CN103623836B - The Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene - Google Patents
The Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene Download PDFInfo
- Publication number
- CN103623836B CN103623836B CN201210305818.5A CN201210305818A CN103623836B CN 103623836 B CN103623836 B CN 103623836B CN 201210305818 A CN201210305818 A CN 201210305818A CN 103623836 B CN103623836 B CN 103623836B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetylene hydrochlorination
- synthesizing chloroethylene
- hydrochlorination synthesizing
- ruthenium
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises inert porous carrier and is carried on ruthenium salt, nickel salt and the platinum salt on described inert porous carrier, the quality of Ru accounts for 0.01 ‰ ~ 5%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:0.1 ~ 10:0.1 ~ 10.The invention has the advantages that: can reaction temperature be reduced with catalyst acetylene hydrochlorination synthesizing chloroethylene of the present invention, make reaction temperature lower than 180 DEG C, and product is selective good, accessory substance is few, and reactivity is high, makes the conversion ratio of acetylene more than 99%, vinyl chloride is selective reaches 99.9%, catalyst strength of the present invention is high, and the life-span is long, and post catalyst reaction regeneration process is simple.Preparation method's technique simply, easily operates.
Description
Technical field
The present invention relates to one and utilize synthesizing chloroethylene by acetylene catalyst without mercury.
Background technology
Along with the development of national economy and the raising day by day of living standards of the people, the demand of polyvinyl chloride is increasing.That applies in current carbide production vinyl chloride process contains mercury catalyst, can produce " mercury pollution " on the one hand, be faced with the problem of mercury scarcity of resources on the other hand.
At present, the research and development of acetylene hydrochlorination preparing chloroethylene catalyst without mercury are faced with activity and the life problems of catalyst.Currently used catalyst most active is poor, although the life-span of the active good catalyst had is shorter, cannot realize industrialization.For this reason, current research wishes that the method by Recompounded multielement and support modification improves the performance of catalyst more.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene is provided.
Technical scheme of the present invention is summarized as follows:
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises inert porous carrier and is carried on ruthenium salt, nickel salt and the platinum salt on described inert porous carrier, the quality of Ru accounts for 0.01 ‰ ~ 5%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:0.1 ~ 10:0.1 ~ 10.
Described inert porous carrier is asphaltic base ball-type active carbon, opaque active carbon or cocoanut active charcoal.
Described ruthenium salt is that nitric acid ruthenium III, acetic acid ruthenium III, ruthenium trichloride, ruthenium sulfate III and pentachloro-monohydroxy close the sour potassium at least one of ruthenium IV.
Described platinum salt is platinous chloride, platinum nitrate II, platinic sulfate II, platinum acetate II and platinum tetrachloride at least one.
Described nickel salt is nickel nitrate II, nickel acetate II, Nickel Chloride, nickelous sulfate II and dichloride hexamine nickel at least one.
Preferably the quality of Ru accounts for 0.01% ~ 1% of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene.Preferably 0.1% ~ 0.5%.
The mol ratio of Ru, Pt and Ni is preferably 1:0.5 ~ 5:0.5 ~ 5.
The invention has the advantages that: can reaction temperature be reduced with catalyst acetylene hydrochlorination synthesizing chloroethylene of the present invention, make reaction temperature lower than 180 DEG C, and product is selective good, accessory substance is few, and reactivity is high, makes the conversion ratio of acetylene more than 99%, vinyl chloride is selective reaches 99.9%, catalyst strength of the present invention is high, and the life-span is long, and post catalyst reaction regeneration process is simple.Preparation method's technique simply, easily operates.
Accompanying drawing explanation
Fig. 1 is evaluating catalyst schematic flow sheet of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises asphaltic base ball-type active carbon and is carried on nitric acid ruthenium III, nickel nitrate II and the platinous chloride on asphaltic base ball-type active carbon, the quality of Ru accounts for 0.3%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:3:3.
Embodiment 2
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprise asphaltic base ball-type active carbon and be carried on acetic acid ruthenium III on asphaltic base ball-type active carbon, nickel acetate II and Nickel Chloride, platinum nitrate II that mass ratio is 1:1, the quality of Ru accounts for 0.1%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:1:5.
Embodiment 3
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises ruthenium trichloride and the ruthenium sulfate III and nickelous sulfate II and platinic sulfate II that opaque active carbon and the mass ratio be carried on opaque active carbon are 1:1, the quality of Ru accounts for 0.5%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:5:1.
Embodiment 4
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises opaque active carbon and is carried on ruthenium sulfate III, Nickel Chloride and the platinum acetate II on opaque active carbon, the quality of Ru accounts for 0.01%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:0.1:10.
Embodiment 5
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises cocoanut active charcoal and the pentachloro-monohydroxy be carried on cocoanut active charcoal closes platinum tetrachloride and the platinous chloride that the sour potassium of ruthenium IV, dichloride hexamine nickel and mass ratio are 1:1, the quality of Ru accounts for 1%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:10:0.1.
Embodiment 6
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprise asphaltic base ball-type active carbon and be carried on acetic acid ruthenium III on asphaltic base ball-type active carbon, nickel acetate II and Nickel Chloride, platinum nitrate II that mass ratio is 1:1, the quality of Ru accounts for 0.01 ‰, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:10:10.
Embodiment 7
A kind of Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, it comprises asphaltic base ball-type active carbon and is carried on nitric acid ruthenium III, nickel nitrate II and the platinous chloride on asphaltic base ball-type active carbon, the quality of Ru accounts for 5%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is Ru, Pt and Ni.
The preparation of the catalyst of each embodiment above-mentioned can be prepared according to a conventional method.
Also can prepare by the method for embodiment 8 or embodiment 9:
Embodiment 8
1. asphaltic base ball-type active carbon (or opaque active carbon, cocoanut active charcoal) is dipped in dust technology, soaks 10h use water and rinse to neutral, dry 8h at 110 DEG C and carry out pretreatment;
2. ruthenium salt chloroazotic acid is made into wang aqueous solution; (ruthenium salt is selected from nitric acid ruthenium III, acetic acid ruthenium III, ruthenium trichloride, ruthenium sulfate III and pentachloro-monohydroxy and closes the sour potassium of ruthenium IV)
3. be dipped in the solution that 2. step prepare by 1. processing the inert porous carrier obtained through step, dipping 8h; Heating water bath evaporates to liquid, by solid in 160 DEG C of dryings 8 hours;
4. nickel salt and platinum salt being added concentration is be made into mixed solution in the aqueous hydrochloric acid solution of 1mol/L; (nickel salt is selected from nickel nitrate II, nickel acetate II, Nickel Chloride, nickelous sulfate II and dichloride hexamine nickel; Platinum salt is selected from platinous chloride, platinum nitrate II, platinic sulfate II, platinum acetate II and platinum tetrachloride)
5. be dipped in by the product that 3. step obtains in the mixed solution that 4. step prepare, flood 8 hours, heating water bath evaporates to liquid, in 160 DEG C of dryings 8 hours, obtains the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene.
Embodiment 9
A preparation method for the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene, comprises the steps:
1. asphaltic base ball-type active carbon (or opaque active carbon, cocoanut active charcoal) is dipped in dust technology, soaks 8h, rinse to neutral with water, dry 6h at 120 DEG C and carry out pretreatment;
2. ruthenium salt, nickel salt and platinum salt being added concentration is be made into mixed solution in the aqueous hydrochloric acid solution of 1mol/L; (ruthenium salt closes the sour potassium of ruthenium IV from nitric acid ruthenium III, acetic acid ruthenium III, ruthenium trichloride, ruthenium sulfate III and pentachloro-monohydroxy; Nickel salt is selected from nickel nitrate II, nickel acetate II, Nickel Chloride, nickelous sulfate II and dichloride hexamine nickel; Platinum salt is selected from platinous chloride, platinum nitrate II, platinic sulfate II, platinum acetate II and platinum tetrachloride)
3. be dipped in by the product that 1. step obtains in the mixed solution that 2. step prepare, flood 5 hours, heating water bath evaporates to liquid, puts into 110 DEG C, baking oven and dries 24 hours, obtain the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene.
Embodiment 10
The stainless steel fixed bed reactors utilizing internal diameter to be 10mm carry out performance evaluation to catalyst of the present invention.The device evaluated is shown in Fig. 1.
Hydrogen chloride 1(purity more than 96%) by pipeline successively through valve 3a, filter 4a, mass flowmenter 5a and one way stop peturn valve 6a;
Acetylene 2(purity more than 99%) by pipeline successively through valve 3b, filter 4b, mass flowmenter 5b and one way stop peturn valve 6b;
Enter after above-mentioned two strands of gas and vapor permeation in the stainless steel fixed bed reactors 8 that catalyst 9 of the present invention is housed, catalyst 9 loadings is 5ml, and tail gas stream adopts gas chromatograph analysis through surge tank 11 and absorption bottle 12 after alkali liquor absorption.Fid detector, GDX-301(2m × 3mm) packed column.
Filter 4a and 4b can remove the impurity such as sulphur, phosphorus, arsenic in unstripped gas stock.
Stainless steel fixed bed reactors adopt temperature controller temperature control, and the temperature in heating furnace 7 and stainless steel fixed bed reactors 8 is detected by thermocouple 10.
Wherein hydrogen chloride and acetylene flow rate ratio are 1.05.Reaction temperature is 150 DEG C.
Utilize the apparatus and method of embodiment 10 to the evaluation of catalyst in table 1
Table 1
| Embodiment | Prepare the embodiment adopted | Conversion of alkyne % | Chloro ethylene yield % |
| 1 | 8 | 65 | 57 |
| 2 | 8 | 72 | 74 |
| 3 | 8 | 81 | 85 |
| 4 | 9 | 66 | 68 |
| 5 | 8 | 89 | 91 |
| 6 | 8 | 94 | 98 |
| 7 | 8 | 97 | 99 |
Claims (8)
1. the Ru-Pt-Ni catalyst of an acetylene hydrochlorination synthesizing chloroethylene, be made up of inert porous carrier and ruthenium salt, nickel salt and the platinum salt be carried on described inert porous carrier, the quality of Ru accounts for 0.01 ‰ ~ 5%, Ru of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene, the mol ratio of Pt and Ni is 1:0.1 ~ 10:0.1 ~ 10.
2. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that described inert porous carrier is asphaltic base ball-type active carbon, opaque active carbon or cocoanut active charcoal.
3. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that described ruthenium salt is that nitric acid ruthenium (III), acetic acid ruthenium (III), ruthenium trichloride, ruthenium sulfate (III) and pentachloro-monohydroxy close ruthenium (IV) sour potassium at least one.
4. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that described platinum salt is platinous chloride, platinum nitrate (II), platinic sulfate (II), platinum acetate (II) and platinum tetrachloride at least one.
5. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that described nickel salt is nickel nitrate (II), nickel acetate (II), Nickel Chloride, nickelous sulfate (II) and dichloride hexamine nickel at least one.
6. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that the quality of described Ru accounts for 0.01% ~ 1% of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene.
7. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 6, is characterized in that the quality of described Ru accounts for 0.1% ~ 0.5% of the Ru-Pt-Ni catalyst quality of described acetylene hydrochlorination synthesizing chloroethylene.
8. the Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that the mol ratio of described Ru, Pt and Ni is 1:0.5 ~ 5:0.5 ~ 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210305818.5A CN103623836B (en) | 2012-08-24 | 2012-08-24 | The Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210305818.5A CN103623836B (en) | 2012-08-24 | 2012-08-24 | The Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103623836A CN103623836A (en) | 2014-03-12 |
| CN103623836B true CN103623836B (en) | 2015-12-02 |
Family
ID=50205500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210305818.5A Active CN103623836B (en) | 2012-08-24 | 2012-08-24 | The Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103623836B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238095A (en) * | 2015-06-05 | 2016-12-21 | 天津大学 | Sulfur non-metallic catalyst and preparation method and application is mixed for what acetylene hydrochlorination reacted |
| CN106215977B (en) * | 2016-07-25 | 2018-12-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of synthesis vinyl chloride thereof that catalytic activity is high no mercury catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670293A (en) * | 2009-03-06 | 2010-03-17 | 清华大学 | Method for synthesizing and regenerating mercury-free catalyst for hydrochlorination of acetylene and application thereof |
| CN101947465A (en) * | 2010-09-03 | 2011-01-19 | 清华大学 | Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof |
| CN102259007A (en) * | 2011-06-07 | 2011-11-30 | 李伟 | Method for preparing mercury-free catalyst for synthesis of chloroethylene by acetylene process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2910350B1 (en) * | 2006-12-22 | 2009-01-30 | Solvay | CATALYTIC HYDROCHLORIZATION SYSTEM AND PROCESS FOR PRODUCING VINYL CHLORIDE FROM ACETYLENE AND HYDROGEN CHLORIDE IN THE PRESENCE OF THIS CATALYTIC SYSTEM |
-
2012
- 2012-08-24 CN CN201210305818.5A patent/CN103623836B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670293A (en) * | 2009-03-06 | 2010-03-17 | 清华大学 | Method for synthesizing and regenerating mercury-free catalyst for hydrochlorination of acetylene and application thereof |
| CN101947465A (en) * | 2010-09-03 | 2011-01-19 | 清华大学 | Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof |
| CN102259007A (en) * | 2011-06-07 | 2011-11-30 | 李伟 | Method for preparing mercury-free catalyst for synthesis of chloroethylene by acetylene process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103623836A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Monolithic NF@ ZnO/Au@ ZIF-8 photocatalyst with strong photo-thermal-magnetic coupling and selective-breathing effects for boosted conversion of CO2 to CH4 | |
| CN103623837B (en) | The Ru-Co-Cu catalyst of acetylene hydrochlorination synthesizing chloroethylene | |
| CN105217568B (en) | Method for formate dehydrogenation under catalysis of supported Ag-Pd/C3N4 nano-catalyst | |
| CN108714429B (en) | Rod-shaped CoP/CoP2Preparation method of nano composite electrocatalyst | |
| CN102259007A (en) | Method for preparing mercury-free catalyst for synthesis of chloroethylene by acetylene process | |
| CN104415794B (en) | A kind of P Modification catalyst carrier and preparation method and application | |
| CN107754809B (en) | Cu-Mn-Zr composite catalyst for degrading VOCs waste gas and preparation method thereof | |
| CN102962082A (en) | Low-mercury catalyst used for synthesizing vinyl chloride | |
| CN103668311A (en) | Catalysis electrode for preparing formic acid by electrocatalytic reduction of CO2, application and method for preparing formic acid by electrocatalytic reduction on CO2 | |
| CN109346732B (en) | Nitrogen-doped porous carbon catalyst prepared from potatoes and preparation and application thereof | |
| CN101905157A (en) | Method for preparing mercury-free catalyst for preparing chloroethylene by acetylene hydrochlorination | |
| CN104415793B (en) | A kind of oxygen modified catalyst supports and preparation method and application | |
| CN105521801A (en) | Catalyst for ethyne hydrochlorination for synthesis of chloroethylene and preparation method thereof | |
| CN103623838B (en) | The Ru-Pt-Cu catalyst of acetylene hydrochlorination synthesizing chloroethylene | |
| CN108993595A (en) | A kind of copper-based catalysts and its preparation method and application for acetylene hydrochlorination synthesis vinyl chloride thereof | |
| CN106866349A (en) | A kind of method of low temperature preparing chloroethylene by acetylene hydrochlorination | |
| CN111437838B (en) | Biomass carbon oxygen evolution electrocatalyst and preparation method thereof | |
| CN105126833A (en) | Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride | |
| CN103623836B (en) | The Ru-Pt-Ni catalyst of acetylene hydrochlorination synthesizing chloroethylene | |
| CN102794174A (en) | Au-La catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method thereof | |
| CN103623839B (en) | The Ru-Ni-Cu catalyst of acetylene hydrochlorination synthesizing chloroethylene | |
| CN103566930A (en) | Pd/SiO2 catalyst and preparation method and application thereof | |
| CN104001512B (en) | A kind of non-mercury catalyst for the preparation of vinyl chloride and its preparation method and application | |
| CN115608415B (en) | Supported catalyst, preparation and application thereof | |
| CN102794187A (en) | Au-Co-Cu catalyst used in synthesis of vinyl chloride by hydrochlorination of acetylene and preparation method for Au-Co-Cu catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |