CN110624570B - Preparation method of low-temperature catalyst for preparing vanadium sulfate by wet conversion - Google Patents
Preparation method of low-temperature catalyst for preparing vanadium sulfate by wet conversion Download PDFInfo
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- CN110624570B CN110624570B CN201810660261.4A CN201810660261A CN110624570B CN 110624570 B CN110624570 B CN 110624570B CN 201810660261 A CN201810660261 A CN 201810660261A CN 110624570 B CN110624570 B CN 110624570B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a catalyst for preparing vanadium sulfate by low-temperature wet conversion. A process for preparing vanadium sulfate catalyst by low-temp wet conversion includes such steps as adding silica sol, alkali metal sulfate, assistant and refined diatomite, mixing, rolling, extruding, drying and calcining. The catalyst prepared by the method has the characteristics of pulverization resistance, high strength, good activity stability and the like.
Description
Technical Field
The present invention relates to a method for producing a catalyst. In particular to a preparation method of a catalyst for preparing vanadium sulfate by low-temperature wet conversion.
Background
The wet contact method for preparing acid is to catalytically convert sulfur dioxide into sulfur trioxide in the presence of water vapor without washing and drying, and the sulfur trioxide is directly condensed into acid. Obviously, the wet contact method acid preparation process is simpler and is more beneficial to recycling of system energy. Most hydrogen sulfide sources are relatively clean, so the wet contact method acid preparation process is widely applied. The wet acid making process is the most economical choice. Meanwhile, in many cases, sulfur is not a product required by users, hydrogen sulfide is an attractive option for preparing acid, and a plurality of process procedures can be omitted by using hydrogen sulfide for preparing acid, so that the investment and the production cost are reduced, and the product has stronger market competitiveness.
In the prior art, the domestic production process flow of the catalyst for preparing the sulfuric acid by oxidizing the sulfur dioxide comprises the following steps: refining diatomite; dissolving vanadium pentoxide, alkali metal mother liquor and other auxiliary agents; neutralizing with sulfuric acid; the neutralized product is mixed with refined diatomite and other assistants, and the mixture is formed, dried and calcined to obtain the product.
The wet conversion process for preparing acid from hydrogen sulfide features that the raw material gas contains lots of water vapour. The catalytic oxidation of sulfur dioxide is carried out under conditions that contain a large amount of water vapor. The catalyst prepared by the prior art cannot meet the wet process, the traditional vanadium-silicon catalyst is seriously pulverized, and the pressure drop is increased after the catalyst is used for a period of time. And the import operating temperature of the catalyst for preparing acid by the domestic wet contact method is generally between 410 and 420 ℃. However, as the environmental protection requirements become more stringent, the catalyst is required to have better low-temperature activity.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for preparing vanadium sulfate by low-temperature wet conversion. The catalyst prepared by the method has the advantages of pulverization resistance, high strength, good low-temperature activity and good stability.
The invention relates to a preparation method of a vanadium sulfate catalyst by low-temperature wet conversion, which is characterized in that when preparing an active phase of the catalyst, silica sol is added, and then the active phase is uniformly mixed with alkali metal sulfate, an auxiliary agent and refined diatomite, rolled and compacted, and then the finished catalyst is prepared by the procedures of extruding, drying, roasting and the like.
Preferably, the average particle diameter of the colloidal particles of the silica sol solution is: 5 nm to 50nm. The pH value is 8 to 11.
SiO in the silica sol 2 The content of the catalyst accounts for 5 to 10 percent of the mass of the catalyst.
The silica sol is JA or JN type silica sol.
The auxiliary agent is methyl cellulose.
Introducing N at the roasting temperature of 450-500 DEG C 2 Roasting for 30 to 40 minutes, and then introducing SO 2 The baking time is 40 to 50, and finally air is introduced at the temperature of 600 to 650 ℃ for 50 to 60 minutes.
SO during the roasting 2 The content is 6 to 9 percent.
The catalyst prepared by the method has the advantages of pulverization resistance, high strength, good activity stability and the like.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
V 2 O 5 6.5%, K 2 O/V 2 O 5 2.66 (molar ratio) sodium sulfate 8%, cesium sulfate 2%, P 2 O 5 1.5 percent of methyl cellulose, and the balance of diatomite. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, K 2 O/V 2 O 5 KVO of 2.66 3 Mixed with KOH to prepare a solution (hereinafter referred to as vanadium solution) of 265.9g/l, K/V =2.66. Then 6.64g of 50% CsOH and 12g of Na were added 2 CO 3 And 45g jN25 type silica sol is added into 48.9 vanadium water, the mixture is neutralized by 1 2 Roasting for 40 min, and introducing 6% SO 2 The calcination time is 40 minutes, and finally air is introduced at 600 ℃ for calcination for 60 minutes, and 200g of the catalyst is prepared. The steps were repeated to prepare 200g of a catalyst.
Example 2
V 2 O 5 6.5%, K 2 O/V 2 O 5 2.66 (molar ratio), sodium sulfate 6.0%, cesium sulfate 4%, P 2 O 5 1.5 percent of methyl cellulose, and the balance of diatomite. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, KVO with K/V of 2.66 3 Mixed with KOH (hereinafter referred to as vanadium water), and the prepared vanadium water is 265.9g/l, and K/V =2.66. 13.26g of 50% CsOH, 9g of Na 2 CO 3 And 40g jN25 type silica sol into 48.9 vanadium water, neutralizing with 1,forming plastic material, extruding, drying, and calcining while introducing N at 450 deg.C 2 Roasting for 30 min, and introducing 7% SO 2 The calcination time is 50 minutes, and finally air is introduced at 600 ℃ for calcination for 60 minutes, so that 200g of the catalyst is prepared.
Example 3
V 2 O 5 6.5%, K 2 O/V 2 O 5 2.66 (molar ratio) sodium sulfate 2.0%, cesium sulfate 8%, P 2 O 5 1.5 percent of methyl cellulose, and the balance of diatomite. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, K 2 O/V 2 O 5 KVO of 2.66 3 Mixed with KOH (vanadium solution) to prepare the vanadium solution of 265.9g/l, K 2 O/V 2 O 5 =2.66. Then 26.52g of 50% CsOH and 3g of Na were added 2 CO 3 And 40g jN25 type silica sol is added into 48.9 vanadium water, neutralized by 1 2 Roasting for 30 min, and introducing 6% SO 2 The calcination time is 50 minutes, and finally air is introduced at 600 ℃ for calcination for 60 minutes, and the like to prepare 200g of the catalyst. To yield 200g of catalyst.
Example 4
V 2 O 5 7%, K 2 O/V 2 O 5 3.0 (molar ratio) sodium sulfate 2.0%, cesium sulfate 8%, P 2 O 5 1.5 percent of methyl cellulose, and the balance of diatomite. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, K 2 O/V 2 O 5 KVO of 3.0 3 Mixed with KOH (vanadium solution) to prepare the vanadium solution of 265.9g/l, K 2 O/V 2 O 5 =3.0. Then 26.52g of 50% CsOH and 3g of Na were added 2 CO 3 And 45g jN25 type silica sol were added to 52.6ml of vanadium water, and then neutralized with 12-3, preparing colloidal precipitate, mixing with 3g phosphoric acid, 2g methylcellulose and 147g diatomaceous earth, adding water, grinding to obtain plastic material, extruding, drying, and calcining at 450 deg.C while introducing N 2 Roasting for 30 min, and introducing 8% SO 2 The calcination time is 50 minutes, and finally air is introduced at 600 ℃ for calcination for 60 minutes, so that 200g of the catalyst is prepared.
Example 5
V 2 O 5 7.9%, K 2 O/V 2 O 5 3.0 Sodium sulfate 2.0%, cesium sulfate 8%, methyl cellulose 1%, and the balance diatomaceous earth. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, K 2 O/V 2 O 5 KVO of 3.0 3 The resulting mixed solution with KOH (hereinafter referred to as vanadium solution) produced 265.9g/l of vanadium solution with K/V =3.0. Then 26.52g of 50% CsOH and 3g of Na were added 2 CO 3 And 60g of a model jA25 silica sol into 59.4ml of vanadium water, neutralizing the solution with 1
Mixing vitamin and 131.5g diatomaceous earth, adding water, grinding tightly to obtain plastic material, extruding, drying, and roasting at 450 deg.C while introducing N 2 Roasting for 30 min, and introducing 7% SO 2 The calcination time is 50 minutes, and finally air is introduced at 600 ℃ for calcination for 60 minutes, so that 200g of the catalyst is prepared.
Example 6
V 2 O 5 7.9%, K 2 O/V 2 O 5 3.2 Sodium sulfate 2.0%, cesium sulfate 8%, methyl cellulose 1%, and the balance diatomaceous earth. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, K 2 O/V 2 O 5 KVO of 3.2 3 Mixed with KOH (vanadium solution) to prepare the vanadium solution of 265.9g/l, K 2 O/V 2 O 5 =3.2. Then 26.52g of 50% CsOH and 3g of Na were added 2 CO 3 And 80g of type jA25 silicaAdding the glue into 59.4ml of vanadium water, then neutralizing with 1 2 Roasting for 30 min, and introducing 7% SO 2 The calcination time is 50 minutes, and finally air is introduced at 600 ℃ for calcination for 60 minutes, and the like to prepare 200g of the catalyst.
Example 7
V 2 O 5 8.2%, K 2 O/V 2 O 5 3.2 Sodium sulfate 2.0%, cesium sulfate 8%, methyl cellulose 1%, and the balance diatomaceous earth. Dissolving KOH with steam, and mixing with V 2 O 5 Prepared under the condition of hot boiling, K 2 O/V 2 O 5 KVO of 3.2 3 Mixed with KOH (vanadium solution) to prepare the vanadium solution of 265.9g/l, K 2 O/V 2 O 5 =3.2. Then 26.52g of 50% CsOH and 3g of Na were added 2 CO 3 And 80g of jA25 type silica sol is added into 59.4ml of vanadium water, then the pH value is neutralized by 1 2 Roasting for 30 min, and introducing 9% SO 2 The calcination time is 50 minutes, and finally air is introduced at 600 ℃, and the calcination time is 50 minutes, and the procedures are carried out to prepare 200g of catalyst.
Sample testing
Catalyst sample: the particle size is psi 9X 3.5X (10-15) mm
Activity test conditions:
the conversion adopts a jacketed single-tube reactor, the tube diameter phi of the single-tube reactor is 36 multiplied by 2.0mm, a temperature thermocouple sleeve is positioned in the center of the converter, and the tube diameter phi of the single-tube reactor is 8 multiplied by 1.5mm;
catalyst loading: 30ml of
The particle size of the catalyst is as follows: 3.35-4 mm
Space velocity: 3600h-1
Inlet SO 2 10 percent +/-1 percent of the total volume, about 10 percent of water vapor and the balance of air
System pressure: atmospheric pressure
Temperature of activity detection: 380 ℃ and 410 DEG C
Heat resistance temperature: 600 ℃ for 5h
With SO 2 The conversion rate indicates the activity.
Strength test
Catalyst sample: the particle size is phi 9 multiplied by 3.5 multiplied by (10 to 15) mm
Strength test conditions:
the method for measuring the radial compressive strength of the particles is carried out according to the regulation of GB/T3635. The strength measurement adopts an intelligent particle strength tester, the precision is 1 grade, and the measuring range is 0-250N.
Acid blister strength test conditions
The sample particles were mixed in a 1:1H 2 SO 4 After soaking for 24h, the acid liquor is sucked dry and the determination is carried out according to the strength test conditions.
Abrasion Rate test
According to the specification HG/T2969, wherein the sample is at (120)+5) Drying at deg.C for 2 hr.
The results of the activity test are shown in Table 1, and the results of the strength test are shown in Table 2.
Table 1: results of Activity test
Table 2: test results of Strength and abrasion Rate
Sample examples | Strength (N/cm) | Acid soak Strength (N/cm) | Rate of wear |
Example 1 | 72.0 | 63.5 | 1 |
Example 2 | 70.2 | 60.6 | 1.3 |
Example 3 | 81.0 | 70 | 2 |
Example 4 | 83.4 | 72.1 | 1.4 |
Example 5 | 86.7 | 74 | 2.2 |
Example 6 | 90.4 | 78.6 | 0.8 |
Example 7 | 85 | 72.6 | 1.1 |
Industry Standard | ≧35 | --------- | ≦5 |
The test results in table 1 show that the low-temperature activity of the catalyst for preparing vanadium sulfate by low-temperature wet conversion prepared by the method is obviously higher than that of the conventional catalyst by wet method, and the test results in table 2 show that the catalyst for preparing vanadium sulfate by low-temperature wet conversion prepared by the method has higher strength and low abrasion rate. Therefore, the catalyst prepared by the method has obviously improved performance and can meet the requirement of higher SO in acid preparation by a wet method 2 The conversion rate is required. The catalyst prepared by the method has the advantages of pulverization resistance, high strength, good low-temperature activity and good stability.
Claims (4)
1. A low-temperature wet conversion method for preparing vanadium sulfate catalyst is characterized in that when preparing catalyst active phase, silica sol is added, then the silica sol, alkali metal sulfate, auxiliary agent and refined diatomite are mixed uniformly and rolled tightly, and the catalyst is prepared through extruding, drying and roasting; introducing N at the roasting temperature of 450-500 DEG C 2 Roasting for 30 to 40 minutes, and then introducing SO 2 The baking time is 40 to 50 minutes, and finally air is introduced at the temperature of 600 to 650 ℃ for 50 to 60 minutes; SO at roasting 2 The content is 6 to 9 percent; siO in silica sol 2 The content of the catalyst accounts for 5 to 10 percent of the mass of the catalyst.
2. The method for preparing a catalyst according to claim 1, wherein the average particle size of colloidal particles of the silica sol solution is: 5 nm to 50nm, and the pH value is 8 to 11.
3. The process for preparing a catalyst according to claim 1, wherein the silica sol is a JA or JN type silica sol.
4. The process for preparing a catalyst according to claim 1, wherein the auxiliary agent is methylcellulose.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE29145E (en) * | 1969-05-23 | 1977-03-01 | Bayer Aktiengesellschaft | Catalyst for sulfuric acid contact process |
DK306084D0 (en) * | 1983-06-25 | 1984-06-22 | Basf Ag | METHOD OF PREPARING A CATALYST FOR THE OXIDATION OF Sulfur Dioxide To Sulfur Trioxide |
CN1417112A (en) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | Roasting process of vanadium catalyst for production of sulfuric acid |
CN101041131A (en) * | 2006-03-20 | 2007-09-26 | 襄樊市精信催化剂有限责任公司 | SCL sulfur dioxide oxidation system producing aulfuric acid and the preparing method |
CN101259417A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Regeneration method of sulphur absorption V2O5/AC catalytic adsorption agent |
CN102266777A (en) * | 2011-06-20 | 2011-12-07 | 河北晶锐瓷业有限公司 | Novel nontoxic catalyst applied to denitration of smoke and preparation method thereof |
CN102921405A (en) * | 2012-09-29 | 2013-02-13 | 重庆大学 | SiO2-containing denitration catalyst and preparation method thereof |
CN103506143A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion |
CN105107514A (en) * | 2015-08-17 | 2015-12-02 | 成都金鑫天蓝科技有限公司 | Honeycomb non-vanadium denitration shaping catalyst, preparation method and application thereof |
CN106311299A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Vanadium catalyst used for producing sulfuric acid by high-density reforming gas and preparation method thereof |
-
2018
- 2018-06-25 CN CN201810660261.4A patent/CN110624570B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE29145E (en) * | 1969-05-23 | 1977-03-01 | Bayer Aktiengesellschaft | Catalyst for sulfuric acid contact process |
DK306084D0 (en) * | 1983-06-25 | 1984-06-22 | Basf Ag | METHOD OF PREPARING A CATALYST FOR THE OXIDATION OF Sulfur Dioxide To Sulfur Trioxide |
CN1417112A (en) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | Roasting process of vanadium catalyst for production of sulfuric acid |
CN101041131A (en) * | 2006-03-20 | 2007-09-26 | 襄樊市精信催化剂有限责任公司 | SCL sulfur dioxide oxidation system producing aulfuric acid and the preparing method |
CN101259417A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Regeneration method of sulphur absorption V2O5/AC catalytic adsorption agent |
CN102266777A (en) * | 2011-06-20 | 2011-12-07 | 河北晶锐瓷业有限公司 | Novel nontoxic catalyst applied to denitration of smoke and preparation method thereof |
CN103506143A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion |
CN102921405A (en) * | 2012-09-29 | 2013-02-13 | 重庆大学 | SiO2-containing denitration catalyst and preparation method thereof |
CN106311299A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Vanadium catalyst used for producing sulfuric acid by high-density reforming gas and preparation method thereof |
CN105107514A (en) * | 2015-08-17 | 2015-12-02 | 成都金鑫天蓝科技有限公司 | Honeycomb non-vanadium denitration shaping catalyst, preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
浅谈国内外钒催化剂的质量差异;郭振兵;《硫酸工业》;20040425(第02期);第6-9页 * |
粘结剂对蜂窝状V_2O_5/ACH同时脱硫脱硝活性的影响;王艳莉等;《过程工程学报》;20090815(第04期);第81-86页 * |
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