CN1003214B - Method for prepn. of flocculating agents - Google Patents
Method for prepn. of flocculating agents Download PDFInfo
- Publication number
- CN1003214B CN1003214B CN85103994A CN85103994A CN1003214B CN 1003214 B CN1003214 B CN 1003214B CN 85103994 A CN85103994 A CN 85103994A CN 85103994 A CN85103994 A CN 85103994A CN 1003214 B CN1003214 B CN 1003214B
- Authority
- CN
- China
- Prior art keywords
- solution
- pac
- flocculant
- sodium carbonate
- sodium
- Prior art date
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000008394 flocculating agent Substances 0.000 title 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 50
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 25
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 17
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 5
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003311 flocculating effect Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000007850 degeneration Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to a method for preparing alkaline aluminum chloride which is used for flocculation treatment for aqueous emulsion containing fine particles. In a previous method, in order to improve the flocculability of alkaline aluminum chloride, various sulfate ions need to be added. Therefore, the defects of high manufacturing cost, incomplete flocculability, alkalinity reduction, etc. exist. In the present invention, reaction products of sodium aluminate and sodium sulfate are added to the alkaline aluminum chloride solution, so the defects are overcome.
Description
The invention relates to the method that adopts basic aluminium chloride (below be abbreviated as pAC) to make flocculant effectively.The water turbidity that this flocculant can be to industry and mining waste water, dyeing waste-water, starch wastewater, contain fine solid particles up and down in water etc. carries out flocculation treatment.
In the past, the pAC solution as flocculant is used in order to improve flocculating property, adds sulfate ion (polymerization accelerant) in adding the Undec concentration range of water
As everyone knows: (1) sodium sulphate, (2) sulfuric acid, (3) aluminum sulfate etc. can produce sulfate ion.But the shortcoming of (1) is the manufacturing cost height, and the shortcoming of (2) is that flocculating property is poor, and the shortcoming of (3) is that the basicity of pAC is low.Yet, though some shortcoming has at first adopted the method for aluminum sulfate.
In addition, though in known technology, as the operation that improves basicity, the compound that calcium such as using calcium hydroxide, calcium oxide, calcium carbonate is often arranged, perhaps sodium carbonate, NaOH and the pAC solution that contains sulfate ion mix so that the method for sex change (below, because of needs abbreviate sex change as).But the compound that adds calcium generates the calcium sulfate that difficult separation is removed, and adds the method for NaOH, because of the aluminium hydroxide that generates indissoluble makes it to be difficult to filter, and can not get shortcoming greater than the pAC solution of 50% basicity in addition.
Owing to this reason, in the above-mentioned all cpds of enumerating, the method for generally taking to add sodium carbonate is carried out reaction of degeneration (RD), still, compares with other compounds, inevitably has manufacturing cost than higher shortcoming.
Therefore, purpose of the present invention relates to and improves or eliminate these shortcomings and make a kind of method of novel flocculant.In other words, be about industrial easy operation, with low cost, can contain the manufacture method of the pAC solution of sulfate ion as flocculant usefulness.
For reaching the above-mentioned purpose of the present invention, can in pAC solution, add the product of sodium carbonate, sodium aluminate and sodium sulphate reaction.Below be about more detailed description of the present invention.
At first, the present invention " is soluble in the aluminium hydroxide of acid " with following method manufacturing.Because the aluminium hydroxide that generates with sodium aluminate and aluminum sulfate is insoluble in acid, and the aluminium hydroxide that sodium carbonate and aluminum sulfate generate, though very easily be dissolved in acid, cost height (as previously mentioned) because of having used the high sodium carbonate of price, this is a well known fact.The aluminium hydroxide that the heart the present invention of institute adopts the mixed solution of sodium aluminate and sodium carbonate and aluminum sulfate to generate finds that it very unexpectedly, very easily be dissolved in the acid.
Like this, core of the present invention is exactly earlier sodium carbonate and sodium aluminate to be mixed stirring, aluminum sulfate is added to makes aluminium hydroxide in the mixed solution then.This charging sequence is also passable conversely, is about to sodium carbonate and sodium aluminate mixed solution and is added in the aluminum sulfate solution also passable.
The concentration of all ingredients among the present invention, for example, its Al of sodium aluminate solution
2O
3Be 10%, its Al of aluminum sulfate solution
2O
3Be 8%, this use amount what, be according to the theoretical amount of basicity that requires in the pAC solution of using as flocculant to contain and sulfate ion concentration and suitable variation.Theoretical amount can be calculated as follows:
For example: when obtaining the flocculant pAC of basicity 55% by the pAC solution of basicity 45%, according to formula (II) m=6 * 0.45=2.7, n=6 * 0.55=3.3, then with respect to 1 mole of pAC in the pAC stoste, the molal quantity X of aluminium hydroxide should be 0.444.The use amount of sodium carbonate, aluminum sulfate and sodium aluminate depends on the aluminium hydroxide molal quantity that is obtained by (I) formula.In addition, at this moment the use amount of sodium sulphate can be determined by the needed sulfate concentration of flocculant pAC, and the mol ratio of sodium carbonate that uses and sodium aluminate is preferably more than 0.14: 1.
The upper limit of the used ratio of above-mentioned sodium carbonate, though have no particular limits from the viewpoint of reaction, from the viewpoint that commercial scale is implemented, this ratio is big more, then production cost is high more, does not have practical significance so surpass necessary usage ratio.
The amount of above-mentioned sodium carbonate, though be not particularly limited, but wish to use 10～30%(weight) concentration.
For the present invention, as note above-mentioned some, just can obtain being soluble in the aluminium hydroxide of acid.
The preparation temperature of this aluminium hydroxide should be lower than 50 ℃.If preparation temperature is higher than 50 ℃, then Zhi Bei aluminium hydroxide will be insoluble in acid, so to adding the technology of mixing later on unfavorable in pAC solution.
The present invention subsequently with above-mentioned reactant liquor intactly perhaps adds the hydroxide aluminium block that filters out to dissolving (sex change) in the pAC solution, the pAC solution that obtains having desired sulfate ion concentration and basicity.
Though wish to give and pAC solution be warmed to 60～70 ℃, not strict restriction earlier.In addition, add above-mentioned reactant liquor or aluminium hydroxide after, temperature need be transferred to 40～50 ℃, about 30 minutes of reaction of degeneration (RD) time.
According to the present invention, with sodium aluminate, sodium carbonate and the sodium sulphate reaction of theoretical amount, it all is desirable can making basicity (below 65%) and sulfate ion concentration, the pAC solution that flocculating property is good.
Because the present invention is in reaction of degeneration (RD), use the amount of sodium carbonate, 1/7 when being original single use sodium carbonate is so be very favorable for industrial production.In addition, because the reaction of degeneration (RD) foaming produces foam less or hardly, thus unlike original technology, must add defoamer, and the reaction of degeneration (RD) time, also shortened 3/4 than original method.
Specifically describe the present invention with embodiment and comparative example below.
Embodiment 1
With producing basicity after the sex change is the theoretical amount sodium aluminate solution (Al that 50% pAC solution is used
2O
310%) 111.5g and sodium carbonate liquor (Na
2CO
320%) 72.5g mixes, and adds aluminum sulfate solution (Al then
2O
38%) 279.0g reacts the aluminium hydroxide reactant liquor that just can obtain to be soluble in acid down at 40 ℃.
This aluminium hydroxide reactant liquor that is soluble in acid is added to and is warmed up to 60 ℃, the pAC stoste (Al of 1kg
2O
3Concentration 19.9%, basicity 48.6%, sulfate radical 0%, S.S0.9%) in, dissolving post curing 30 minutes.Add 794ml water then and make Al
2O
3Concentration reaches 10.3%, and the elimination insoluble matter can obtain the pAC solution of using as flocculant.Table 1 has been listed analysis result.
Comparative example 1
Without sodium carbonate, only will produce basicity after the sex change and be the theoretical amount sodium aluminate solution (Al that 50% pAC solution is used
2O
310%) 171.1g and aluminum sulfate solution (Al
2O
38%) 286.9g mixes, and other steps are the same with embodiment 1, made the pAC solution of using as flocculant.Analysis result is listed at table 1.
Embodiment 2
Theoretical amount sodium aluminate solution (the Al that basicity is used for 55%pAC solution after the sex change will be produced
2O
310%) 267.1g, sodium carbonate liquor (Na
2CO
320%) 77.8g and aluminum sulfate solution (Al
2O
38%) 299.6g mixes, and other steps are identical with embodiment 1, made the pAC solution of using as flocculant.Analysis result is listed in table 1.
Comparative example 2
Without sodium carbonate, only will produce the theoretical amount sodium aluminate solution (Al that basicity is used for 55%pAC solution after the sex change
2O
310%) 336.0g and aluminum sulfate solution (Al
2O
38%) 308.8g mixes, and other steps are identical with embodiment 1, made the pAC solution of using as flocculant.Analysis result is listed in table 1.
Embodiment 3～6
Sodium aluminate solution (the Al of the theoretical amount that basicity after the sex change uses for 60%pAC solution will be produced
2O
310%) sodium carbonate liquor (Na,
2CO
320%) and aluminum sulfate solution (Al
2O
38%) mix, consumption is listed in table 1, and other steps are identical with embodiment 1, made the pAC solution of using as flocculant.Analysis result is listed in table 1.
Comparative example 3
Without sodium carbonate, only will produce the theoretical amount sodium aluminate solution (Al that basicity is used for the 60%pAC dope after the sex change
2O
310%) 447.6g and aluminum sulfate solution (Al
2O
38%) 323.6g mixes, and other steps are identical with embodiment 1, made the pAC solution of using as flocculant.Analysis result is listed in table 1.
Comparative example 4 and example 5
Sodium carbonate liquor (the Na of the theoretical amount that basicity after the sex change uses for 60%pAC solution will be produced
2CO
320%) sodium aluminate solution (Al,
2O
310%) and aluminum sulfate solution (Al
2O
38%) mix, the mol ratio of sodium carbonate and sodium aluminate was less than 0.14: 1, and other steps are identical with embodiment 1, made the pAC solution of using as flocculant.Analysis result is listed in table 1.
Embodiment 7
The pAC solution of using as flocculant to making with the embodiment of the invention 1 carries out the flocculating property compare test.
Sample (1) is a wood river surface water (turbidity 2.3ppm, pH7.5,10 ℃ of water temperatures, basicity 16.3) once.
The pAC solution that makes by embodiment 1 by Al
2O
32ppm is added in the 1000ml sample (1), stirs (100rpm) fast 1 minute, stirs (20rpm) 10 minutes at a slow speed, leaves standstill then 10 minutes.After stirring end at a slow speed, measure the diameter of suspended particles and leave standstill the turbidity of supernatant liquid afterwards, its result is by table 2 illustrate.
Sample (2) is sandstone washing draining (11 ℃ of S.S4.7%, pH8.5, water temperatures).
Table 1
The pAC solution that makes by embodiment 1 by Al
2O
36ppm is added in the 1000ml sample (2), stirs (100rpm) fast, leaves standstill then 3 minutes.Stir fast finish after, measure the diameter of suspended particles and leave standstill the turbidity of back supernatant liquid, its as a result table 2 illustrate.
Sample (8) is for making the draining (S.S1590mg/l, turbidity 259ppm, pH4.3, COD327mg/l) of bread
The NaOH of 220ppm is added in the 1000ml sample (3), stirred (100rpm) fast 1 minute, the pAC solution that embodiment 1 is made is by Al then
2O
320ppm adds, and stirs (100rpm) 1 minute fast, stirs (20rpm) 2 minutes at a slow speed, leaves standstill then 5 minutes.Stir at a slow speed and finish turbidity and the COD value that the back is measured the suspended particles diameter, left standstill the back supernatant liquid.The result is by table 2 illustrate.
Embodiment 8
For the flocculant that makes by embodiment 2 pAC solution, carry out the flocculating property test identical with embodiment 7.The result is by table 2 illustrate.
Embodiment 9
For the flocculant that makes by embodiment 3 pAC solution, carry out the flocculating property test identical with embodiment 7.The result is by table 2 illustrate.
Comparative example 7
For the flocculant that makes by comparative example 1 pAC solution, carry out the flocculating property test identical with embodiment 7.The result is by table 2 illustrate.
Comparative example 8
For the flocculant that makes by comparative example 2 pAC solution, carry out the flocculating property test identical with embodiment 7.The result is by table 2 illustrate.
Comparative example 9
For the flocculant that makes by comparative example 3 pAC solution, carry out the flocculating property test identical with embodiment 7.The result is by table 2 illustrate.
Comparative example 10
The flocculant of market sale with pAC solution (basicity 55%), is carried out the flocculating property test identical with embodiment 7.The result is by table 2 illustrate.
According to result shown in the table 2, can know, according to the prepared flocculant of manufacture method of the present invention pAC solution, be identical with the market sale product, have identical flocculating property in other words.Therefore manufacture method of the present invention is in industrial easy production, and manufacturing cost is cheap, demonstrates very big superiority.
Table 2
Annotate: 1, nephelometer is with Japanese precision optics (strain) SEp-pT901B type, particle tester usefulness (strain) イ ヮ ≠ 6 formulas
2, particle diameter D
1＜0.5mm, D
20.5～0.75mm, D
30.75～1.0mm, D
41.0～1.5mmD
51.5～2.25mm
3, the mensuration KMnO of COD
4Under 100 ℃, carry out.
Claims (1)
1, the manufacture method of flocculant, it is characterized in that: by in basic aluminium chloride solution, interpolation is reacted the mixed solution of sodium carbonate, sodium aluminate and aluminum sulfate to the aluminium hydroxide (mol ratio of sodium carbonate and sodium aluminate is 0.14: 1～2.10: 1) that generates under 50 ℃～room temperature, thereby makes this basic aluminium chloride sex change.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59132202A JPS6114126A (en) | 1984-06-27 | 1984-06-27 | Manufacture of high concentration solution of polyaluminum chloride having high basicity |
| CN85103994A CN1003214B (en) | 1984-06-27 | 1985-05-24 | Method for prepn. of flocculating agents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59132202A JPS6114126A (en) | 1984-06-27 | 1984-06-27 | Manufacture of high concentration solution of polyaluminum chloride having high basicity |
| CN85103994A CN1003214B (en) | 1984-06-27 | 1985-05-24 | Method for prepn. of flocculating agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103994A CN85103994A (en) | 1986-11-19 |
| CN1003214B true CN1003214B (en) | 1989-02-08 |
Family
ID=25741679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85103994A Expired CN1003214B (en) | 1984-06-27 | 1985-05-24 | Method for prepn. of flocculating agents |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6114126A (en) |
| CN (1) | CN1003214B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055106C (en) * | 1995-06-16 | 2000-08-02 | 法国石油公司 | Catalysts containing doping metal for use in hydrocarbon conversion reactions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100380926B1 (en) * | 2000-09-21 | 2003-04-26 | (주)이앤텍 | A method for production of polymeric aluminum coagulant using wasted aluminum chloride solution |
| CN100355656C (en) * | 2004-07-09 | 2007-12-19 | 中国石油天然气股份有限公司 | Preparation method of polyaluminum chloride with high aluminum content |
| JP5877600B2 (en) * | 2011-03-31 | 2016-03-08 | アクアス株式会社 | Aggregation processing equipment |
| JP6998729B2 (en) * | 2017-10-31 | 2022-01-18 | 東亞合成株式会社 | Ground improver composition and its use |
| CN113292091A (en) * | 2021-05-17 | 2021-08-24 | 太仓市业洪净水新材料有限公司 | Preparation process of polyaluminum chloride polysulfide flocculant for low-temperature high-turbidity water treatment |
| CN117339552B (en) * | 2023-11-21 | 2024-06-21 | 陕西科技大学 | Gas-based residue adsorption-flocculation multifunctional water purifying agent and preparation method and application thereof |
-
1984
- 1984-06-27 JP JP59132202A patent/JPS6114126A/en active Granted
-
1985
- 1985-05-24 CN CN85103994A patent/CN1003214B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055106C (en) * | 1995-06-16 | 2000-08-02 | 法国石油公司 | Catalysts containing doping metal for use in hydrocarbon conversion reactions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6114126A (en) | 1986-01-22 |
| JPH024534B2 (en) | 1990-01-29 |
| CN85103994A (en) | 1986-11-19 |
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