GB446-93 simultaneously.
Claims (7)
1, a kind of method for preparing the paraffin treating adsorbent by shale ashes, comprise the steps: that it is 0.1～3.0mm that shale ashes are crushed to granularity, be to add in the reactor in 1: 1～1: 6 with mineral acid with weight ratio then, under agitation condition, be warming up to 60～150 ℃ and carry out priming reaction, constant temperature 1～8 hour; After priming reaction is finished, after filtration, washing, drying make sorbent material.
2, in accordance with the method for claim 1, it is characterized in that described shale ashes are the solid residues that obtained by oil shale behind destructive distillation and burning carbon residue.
3, in accordance with the method for claim 1, it is characterized in that described mineral acid is one or more in sulfuric acid, hydrochloric acid, nitric acid and the phosphoric acid.
4, in accordance with the method for claim 1, the solid-liquid weight ratio that it is characterized in that described shale ashes and mineral acid is 1: 1～1: 4.
5, in accordance with the method for claim 1, it is characterized in that the temperature that priming reaction is carried out in described shale ashes and acid is 80～120 ℃, the reaction times is 1～6 hour.
6, in accordance with the method for claim 1, it is characterized in that described washing be with the activation after shale ashes directly wash with water to the pH value be 5～7, or the shale ashes after the activation are earlier with diluted hydrochloric acid aqueous solution washing 1～2 time, being washed with water to the pH value again is 5～7, and the weight concentration of aqueous hydrochloric acid is 5%～15%.
7, in accordance with the method for claim 1, it is characterized in that described drying is meant is dried to the moisture 6～8wt% of product under 105～140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104976 CN1243084C (en) | 2003-10-31 | 2003-10-31 | Method for preparing adsorbent for paraffin refining from shale ashes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104976 CN1243084C (en) | 2003-10-31 | 2003-10-31 | Method for preparing adsorbent for paraffin refining from shale ashes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1611580A CN1611580A (en) | 2005-05-04 |
| CN1243084C true CN1243084C (en) | 2006-02-22 |
Family
ID=34757134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310104976 Expired - Lifetime CN1243084C (en) | 2003-10-31 | 2003-10-31 | Method for preparing adsorbent for paraffin refining from shale ashes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1243084C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527324A (en) * | 2012-01-05 | 2012-07-04 | 张泉 | Porous adsorbing material with health care function and preparation method of porous adsorbing material |
| CN103601229B (en) * | 2013-11-01 | 2015-04-01 | 青岛星火化工技术有限公司 | Method for preparation of chemical raw materials by using of potassium-containing shale |
-
2003
- 2003-10-31 CN CN 200310104976 patent/CN1243084C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1611580A (en) | 2005-05-04 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
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Granted publication date: 20060222 |