CN103920501B - By the Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan - Google Patents
By the Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan Download PDFInfo
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Abstract
By the Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan, relate to the catalyst of methyl mercaptan processed.Described catalyst with the compound of tungsten for main active component, with the oxygenatedchemicals of the oxygenatedchemicals of cobalt and potassium for cocatalyst, with spherical gamma-Al
2o
3for carrier; With CoO-K
2o-WO
3/ γ-Al
2o
3definition and metering, CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be (0.05 ~ 0.35): (5 ~ 8): (10 ~ 18): 100.The ammonium metatungstate of metering and Anhydrous potassium carbonate are dissolved in the deionized water of metering, then add the organic acid of metering, then regulate solution ph to 8 ~ 10 with ammoniacal liquor, after leaving standstill, add the cobalt salt of metering again, then leave standstill aging, obtain maceration extract; Join in maceration extract by spherical gama-alumina, filter after dipping and remove maceration extract, obtain mercaptan catalyst agent presoma, dry, dry, calcining, obtains product.
Description
Technical field
The present invention relates to the catalyst of methyl mercaptan processed, especially relate to a kind of Catalysts and its preparation method by carbon disulfide and Methanol methyl mercaptan.
Background technology
As the methyl mercaptan (CH of the important chemical intermediate of synthetic methionine, medicine, agricultural chemicals
3sH), its traditional preparation method reacts obtained by hydrogen sulfide and methyl alcohol, and catalyst generally selects gama-alumina as carrier, carrying alkali metal tungstates or alkali metal molybdate.The catalyst K of such as publication No. described by the Chinese patent of CN102658208A
2wO
4/ γ-Al
2o
3, be 350 ~ 400 DEG C in temperature, pressure is 0.9 ~ 1.1MPa, and the gas space velocity of hydrogen sulfide and carbinol mixture is 1100 ~ 2400h
-1, the mol ratio of material benzenemethanol and hydrogen sulfide is under the condition of 1: 1 ~ 4, and the selective of methyl mercaptan is greater than 85%, and methyl mercaptan yield is greater than 80%.And Chinese patent CN102247833A and the catalyst described by US Patent No.-PS2820062.
And the raw material hydrogen sulfide of conventional method methyl mercaptan is mainly obtained by natural gas and sulfur burning reaction, CH
4+ 4S → 2H
2s+CS
2, CS in this product
2account for 50%, and current CS
2the market demand is few, hoards surplus, and price is low again.Thus to adopt by carbon disulfide-methyl alcohol legal system for methyl mercaptan, can make up by the defect of hydrogen sulfide-methyl alcohol legal system methyl mercaptan.
What study carbon disulfide-methyl alcohol legal system methyl mercaptan the earliest is Japanese Sanko Co., Ltd., and deliver the clear 32-7419 of patent and clear 37-15608, carbon disulfide and methyl alcohol is adopted to react, with activated alumina or the aluminium oxide that is loaded with cadmium or thorium for catalyst produces methyl sulfide and methyl mercaptan, the product obtained after reaction mainly methyl sulfide and reaction temperature generally wants more than 400 DEG C.
Within 1972, Tso Tat Co., Ltd., Japan further study this method, deliver the clear 47-41327 of patent, the aqueous solution of alkali metal salt having dissolved the 6th subgroup element (molybdenum, tungsten) is added active alumina powder carry out mixing and adopt infusion process and obtain catalyst, the mol ratio of reactant carbon disulfide and methyl alcohol is 1: (2.6 ~ 3.0), reaction temperature 300 ~ 350 DEG C, load is (0.17 ~ 0.30) gCS
2/ (ml
catalysth), after reaction, the conversion ratio of methyl alcohol is the highest also only has 75%.
Shenyang Chemical Engineering Design research institute of nineteen eighty-two China is also studied the method for carbon disulfide and methanol-fueled CLC methyl mercaptan, the people such as Lu Chuande (research of methyl mercaptan synthesis) select gama-alumina to be carrier, load regulation six subgroup element, makes the selective and yield of methyl mercaptan all reach foreign level.And over nearly more than 20 years, about the catalyst research of carbon disulfide and methanol-fueled CLC methyl mercaptan is very few.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method by carbon disulfide and Methanol methyl mercaptan.This mercaptan catalyst agent is a kind of catalyst with greater activity and optionally synthesis of methyl mercaptan, obtained mercaptan catalyst agent can be used in catalysis carbon disulfide and methyl alcohol Reactive Synthesis methyl mercaptan, for commercial synthesis methyl mercaptan provides a simple and practical novel synthetic.
The described catalyst by carbon disulfide and Methanol methyl mercaptan with the compound of tungsten for main active component, with the oxygenatedchemicals of the oxygenatedchemicals of cobalt and potassium for cocatalyst, with spherical gamma-Al
2o
3for carrier; Described catalyst is with CoO-K
2o-WO
3/ γ-Al
2o
3definition and metering; In described catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be (0.05 ~ 0.35): (5 ~ 8): (10 ~ 18): 100, be preferably (0.1 ~ 0.25): (6.5 ~ 8): (16 ~ 18): 100.
The described preparation method by the catalyst of carbon disulfide and Methanol methyl mercaptan, comprises the following steps:
1) by the ammonium metatungstate { (NH of metering
4)
6h
2w
12o
40xH
2o} and Anhydrous potassium carbonate (K
2cO
3) be dissolved in the deionized water of metering, then add the organic acid of metering, then regulate solution ph to 8 ~ 10 with ammoniacal liquor, after leaving standstill, add the cobalt salt of metering again, then leave standstill aging, obtain maceration extract;
2) spherical gama-alumina is joined step 1) in gained maceration extract, after dipping, filter and remove maceration extract, obtain mercaptan catalyst agent presoma;
3) by step 2) gained mercaptan catalyst agent presoma dries, and after oven dry, calcining, obtains the catalyst by carbon disulfide and Methanol methyl mercaptan.
In step 1) in, described organic acid can be selected from least one in citric acid, oxalic acid, Pidolidone etc.; The described standing time can be 0.5h; Described cobalt salt can be selected from the one in cobalt nitrate, cobalt oxalate etc.; The described standing aging time again can be 1h.
In step 2) in, the diameter of described spherical gama-alumina can be Ф 2 ~ 4mm; The time of described dipping can be 10 ~ 14h.
In step 3) in, the method for described oven dry can be: dry to constant weight at 80 DEG C, then dries 4h under 120 DEG C of conditions; Described calcining can be placed in Muffle furnace in 400 DEG C of calcining 3h; Gained can adopt Xray fluorescence spectrometer (XRF) to measure the content of each active component by the catalyst of carbon disulfide and Methanol methyl mercaptan.
Described organic acid: spherical gama-alumina: the mass ratio of deionized water can be (10 ~ 15): 100: 140.
The activity rating of mercaptan catalyst agent carries out in fixed bed flowing reactive system, and reaction tube specification is Ф 10mm × 56mm, and catalyst is positioned at stove temperature controlling point place, and loadings is 2mL, and particle diameter is 30 ~ 60 orders; Controlling reaction temperature is 340 DEG C; The mol ratio of reactant feed methyl alcohol and carbon disulfide is 2.2; Reactant feed air speed is 1000h
-1; Reaction pressure is 0.3MPa.
Unstripped gas and product composition are by gas-chromatography on-line analysis.Chromatogram adopts Shanghai China to love the full-automatic chromatograph of GC9560, chromatographic column: PorapakQ; Column length: 3m; Caliber: Ф 3 × 0.5mm.
The invention has the advantages that: because the raw material hydrogen sulfide of industrial synthesis of methyl mercaptan is mainly by natural gas (CH
4) and sulphur (S) combustion reaction obtain, while obtained hydrogen sulfide, have also been obtained a large amount of accessory substance carbon disulfide (CS
2), and carbon disulfide intractability is large; The catalyst that the present invention relates to not only can realize carbon disulfide to turn waste into wealth, and reduces because of a large amount of manpower and materials spent by process carbon disulfide, and provides new scheme for the synthesis of methyl mercaptan.
Mercaptan catalyst agent disclosed by the invention can efficient catalytic carbon disulfide and methyl alcohol Reactive Synthesis methyl mercaptan, and its preparation method is simple, does not need special installation, is convenient to suitability for industrialized production, be with a wide range of applications.
Detailed description of the invention
Embodiment 1: by 3.02g ammonium metatungstate { (NH
4)
6h
2w
12o
40xH
2o} and 1.70g Anhydrous potassium carbonate (K
2cO
3) add in 14ml deionized water and make it dissolve under constantly stirring, then 1.0g citric acid is added, 2ml ammoniacal liquor (concentration is 25 ~ 28%) is used to regulate solution ph to 10 again after continuing to stir 5min, 0.10g cobalt nitrate is under agitation added after leaving standstill 0.5h, aged at room temperature 1h after dissolving, obtains maceration extract.Then take the spherical gama-alumina of 10.0g (Ф 2 ~ 4mm, Shandong Zibo Xin Peng Chemical Co., Ltd.) to join in maceration extract and flood 14h, filter and remove maceration extract, obtain mercaptan catalyst agent presoma; Gained mercaptan catalyst agent presoma is dried, after drying to constant weight under 80 DEG C of conditions, dries 4h in 120 DEG C and be placed in Muffle furnace again at 400 DEG C of calcining 3h, obtain mercaptan catalyst agent.Characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.13: 5.1: 11.4: 100.Be designated as 1. Co-K
2w/Al
2o
3.
The activity rating of gained mercaptan catalyst agent carries out in fixed bed flowing reactive system, and reaction tube specification is Ф 10mm × 56mm, and catalyst is positioned at stove temperature controlling point place, and loadings is 2mL, and particle diameter is 30 ~ 60 orders; Reaction temperature is 340 DEG C; The mol ratio of reactant feed methyl alcohol and carbon disulfide is 2.2; Reactant feed air speed is 1000h
-1; Reaction pressure is 0.3MPa.Unstripped gas and product composition are by gas-chromatography on-line analysis, and chromatogram adopts Shanghai China to love the full-automatic chromatograph of GC9560, chromatographic column: PorapakQ; Column length: 3m; Caliber: Ф 3 × 0.5mm.Activity evaluation is in table 1.
Embodiment 2: the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate is made into 3.78g and 2.12g respectively, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.17: 7.7: 17.5: 100.Be designated as 2. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 3: the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate is made into 4.53g and 2.54g respectively, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.18: 8.2: 17.7: 100.Be designated as 3. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 4: the consumption of the ammonium metatungstate in embodiment 1, Anhydrous potassium carbonate and cobalt nitrate is made into 3.78g and 2.12g and 0.2g respectively, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.25: 7.8: 17.6: 100.Be designated as 4. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 5: the consumption of the ammonium metatungstate in embodiment 1, Anhydrous potassium carbonate and cobalt nitrate is made into 3.78g and 2.12g and 0.3g respectively, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.3: 7.6: 17.9: 100.Be designated as 5. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 6: the consumption of the ammonium metatungstate in embodiment 1, Anhydrous potassium carbonate and cobalt nitrate is made into 3.78g and 2.12g and 0.4g respectively, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.34: 7.8: 17.5: 100.Be designated as 6. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 7: the consumption of the ammonium metatungstate in embodiment 1, Anhydrous potassium carbonate and citric acid is made into 3.78g, 2.12g and 1.5g respectively, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.17: 7.4: 17.6: 100.Be designated as 7. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 8: the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate is made into 3.78g, 2.12g respectively, and 1.0g citric acid makes 1.0g oxalic acid into, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.16: 7.5: 18: 100.Be designated as 8. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 9: the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate is made into 3.78g, 2.12g respectively, and 1.0g citric acid makes 1.0gL-glutamic acid into, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.12: 7.6: 17.3: 100.Be designated as 9. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Embodiment 10: the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate is made into 3.78g, 2.12g respectively, and 0.1g cobalt nitrate makes 0.1g cobalt oxalate into, all the other steps, with embodiment 1, characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.11: 7.5: 17.8: 100.Be designated as 10. Co-K
2w/Al
2o
3, Activity evaluation is in table 1.
Comparative example 1: make the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate into 3.78g and 2.12g respectively, do not add organic acid in preparation process, all the other steps are with embodiment 1.Characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.05: 6.7: 16.4: 100, be designated as Co-K
2w/Al
2o
3.Activity rating condition is with embodiment 1, and Activity evaluation is in table 1.
Comparative example 2: by 5.0g potassium tungstate (AR, Chemical Reagent Co., Ltd., Sinopharm Group) join in 14ml distilled water and make it dissolve under constantly stirring, 1.0g citric acid is added wherein after dissolving, 2ml ammoniacal liquor adjust ph to 10 is used after stirring 5min, 0.10g cobalt nitrate is under agitation added after leaving standstill 0.5h, leave standstill aged at room temperature 1h, then the spherical gama-alumina of 10.0g (Ф 3mm is taken, Shandong Zibo Xin Peng Chemical Co., Ltd.) flood wherein 14h, filter and remove maceration extract, obtain mercaptan catalyst agent presoma; Gained mercaptan catalyst agent presoma is dried, after drying to constant weight under 80 DEG C of conditions, dries 4h in 120 DEG C and be placed in Muffle furnace again at 400 DEG C of calcining 3h, obtain mercaptan catalyst agent.Characterize through XRF and to learn in the agent of gained mercaptan catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be 0.13: 5.9: 10.1: 100.Be designated as Co-K
2wO
4/ Al
2o
3, activity rating condition is with embodiment 1, and Activity evaluation is in table 1.
Comparative example 3: make the consumption of the ammonium metatungstate in embodiment 1 and Anhydrous potassium carbonate into 3.78g and 2.12g respectively, do not add cobalt nitrate in preparation process, all the other steps are with embodiment 1.Characterize through XRF and learn K in the agent of gained mercaptan catalyst
2o: WO
3: γ-Al
2o
3mass ratio be 7.4: 17.7: 100, be designated as K
2w/Al
2o
3.Activity rating condition is with embodiment 1, and Activity evaluation is in table 1.
The catalyst activity evaluation result of table 1 embodiment 1 ~ 10 and comparative example 1 ~ 3
| Embodiment/comparative example | Catalyst | S Methyl mercaptan(％) | X Methyl alcohol(％) | Y Methyl mercaptan(％) |
| Embodiment 1 | ①Co-K 2W/Al 2O 3 | 82.45 | 99.53 | 82.06 |
| Embodiment 2 | ②Co-K 2W/Al 2O 3 | 87.56 | 99.39 | 87.03 |
| Embodiment 3 | ③Co-K 2W/Al 2O 3 | 86.33 | 99.40 | 85.81 |
| Embodiment 4 | ④Co-K 2W/Al 2O 3 | 87.25 | 99.28 | 86.62 |
| Embodiment 5 | ⑤Co-K 2W/Al 2O 3 | 86.17 | 99.35 | 85.61 |
| Embodiment 6 | ⑥Co-K 2W/Al 2O 3 | 86.21 | 99.66 | 85.92 |
| Embodiment 7 | ⑦Co-K 2W/Al 2O 3 | 87.01 | 99.43 | 86.51 |
| Embodiment 8 | ⑧Co-K 2W/Al 2O 3 | 87.18 | 99.37 | 86.63 |
| Embodiment 9 | ⑨Co-K 2W/Al 2O 3 | 86.97 | 99.32 | 86.34 |
| Embodiment 10 | ⑩Co-K 2W/Al 2O 3 | 87.21 | 99.28 | 86.56 |
| Comparative example 1 | Co-K 2W/Al 2O 3 | 80.09 | 99.83 | 79.95 |
| Comparative example 2 | Co-K 2WO 4/Al 2O 3 | 71.88 | 99.21 | 71.31 |
| Comparative example 3 | K 2W/Al 2O 3 | 81.16 | 99.65 | 80.88 |
Activity rating condition: T=340 DEG C, P=0.3MPa, CH
3oH/CS
2=2.2, GHSV=1000h
-1.
Loaded catalyst: 2ml, 30 ~ 60 orders.
Claims (10)
1. by the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that with the compound of tungsten for main active component, with the oxygenatedchemicals of the oxygenatedchemicals of cobalt and potassium for co-catalyst, with spherical gamma-Al
2o
3for carrier; Described catalyst is with CoO-K
2o-WO
3/ γ-Al
2o
3definition and metering; In described catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be (0.05 ~ 0.35): (5 ~ 8): (10 ~ 18): 100.
2., as claimed in claim 1 by the catalyst of carbon disulfide and Methanol methyl mercaptan, to it is characterized in that in described catalyst CoO: K
2o: WO
3: γ-Al
2o
3mass ratio be (0.1 ~ 0.25): (6.5 ~ 8): (16 ~ 18): 100.
3., as claimed in claim 1 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that comprising the following steps:
1) by the ammonium metatungstate (NH of metering
4)
6h
2w
12o
40xH
2o and Anhydrous potassium carbonate are dissolved in the deionized water of metering, then add the organic acid of metering, then regulate solution ph to 8 ~ 10 with ammoniacal liquor, add the cobalt salt of metering after leaving standstill again, then leave standstill aging, obtain maceration extract;
2) spherical gama-alumina is joined step 1) in gained maceration extract, after dipping, filter and remove maceration extract, obtain mercaptan catalyst agent presoma;
3) by step 2) gained mercaptan catalyst agent presoma dries, and after oven dry, calcining, obtains the catalyst by carbon disulfide and Methanol methyl mercaptan.
4., as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that in step 1) in, described organic acid is selected from least one in citric acid, oxalic acid, Pidolidone.
5., as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that in step 1) in, the described standing time is 0.5h; The described standing aging time is again 1h.
6., as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that in step 1) in, described cobalt salt is selected from the one in cobalt nitrate, cobalt oxalate.
7., as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that in step 2) in, the diameter of described spherical gama-alumina is Ф 2 ~ 4mm; The time of described dipping is 10 ~ 14h.
8., as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that in step 3) in, the method for described oven dry is: dry to constant weight at 80 DEG C, then dries 4h under 120 DEG C of conditions.
9., as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that in step 3) in, described calcining is placed in Muffle furnace in 400 DEG C of calcining 3h.
10. as claimed in claim 3 by the preparation method of the catalyst of carbon disulfide and Methanol methyl mercaptan, it is characterized in that described organic acid: spherical gama-alumina: the mass ratio of deionized water is (10 ~ 15): 100: 140.
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|---|---|---|---|
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|---|---|---|---|
| CN201410168867.8A CN103920501B (en) | 2014-04-25 | 2014-04-25 | By the Catalysts and its preparation method of carbon disulfide and Methanol methyl mercaptan |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6198003B1 (en) * | 1999-04-20 | 2001-03-06 | Albemarle Corporation | Method for producing alkyl mercaptans and/or dialkyl monosulfides |
| CN102196861A (en) * | 2008-10-24 | 2011-09-21 | 阿肯马法国公司 | Hydrogenation catalyst, particularly for carbon disulphide |
-
2014
- 2014-04-25 CN CN201410168867.8A patent/CN103920501B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6198003B1 (en) * | 1999-04-20 | 2001-03-06 | Albemarle Corporation | Method for producing alkyl mercaptans and/or dialkyl monosulfides |
| CN102196861A (en) * | 2008-10-24 | 2011-09-21 | 阿肯马法国公司 | Hydrogenation catalyst, particularly for carbon disulphide |
Non-Patent Citations (2)
| Title |
|---|
| The promoting effects of La2O3 and CeO2 on K2MoS4/SiO2 catalyst for methanthiol synthesis from syngas blending with H2S;YiQuan Yang等;《Applied Catalysis A:General》;20001231;第192卷;第175–180页 * |
| 钴对高硫合成气制甲硫醇负载型钼酸钾催化剂的促进作用;王琪等;《厦门大学学报(自然科学版)》;20030131;第42卷(第1期);第64-68页 * |
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