CN1408476A - High active long-acting fluorating catalyst and its producing method - Google Patents
High active long-acting fluorating catalyst and its producing method Download PDFInfo
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- CN1408476A CN1408476A CN 01141970 CN01141970A CN1408476A CN 1408476 A CN1408476 A CN 1408476A CN 01141970 CN01141970 CN 01141970 CN 01141970 A CN01141970 A CN 01141970A CN 1408476 A CN1408476 A CN 1408476A
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Abstract
The present invention relates to fluorating catalyst with high and lasting activity and its production process. Chromium radical and two synergistic metal radicals are introduced to inhibit crystallization, the catalyst precursor is roasted at 200-400 deg.c in reducing atmosphere to avoid sintering and increase specific surface area and porosity. The catalyst of the present invention is used in the two-step reaction to fluorizate and synthesize HFC-134a with material vinyl trichloride and HF. It has high activity, high stability and long service life.
Description
The present invention relates to a high-activity long-acting fluorination catalyst (catalyst for short) and its preparation method.
In recent years, the problem of destroying the ozone layer in the atmosphere by chlorofluorocarbons containing chlorine atoms has been highlighted, and 1, 1, 1, 2-tetrafluoroethane (abbreviated as HFC-134a) compounds have solved the problem. The compound is synthesized by the reaction of trichloroethylene and hydrogen fluoride in a gas phase, and most of the used catalysts are chromium-based catalysts. The Cr-based catalyst has good activity, but is easy to coke, and the early stage HFC-134a synthesis is mainly characterized by introducing O into the reaction gas2Gas preserves catalyst activity and life, but increases by-product and equipment corrosivity. The Cr-based catalyst may be classified into an impregnation method, a wet chemical method, a blending method, a thermal decomposition method, and the like according to the preparation method. The impregnation method is mostly gamma-AlF3Partially fluorinated gamma-Al2O3Activated carbon, gamma-Al2O3And the like are taken as carriers, and Cr and the like are taken as active components. Because of the limitation of the specific surface area, pore volume and the like of the carrier, the content of themain active component Cr is generally lower (<10%), the activity is limited, and the space-time yield is generally lower. The direct fluorination of trichloroethylene can only obtain HFC-134a with a yield of 3%, and moreover, the activity of the catalyst is rapidly reduced, so that the catalyst needs to be regenerated and replaced frequently, which is obviously not beneficial to industrial production. Chinese patent 95115476.1 reports that "a fluorination catalyst for fluorinating halogenated hydrocarbon" improves the yield of the product HFC-134a and slows down the decay of the catalyst activity. However, as the scale of industrial production is increased, the activity and service life of the catalyst are still not satisfactory, especially the activity of the catalyst is increased with the space velocity of the material and the reaction temperatureThe high and fast rate of decline affects the service life.
Chinese patent 94115127.1 reports "a chromium-based fluorination catalyst and a method for producing the same and a fluorination method using the catalyst" to indicate that: heat during the preparation of the catalystThe treatment conditions have a great influence on the performance of the catalyst, and it has also been found that a chromium-based fluorination catalyst produced by calcining or heating a substance mainly composed of a chromium (III) hydroxide at 350 to 500 ℃ in the presence of hydrogen to prepare a precursor of the catalyst and partially fluorinating the catalyst precursor in a gas stream containing hydrogen fluoride is superior to conventional fluorination catalysts in both selectivity and activity. From the above patents, it is seen that the heat treatment conditions have a great influence on the catalyst performance, but the solution to this problem is only from the external heat treatment conditions, and the solution to the problem is not from the prepared catalyst itself, so that the obtained effect is limited. Further, the catalyst precursor is limited to a chromium base, and the advantageous effects of the invention are small or not obtained if a carrier is used. Chinese patent 96121696.6 reports "a chromium oxide based amorphous catalyst, its preparation and its use in halocarbon fluorination" indicating: chromium oxide or chromium and possibly at least one further catalytically active metal oxide, with a fluorine-containing fluorination catalyst specific surface area of>25m2(ii) in terms of/g. By means of a supercritical fluid drying of amorphous chromium oxide based catalysts, catalysts with improved reactivity are obtained, with a significantly improved fluorination rate and by itself limiting the formation of water in industrial reactors. Although the invention improves the activity and the fluorination rate to a certain extent, the fluorination catalyst has lower specific surface area and shorter service life.
The invention aims to overcome the defects of the background technology and designs a catalyst with high activity, non-crystalline and long service life and a preparation method thereof.
The conception of the invention is as follows: in order to achieve the above purpose, to obtain a catalyst with high activity, amorphous form and long service life, two technical difficulties must be solved, one is to solve the problem that the sintering phenomenon is generated due to the decomposition and heat release local overheating in the roasting process and the sintering phenomenon is easily generated due to the heat release effect when the catalyst precursor is subjected to fluorination treatment, both the specific surface area of the catalyst can be greatly reduced, and the activity of the catalyst is influenced. Secondly, the catalyst is easy to generate a crystal structure or a microcrystal structure by crystal phase conversion, particularly a single chromium base, and the existence of the crystal influences the stability of the catalyst, namely influences the service life of the catalyst, so that the amorphous formation of the catalyst is a technical key. In order to obtain the amorphous fluorination catalyst, two metal bases which play a role in synergy and assistance are required to be added besides the chromium base, and the metal compounds preferably do not belong to the same crystal system, the growth speeds of crystals are different, so that the formation of a dot matrix in the crystal growth process is damaged, and the three metal compounds mutually inhibit the formation of the crystals; in order to prevent the sintering of the catalyst, the first step is to prevent the sintering of the catalyst precursor, and firstly to overcome the problem that the chromium-based hydroxide is violently decomposed at 405 ℃ to generate local overheating, the method is to select one metal base with lower decomposition temperature from two metal bases, active hydroxyl free radicals can be generated to act on the chromium-based hydroxide when the metal-based hydroxide with lower decomposition temperature is decomposed, so that the decomposition activation energy of the chromium-based hydroxide is reduced, and in a graph 1 measured by a TA and DSC2910 instrument, a strong exothermic peak of the Cr-based hydroxide is eliminated in a graph 2, which illustrates that the Cr-based hydroxide is slowly decomposed at lower temperature. In the second step, the catalyst is prevented from being sintered by adopting inert gas dilution, the temperature is slowly increased and controlled, in addition, the hydrogen is introduced as the inert gas after drying and laser irradiation, the hydrogen generates a small amount of free radicals of hydrogen under the laser irradiation, the reducibility is realized, the fluorination activation energy can be reduced, the strong heat release effect of the fluorination reaction is also reduced, and the micropore sintering of the catalyst is avoided.
The catalyst of the invention is characterized by comprising a multi-metal base, oxygen and fluorine, and the combination formula is as follows:
CrX0.005～0.5Y0.005～0.3O0.1～1.0F1.0～3.0
wherein X is Mn, Co or Zn; y is Mg or Ni.
The invention has another characteristic that the alloy consists of Cr, Mn, Mg, O and F preferably, and the combination formula is as follows:
CrMn0.05～0.4Mg0.05～0.2O0.5～1.0F1.0～2.5
still another feature of the present invention is that the atomic ratio is more preferable in the following combination:
CrMn0.3Mg0.1O0.5F2.0
the preparation method comprises the steps of dissolving the soluble salt of the multi-metal group, reacting with a precipitator at the temperature of 20-100 ℃, stirring, precipitating and filtering at the pH value of 6.5-9.5, drying and roasting at the temperature of 100-200 ℃ to form the catalyst precursor, and is characterized in that the catalyst precursor is roasted at the lower temperature of 200-400 ℃, wherein N is introduced during roasting and activating treatment2、H2H in the mixed gas of2Is a nascent state which is treated by drying and laser irradiation.
The invention has the following advantages:
1. the catalyst has high activity and good stability, the space-time yield of the first step reaction is more than 290g/Lh, and the space-time yield of the second step reaction is more than 180 g/Lh. After 1000 hours of continuous evaluation of the service life of the catalyst, the activity remained unchanged.
2. The coprecipitation method has simple preparation process, good repeatability, large specific surface area and pore volume, and the specific surface area of the catalyst precursor is more than 200m2The pore volume is more than 0.3ml/g, the specific surface area of the catalyst is more than 60m2The pore volume is more than 0.15 ml/g.
3. The multi-metal base mutual cooperation, the auxiliary catalysis and the crystal generation inhibition improve the stability of the catalyst precursor, avoid the crystal generation in the curing and activating processes, and make the catalyst precursor and the catalyst both amorphous, thereby playing a key role in prolonging the service life.
4. In the process of curing and activating, the sintering phenomenon is prevented, the specific surface area and the pore volume are greatly improved, and the activity of the catalyst is high.
The drawings of the invention are illustrated as follows:
FIG. 1 shows Cr (OH)3Differential thermogram of
FIG. 2 shows Cr (OH)3、Mn(OH)2And Mg (OH)2Differential thermogram of
FIG. 3 is an XRD spectrum of the catalyst
FIG. 4 is a catalyst life test chart
Example 1. the manufacturing method of the present invention was carried out with reference to the following combination: CrMn0.3Mg0.1O0.5F2.01.1 preparation of catalyst precursor
Preparing soluble salt (nitrate, sulfate, chloride, etc.) of active component into solution with certain concentration, and mixing with precipitant (NaOH,KOH, (NH) at 20-100 deg.C4)2CO3Ammonia water, etc.) to react, the final PH value is controlled to be 6.5-9.5, strong stirring is carried out during the reaction to ensure that the active components are fully precipitated, then filtration is carried out, deionized water or methanol is used for washing until the active components are neutral, then a filter cake is dried at 100-200 ℃, and the specific area is more than 200m2g-1Pore volume of more than 0.3mlg-1The amorphous catalyst precursor of (a). 1.2 curing, activating treatment
Adding the precursor into graphite equal-pressure sheets for molding, then filling the graphite equal-pressure sheets into a reactor, fully curing the graphite equal-pressure sheets at the temperature of 200-400 ℃ by using inert gas, then introducing mixed gas of the inert gas and hydrogen fluoride for activation at the temperature of 200-400 ℃, and finally introducing pure hydrogen fluoride to enable the catalyst to reach a certain fluorination degree, thereby preparing the oxyfluoride amorphous catalyst. In the course of activation, fluorinationThe strong exothermic effect should be such that the micropores of the catalyst sinter and, in severe cases, the catalyst can be completely deactivated by sintering. The ratio of hydrogen fluoride to inert gas must be strictly controlled so that the activation treatment is carried out under milder conditions. The temperature rise of the fluorination reaction is controlled to be less than 50 ℃. The inert gas being N2、H2Mixed gas of (2), N2∶H21: 0.1-1.0, wherein H2Is a nascent state which is treated by drying and laser irradiation.
Since the reaction for synthesizing HFC-134a is carried out in HF medium, the catalyst exists in the form of fluoride. In the process of activating the precursor to obtain the catalyst, in order to prevent sintering deactivation, the ratio of hydrogen fluoride to inert gas and the reaction temperature must be strictly controlled, the fluorination reaction is carried out under a relatively mild condition, and the catalyst with higher fluorination degree has higher activity.
TABLE 1 influence of degree of fluorination of catalyst on reaction Activity number F/Cr O/Cr HFC-134a yield%
1 2.32 1.01 25.4
2 1.66 0.49 24.3
3 1.58 0.96 23.6
40.431.488.5 reaction conditions: HF to HCFC-133a is 4 to 1, the temperature is 350 ℃, and the space velocity is 1320/h-11.3 reactivity of the catalyst
50ml (10-18 mesh) of the above catalyst was charged into a phi 19 x 2 nickel tube reactor heated with molten salt to carry out the following two reactions, and the results are shown in tables 2 and 3.
TCE AHF HCFC-133a
HCFC-133a HFC-134a
TABLE 2 Activity number of catalyst in reaction (1) reaction temperature/. degree.C.HF/TCE GHSV/h-1HCFC-133a yield,% 128010: 1132095.1228010: 1132094.3
TABLE 3 Activity number reaction temperature of catalyst in reaction (2)/HF/HCFC 33a GHSV/h-1HFC-133a yield,% 13504.5: 1132022.623504.5: 1165022.833504.5: 1198020.643504.6: 1134421.31.4 catalyst Performance test 1.4.1 amorphous determination
XRD characterization results show that the catalyst prepared by the coprecipitation method is amorphous, and the crystal phase structure of the catalyst is not changed before and after the fluorination reaction, as shown in figure 3 measured by a D/MAX-2400 instrument. 1.4.2 measurement of specific surface area and pore volume
The specific surface area, the pore volume and the pore size distribution of the catalyst are measured by a BET physical adsorption instrument, and the test result is as follows: the specific surface area is more than 60m2·g-1Pore volume of more than 0.15ml g-1Has better reactivity, and the reactivity is increased along with the increase of the specific surface area and the pore volume. And (3) actually measuring results: specific surface area pore volume reaction (1) space time yield reaction (2) space time yield m2·g-1ml·g-1g·L-1·h-1g·L-1·h-163 0.17 302 184Reaction (1) conditions: 280 deg.C, HF/TCE 10: 1, GHSV1320h-1Reaction (2) conditions: 350 deg.C, HF/HCFC133a ═ 4: 1, GHSV1320h-11.4.3 enhanced Life test
The reaction of HCFC-133a with HF was chosen at 350 ℃, HF: HCFC133a ═ 4: 1, space velocity 1320h-1Under the condition, the screened catalyst still has better activity after more than 1000h of life test, as shown in figure 4. 1.5 catalyst application test
The catalyst is loaded in a 200t/aHFC-134a industrial test device and runs for a long time, and the catalyst presents good coking resistance and regenerability. The manufacturing method of the present invention is carried out by referring to the following combination:
CrCo0.1Mg0.7O0.6F1.0
the manufacturing process is the same as that of the embodiment 1, the performance isbasically the same, and the specific surface area, the pore volume and other test results: specific surface area pore volumeReaction (1) space-time yield reaction (2) space-time yield m2·g-1ml·g-1g·L-1·h-1g·L-1·h-1650.16299182 the reaction conditions were the same as in example 1. The manufacturing method of the invention is implemented by the following combination:
CrZn0.2Mg0.9O0.7F1.2
the manufacturing process is the same as that of the embodiment 1, the performance is basically the same, and the specific surface area, the pore volume and other test results:specific surface area pore volume reaction (1) space time yield reaction (2) space time yield m2·g-1ml·g-1g·L-1·h-1g·L-1·h-1610.19304194 the reaction conditions were the same as in example 1. The manufacturing method of the invention is implemented by the following combination:
CrMn0.4Ni0.12O1.0F1.4
the manufacturing process is the same as that of the embodiment 1, the performance is basically the same, and the specific surface area, the pore volume and other test results: specific surface area pore volume reaction (1) space time yield reaction (2) space time yield m2·g-1ml·g-1g·L-1·h-1g·L-1·h-1650.18302189 the reaction conditions were the same as in example 1. The manufacturing method of the invention is implemented by the following combination:
CrCo0.05Ni0.16O0.8F1.6
the manufacturing process is the same as thatof the embodiment 1, the performance is basically the same, and the specific surface area, the pore volume and other test results: specific surface area pore volume reaction (1) space time yield reaction (2) space time yieldRate m2·g-1ml·g-1g·L-1·h-1g·L-1·h-1640.19311198 the reaction conditions were the same as in example 1. The manufacturing method of the invention is implemented by the following combination:
CrZn0.08Ni0.2O0.9F1.8
the manufacturing process is the same as that of example 1, and the performance is close to that of example 5.
Claims (4)
1. The invention relates to a high-activity long-acting fluorination catalyst, which is characterized by comprising a multi-metal base, oxygen and fluorine, and the combination formula is as follows:
CrX0.005～0.5Y0.005～0.3O0.1～1.0F1.0～3.0
wherein X is Mn, Co or Zn; y is Mg or Ni.
2. The catalyst according to claim 1, characterized by a preferred composition of Cr, Mn, Mg, O and F, in combination as follows:
CrMn0.05～0.4Mg0.05～0.2O0.5～1.0F1.0～2.5
3. the catalyst according to claim 2, characterized by more preferred atomic ratios, in combination:
CrMn0.3Mg0.1O0.5F2.0
4. a process for preparing the high-activity long-acting fluorizating catalyst as claimed in claim 1, which includes dissolving soluble multi-metal salt, reaction with precipitant at 20-100 deg.C, stirring at 6.5-9.5 pH value, deposition, filtering, drying at 100-200 deg.C and calcining to obtain the catalyst precursor, calcining at 200-400 deg.C, and introducing N during calcining and activating treatment2、H2H in the mixed gas of2Is a nascent state which is treated by drying and laser irradiation.
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Cited By (10)
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| CN1308072C (en) * | 2005-09-30 | 2007-04-04 | 山东东岳化工有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
| CN101041132B (en) * | 2007-04-23 | 2010-05-26 | 浙江师范大学 | Vapor-phase fluorination catalysts for producing HFC-134a and the preparing method |
| CN102001912A (en) * | 2010-10-24 | 2011-04-06 | 浙江衢化氟化学有限公司 | Method for synthesizing 3,3,3-trifluoropropene |
| CN1911512B (en) * | 2005-07-07 | 2011-12-07 | 独立行政法人产业技术综合研究所 | Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts |
| WO2013037286A1 (en) * | 2011-09-14 | 2013-03-21 | 中化蓝天集团有限公司 | Method for preparing 2,3,3,3-tetrafluoropropene |
| CN103143344A (en) * | 2011-12-06 | 2013-06-12 | 中化蓝天集团有限公司 | Chromium-based fluorination catalyst with high specific surface, and preparation method thereof |
| WO2014094590A1 (en) | 2012-12-19 | 2014-06-26 | 中化近代环保化工(西安)有限公司 | Hfo-1234ze and hfc-245fa co-production preparation process |
| CN103896721A (en) * | 2014-04-11 | 2014-07-02 | 太仓中化环保化工有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane |
| CN105344365A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Method for preparing fluorinated catalyst by homogeneous precipitation method |
| US9845274B2 (en) | 2013-12-12 | 2017-12-19 | Xi'an Modern Chemistry Research Institute | Chromium-free catalyst for gas-phase fluorination and application thereof |
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- 2001-09-26 CN CNB011419709A patent/CN1169620C/en not_active Expired - Lifetime
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| CN1911512B (en) * | 2005-07-07 | 2011-12-07 | 独立行政法人产业技术综合研究所 | Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts |
| CN1308072C (en) * | 2005-09-30 | 2007-04-04 | 山东东岳化工有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
| CN101041132B (en) * | 2007-04-23 | 2010-05-26 | 浙江师范大学 | Vapor-phase fluorination catalysts for producing HFC-134a and the preparing method |
| CN102001912A (en) * | 2010-10-24 | 2011-04-06 | 浙江衢化氟化学有限公司 | Method for synthesizing 3,3,3-trifluoropropene |
| US9115042B2 (en) | 2011-09-14 | 2015-08-25 | Sinochem Lantian Co., Ltd. | Method for preparing 2,3,3,3-tetrafluoropropene |
| CN102989489A (en) * | 2011-09-14 | 2013-03-27 | 中化蓝天集团有限公司 | 2,3,3,3-tetrafluoropropylene preparation method |
| JP2014530088A (en) * | 2011-09-14 | 2014-11-17 | シノケム ランティアン カンパニー リミテッドＳｉｎｏｃｈｅｍ Ｌａｎｔｉａｎ Ｃｏ．， Ｌｔｄ． | Process for preparing 2,3,3,3-tetrafluoropropene |
| CN102989489B (en) * | 2011-09-14 | 2015-04-22 | 中化蓝天集团有限公司 | 2,3,3,3-tetrafluoropropylene preparation method |
| EP2756883A4 (en) * | 2011-09-14 | 2015-05-06 | Sinochem Lantian Co Ltd | Method for preparing 2,3,3,3-tetrafluoropropene |
| WO2013037286A1 (en) * | 2011-09-14 | 2013-03-21 | 中化蓝天集团有限公司 | Method for preparing 2,3,3,3-tetrafluoropropene |
| CN103143344A (en) * | 2011-12-06 | 2013-06-12 | 中化蓝天集团有限公司 | Chromium-based fluorination catalyst with high specific surface, and preparation method thereof |
| CN103143344B (en) * | 2011-12-06 | 2015-10-14 | 中化蓝天集团有限公司 | A kind of high than table chromium-based fluorination catalyst and preparation method thereof |
| WO2014094590A1 (en) | 2012-12-19 | 2014-06-26 | 中化近代环保化工(西安)有限公司 | Hfo-1234ze and hfc-245fa co-production preparation process |
| US9845274B2 (en) | 2013-12-12 | 2017-12-19 | Xi'an Modern Chemistry Research Institute | Chromium-free catalyst for gas-phase fluorination and application thereof |
| US10087125B2 (en) | 2013-12-12 | 2018-10-02 | Xi'an Modern Chemistry Research Institute | Chromium-free catalyst for gas-phase fluorination and application thereof |
| CN103896721A (en) * | 2014-04-11 | 2014-07-02 | 太仓中化环保化工有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane |
| CN105344365A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Method for preparing fluorinated catalyst by homogeneous precipitation method |
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Assignee: Sinochem Taicang Environmental Protection Chemical Co., Ltd. Assignor: Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. Contract record no.: 2012320010044 Denomination of invention: High active long-acting fluorating catalyst and its producing method Granted publication date: 20041006 License type: Exclusive License Open date: 20030409 Record date: 20120322 |
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