Ultrahigh-precision conversion absorption type dechlorination purifying agent and preparation method thereof

Abstract

The invention belongs to the field of coal chemical industry purification, and particularly relates to an ultrahigh-precision conversion absorption type dechlorination purifying agent and a preparation method thereof. Wherein the dechlorination purifying agent is prepared from the following components in percentage by weight: 5%-30% of Fe2O3, 1%-10% of CuO, 10%-30% of ZrO2, 20%-40% of Al2O3, 10%-20% of ZnO and the balance of auxiliaries. The preparation method comprises the following steps: preparing ferric nitrate, copper nitrate, zirconium nitrate, aluminum nitrate and zinc nitrate into a solution, carrying out co-precipitation by using alkali liquor as a precipitator, washing, drying and calcining the obtained material to obtain a precursor, dipping the precursor powder with ammonium dihydrogen phosphate or phosphoric acid, drying and calcining, and carrying out compression molding. The dechlorination purifying agent can reduce the total amount of organic chlorine and inorganic chlorine in raw gas such as raw coke oven gas, coke oven gas, natural gas and gaseous hydrocarbon to 0.01 ppm or below, has the capacity of converting and absorbing organic chlorine, and meanwhile has extremely high dechlorination precision.

Description

Technical Field

[0001] The invention belongs to the field of coal chemical purification, and relates to an industrially applicable process for deep removal of organic chlorine from gaseous hydrocarbons and synthesis gas, and specifically relates to an ultra-high precision conversion absorption type dechlorination purifier and a preparation method thereof. Background Art

[0002] After the pyrolysis of this coal at medium and low temperature, a raw gas will be produced as a byproduct. This raw gas contains a large amount of organochlorine, because the presence of organochlorine will cause the catalyst poisoning of the subsequent process, and organochlorine will undergo chemical reaction to generate hydrogen chloride under the conditions of high temperature, high pressure and hydrogen, causing serious corrosion to the equipment pipeline, which has caused considerable difficulties for the extension of the gas to downstream products (methanol, natural gas, ethylene glycol, etc.). The domestic development of the catalyst for the removal of organochlorine has been started very early, but the technology of large-scale industrial removal of organochlorine has not yet been developed. The existing technology of removing organochlorine at home and abroad mainly includes catalyst hydrogenation method, adsorption method, acid washing method, etc., but the relevant organochlorine removal catalyst reported at present has low precision, and most of them can only reach 0.1ppm. With the increasing development of the new energy industry, the variety of downstream products is increasingly rich, and the corresponding catalyst has higher and higher requirements for gas purification, generally requiring chloride to be less than or equal to 10ppb, or even lower. Therefore, it is of great significance to provide a low-cost, simple production process, and high dechlorination precision organochlorine removal catalyst.

[0003] Patent CN114367303A describes a dechlorination catalyst, which contains 1% to 35% of activated alumina, 1% to 25% of activated carbon, 1% to 15% of hydrotalcite and 30% to 80% of molecular sieves, and the rest are additives. The catalytic additive is one or more of Na, Cs, Ca, Cu, Zn, Fe, and Ce. The component content is 0.1% to 10%. The dechlorination catalyst has obvious removal effects on organic chlorine impurities such as chloromethane, dichloromethane, chloroethane, and dichloroethane in chemical raw materials and products. However, it can only remove the organic chlorine in the raw gas to below 0.1ppm, which cannot meet the accuracy requirements of related catalysts such as methanol, methanation, and conversion for chlorides.

[0004] Patent CN 108636348 A provides an adsorbent loaded with an alkali active component. The preparation method of the adsorbent is as follows: a molecular sieve, a binder and a pore-forming agent are kneaded and formed, and an adsorbent carrier is prepared after drying and roasting; the adsorbent carrier is impregnated with an aqueous solution of an alkali active metal component, and the adsorbent loaded with the alkali active component is obtained after filtering, drying and roasting. The adsorbent is applied to the dechlorination process of ionic liquid alkylate oil in a fixed bed process, and has an excellent dechlorination effect, but can only remove chloride to 1 ppm, which cannot meet the purification requirements of subsequent catalysts.

[0005] Patent CN111068613A describes an organic chlorine removal agent, which is mainly composed of two or more molecular sieves. The skeleton pore structure of the molecular sieves of the organic chlorine removal agent mainly includes two types of pore structures. The skeleton pores of the A-type molecular sieve are tunnel-shaped, and the skeleton pores of the B-type molecular sieve are cage-shaped. The organic chlorine removal agent is composed of the A-type molecular sieve, the B-type molecular sieve, a reinforcing auxiliary agent, and a binder. The organic chlorine removal agent has a penetration chlorine capacity of ≥1.5%, a high dechlorination accuracy (≤1ppm), and a saturated chlorine capacity of ≥2%. The dechlorination agent has a low accuracy and a low chlorine capacity. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing an ultra-high precision conversion absorption type dechlorination purifier in view of the technical problems existing in the prior art. The preparation method has low cost and simple production process. The prepared purifier has high chlorine penetration capacity and high dechlorination precision. The dechlorination purifier can deeply remove a large amount of chloride (organic chlorine and inorganic chlorine) in raw coal gas and coke oven gas at 220-350°C, and can remove chloride in raw gas to below 0.01ppm.

[0007] In order to achieve the purpose of the present invention, the specific technical scheme of the present invention is as follows:

[0008] An ultra-high precision conversion absorption type dechlorination purifier, comprising the following components in mass percentage: Fe 2 O 3 : 5%~30%, CuO: 1%~10%, ZrO 2 :10%~30%,Al 2 O 3 : 20%~40%, ZnO: 10~20%, additives 0.5%~2%, the total mass percentage is 100%.

[0009] Preferably, the ultra-high precision conversion absorption type dechlorination purifier comprises the following components in percentage by mass: Fe 2 O 3 :10%~30%, CuO:4%~10%, ZrO 2 :15%~30%,Al 2 O 3 : 25%~40%, ZnO: 10~20%, additives 0.5%~2%, the total mass percentage is 100%.

[0010] As a better embodiment of the present application, the preparation method of the ultra-high precision conversion absorption type dechlorination purifier described above comprises the following main steps:

[0011] e) Weigh the corresponding iron salt, copper salt, zirconium salt, aluminum salt and zinc salt of each component in proportion, dissolve them in deionized water at 80-100° C. to prepare a mixed solution for standby use;

[0012] f) preparing an alkaline solution with a concentration of 10 to 15 wt %, and then co-precipitating it with the mixed solution in a), stirring rapidly during the precipitation process, aging after precipitation, filtering, washing, drying, and calcining to obtain a precursor;

[0013] g) crushing the precursor obtained in b), then impregnating it with equal volume / excessive volume of ammonium dihydrogen phosphate or phosphoric acid, and then drying and calcining the precursor to obtain a semi-finished product;

[0014] h) adding a small amount of graphite and deionized water to the semi-finished product in c), mixing evenly, and pressing into a φ5×5mm column or a 2-8mm diameter strip to obtain the dechlorination purifier.

[0015] Preferably, in step a) of the method for preparing an ultra-high precision conversion absorption type dechlorination purifier, the iron salt, copper salt, zirconium salt, aluminum salt and zinc salt are respectively Fe(NO 3 ) 3 9H 2 O, Cu(NO 3 ) 2 ·3H 2 O, Zr(NO 3 ) 4 ·5H 2 O、Al(NO 3 )·9H 2 O、Zn(NO 3 ) 2 6H 2 O.

[0016] Preferably, in step b) of the method for preparing an ultra-high precision conversion absorption type dechlorinating agent catalyst, the alkaline solution is K-containing 2 CO 3 , ammonium bicarbonate, ammonia water, sodium hydroxide, potassium hydroxide or Na 2 CO 3 One or two of the aqueous solutions.

[0017] Preferably, in step b) of the preparation method of the ultra-high precision conversion absorption type dechlorination purifier, the precipitation temperature is maintained at 50-100°C, the pH of the precipitation process is 7.5-9.0, and the end point pH is 7.5-9.5; the aging time is 1-8h; it is filtered and washed to neutrality, and then dried at 80-120°C; and calcined at 350-500°C for 3-5h to obtain a precursor.

[0018] Preferably, in step c) of the method for preparing an ultra-high precision conversion absorption type dechlorination purifier, the precursor is crushed to a size of 200 mesh or more; the precursor is dried at 80-200° C. and calcined at 350-500° C. for 3-5 hours.

[0019] Preferably, in step c) of the method for preparing an ultra-high precision conversion absorption type dechlorination purifier, the auxiliary agent is diammonium phosphate or phosphoric acid.

[0020] The present application also protects the use of the ultra-high precision conversion absorption type dechlorination purifier prepared by the above method in the deep removal of large amounts of organic chlorine and inorganic chlorine in raw gases such as waste coal gas, coke oven gas, natural gas or gaseous hydrocarbons.

[0021] Preferably, in the above-mentioned application, the dechlorination purifier can deeply remove a large amount of chlorides at 220-350°C, and can remove chlorides in the raw gas to below 0.01 ppm.

[0022] The activity detection conditions of the above obtained dechlorination purifier are:

[0023] The reaction system temperature is 220-350°C, the pressure is 0.5-1.0 MPa, and the raw gas space velocity is 5000-20000 h -1 .

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (i) In this scheme, the combined use of iron oxide and copper oxide improves the conversion and absorption capacity of organic chlorine, and is also beneficial to improving the removal accuracy of organic chlorine and inorganic chlorine, and can reduce the total chlorine at the outlet to 0.01ppm.

[0026] (ii) In this scheme, Al 2 O 3 / ZrO 2 The composite carrier has high mechanical strength and good stability. And further ZrO is added to the carrier 2 To further isolate the active components, improve the sintering resistance of the active components, and thus improve the thermal stability.

[0027] (III) In this scheme, alkali metal oxides for removing inorganic chlorine are added to increase the chlorine capacity of the dechlorinating agent. On this basis, phosphate is impregnated to generate phosphide, thereby increasing the performance of hydrogenation dechlorination.

[0028] (iv) The preparation process is simple, the production cost is low, and it is suitable for large-scale industrial application. DETAILED DESCRIPTION

[0029] All features disclosed in this specification, or steps in all methods or processes disclosed, except mutually exclusive features and / or steps, can be combined in any manner.

[0030] Any feature disclosed in this specification (including claims and abstract), unless otherwise stated, may be replaced by other equivalent or alternative features having similar purposes. That is, unless otherwise stated, each feature is only an example of a series of equivalent or similar features.

[0031] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0032] In the present invention, % not specifically indicated represents mass percentage, that is, wt%.

[0033] Embodiment 1:

[0034] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0035] F 2 O 3 : 10%, CuO: 10%, Al 2 O 3 : 38.0%, ZrO 2 : 30.0%, ZnO: 10%, auxiliary agent: 2%.

[0036] The specific preparation process is:

[0037] 1. According to the proportion of each component in the dechlorination purifier finished product, weigh 101.25g Fe(NO 3 ) 3 9H 2 O, 60.78 g Cu(NO 3 ) 2 ·3H 2 O, 209.05g Zr(NO 3 ) 4 ·5H 2 O, 559.02 g Al(NO 3 ) 3 9H 2 O, 73.11gZn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 90 °C and set aside.

[0038] 2. Prepare 15% concentration of NaHCO 3The solution is then precipitated in parallel with the mixed solution obtained in step 1. The precipitation process is rapidly stirred, the precipitation temperature is maintained at 90°C, the pH of the precipitation process is ≈ 9.0, the end point pH is 9.0, and it is aged for 1h. It is filtered and washed to neutrality, and then the filter cake is dried at 120°C and calcined at 400°C to obtain a precursor.

[0039] 3. Weigh 6.4 g of ammonium dihydrogen phosphate and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then the ammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 80-120°C and calcined at 500°C for 3h to obtain a semi-finished product.

[0040] 4. The calcined semi-finished material in step 3 is crushed to above 200 meshes, 3% of graphite and 6% of deionized water are added thereto, mixed evenly and pressed into shape.

[0041] That is, the finished product 1# of the dechlorination purifier is obtained.

[0042] Example 2

[0043] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0044] The specific preparation process is:

[0045] F 2 O 3 : 18%, CuO: 8%, Al 2 O 3 : 35%, ZrO 2 : 22.2%, ZnO: 15%, additives: 1.8%.

[0046] 1. According to the proportion of each component in the finished dechlorination purifier, weigh 182.26gFe(NO 3 ) 3 9H 2 O, 48.62 g Cu(NO 3 ) 2 ·3H 2 O, 154.69 g Zr(NO 3 ) 4 ·5H 2 O, 514.88 g Al(NO 3 ) 3 9H 2 O, 109.67 g Zn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 80 °C and set aside.

[0047] 2. Prepare 12% Na 2 CO 3 The solution is then precipitated in parallel with the mixed solution obtained in step 1. The precipitation process is rapidly stirred, the precipitation temperature is maintained at 80°C, the pH of the precipitation process is ≈8.5, the end point pH is 9.0, and it is aged for 2h. It is filtered and washed to neutrality, and then the filter cake is dried at 100°C and calcined at 420°C to obtain a precursor.

[0048] 3. Weigh 5.83 g of ammonium dihydrogen phosphate and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then the ammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 450°C for 3 hours to obtain a semi-finished product.

[0049] 4. The calcined semi-finished product material in step 3 is crushed to above 200 mesh, 4% of graphite and 6% of deionized water are added thereto, mixed evenly and pressed into shape.

[0050] That is, the finished product 2# of the dechlorination purifier is obtained.

[0051] Example 3

[0052] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0053] F 2 O 3 : 20%, CuO: 7%, Al 2 O 3 : 28.0%, ZrO 2 : 26.4%, ZnO: 17%, additives: 1.6%.

[0054] The specific preparation process is:

[0055] 1. According to the proportion of each component in the dechlorination purifier finished product, weigh 202.5g Fe(NO 3 ) 3 9H 2 O, 42.55 g Cu(NO 3 ) 2 ·3H 2 O, 183.96g Zr(NO 3 ) 4 ·5H 2 O, 411.91 g Al(NO 3 ) 3 9H 2 O, 124.29 g Zn(NO 3 ) 2 6H2 Prepare the mixed solution with 1 L of deionized water at 80 °C and set aside.

[0056] 2. Prepare 10% concentration of K 2 CO 3 The solution is then precipitated in parallel with the mixed solution obtained in step 1. The precipitation process is rapidly stirred, the precipitation temperature is maintained at 70°C, the pH of the precipitation process is ≈8.0, the end point pH is 9.0, and it is aged for 1.5h. It is filtered and washed to neutrality, and then the filter cake is dried at 120°C and calcined at 450°C to obtain a precursor.

[0057] 3. Weigh 5.18 g of ammonium dihydrogen phosphate and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then the ammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 400°C for 3 hours to obtain a semi-finished product.

[0058] 4. The calcined semi-finished material in step 3 is crushed to above 200 meshes, 2% of graphite and 5% of deionized water are added thereto, mixed evenly and pressed into shape.

[0059] That is, the finished desulfurizer product 3# is obtained.

[0060] Example 4

[0061] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0062] Fe 2 O 3 : 25%, CuO: 6%, Al 2 O 3 : 26.0%, ZrO 2 : 27.6%, ZnO: 14%, additives: 1.4%.

[0063] The specific preparation process is:

[0064] 1. According to the proportion of each component in the dechlorination purifier, weigh 253.13g Fe(NO 3 ) 3 9H 2 O, 36.47 gCu(NO 3 ) 2 ·3H 2 O, 192.33 g Zr(NO 3 ) 4 ·5H 2 O, 382.49 g Al(NO 3 ) 3 9H 2O, 102.36gZn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 75 °C and set aside.

[0065] 2. Prepare a 10% concentration of ammonium bicarbonate solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, keep the precipitation temperature at 75°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 9.0. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 350°C to obtain the precursor.

[0066] 3. Weigh 4.53 g of phosphoric acid and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then the phosphoric acid is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 350°C for 5 hours to obtain a semi-finished product.

[0067] 4. The calcined semi-finished product material in step 3 is crushed to above 200 meshes, 5% of graphite and 5% of deionized water are added thereto, mixed evenly and pressed into shape.

[0068] The finished catalyst product 4# is obtained.

[0069] Example 5

[0070] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0071] Fe 2 O 3 :30%,CuO:4%,Al 2 O 3 : 25.0%, ZrO 2 : 19.8%, ZnO: 20%, additives: 1.2%.

[0072] The specific preparation process is:

[0073] 1. According to the proportion of each component in the dechlorination purifier, weigh 303.76g Fe(NO 3 ) 3 9H 2 O, 24.31 gCu(NO 3 ) 2 ·3H 2 O, 137.97 g Zr(NO 3 ) 4 ·5H 2 O, 367.77 g Al(NO 3 ) 3 9H2 O, 146.22gZn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 70 °C and set aside.

[0074] 2. Prepare a 10% concentration of ammonia solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, maintain the precipitation temperature at 72°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 8.5. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 380°C to obtain the precursor.

[0075] 3. Weigh 3.28 g of phosphoric acid and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then diammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 380°C for 5 hours to obtain a semi-finished product.

[0076] 4. The calcined semi-finished product material in step 3 is crushed to above 200 meshes, 4% of graphite and 3% of deionized water are added thereto, mixed evenly and pressed into shape.

[0077] The finished catalyst product 5# is obtained.

[0078] Example 6

[0079] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0080] Fe 2 O 3 :30%,CuO:4%,ZrO 2 : 44.8%, ZnO: 20%, additives: 1.2%.

[0081] The specific preparation process is:

[0082] 1. According to the proportion of each component in the dechlorination purifier, weigh 303.76g Fe(NO 3 ) 3 9H 2 O, 24.31 gCu(NO 3 ) 2 ·3H 2 O, 312g Zr(NO 3 ) 4 ·5H 2 O, 146.22 g Zn(NO 3 ) 2 6H 2Prepare the mixed solution with 1 L of deionized water at 70 °C and set aside.

[0083] 2. Prepare a 10% concentration of ammonia solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, maintain the precipitation temperature at 72°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 8.5. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 380°C to obtain the precursor.

[0084] 3. Weigh 3.28 g of phosphoric acid and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then diammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 380°C for 5 hours to obtain a semi-finished product.

[0085] 4. The calcined semi-finished product material in step 3 is crushed to above 200 meshes, 4% of graphite and 3% of deionized water are added thereto, mixed evenly and pressed into shape.

[0086] The finished catalyst product 6# is obtained.

[0087] Example 7

[0088] Fe 2 O 3 :30%,CuO:4%,Al 2 O 3 : 44.80%, ZnO: 20%, additives: 1.2%.

[0089] The specific preparation process is:

[0090] 1. According to the proportion of each component in the dechlorination purifier, weigh 303.76g Fe(NO 3 ) 3 9H 2 O, 24.31 gCu(NO 3 ) 2 ·3H 2 O,659.05Al(NO 3 ) 3 9H 2 O, 146.22 g Zn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 70 °C and set aside.

[0091] 2. Prepare a 10% concentration of ammonia solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, maintain the precipitation temperature at 72°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 8.5. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 380°C to obtain the precursor.

[0092] 3. Weigh 3.28 g of phosphoric acid and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then diammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 380°C for 5 hours to obtain a semi-finished product.

[0093] 4. The calcined semi-finished product material in step 3 is crushed to above 200 meshes, 4% of graphite and 3% of deionized water are added thereto, mixed evenly and pressed into shape.

[0094] The finished catalyst product 7# is obtained.

[0095] Example 8

[0096] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0097] Fe 2 O 3 :30%,CuO:4%,Al 2 O 3 : 26.2%, ZrO 2 : 19.8%, ZnO: 20%.

[0098] The specific preparation process is:

[0099] 1. According to the proportion of each component in the dechlorination purifier, weigh 303.76g Fe(NO 3 ) 3 9H 2 O, 24.31 gCu(NO 3 ) 2 ·3H 2 O, 137.97 g Zr(NO 3 ) 4 ·5H 2 O, 367.77 g Al(NO 3 ) 3 9H 2 O, 146.22gZn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 70 °C and set aside.

[0100] 2. Prepare a 10% concentration of ammonia solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, maintain the precipitation temperature at 72°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 8.5. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 380°C to obtain the precursor.

[0101] 3. The calcined semi-finished material in step 2 is crushed to above 200 meshes, 4% of graphite and 3% of deionized water are added thereto, mixed evenly and pressed into shape.

[0102] The finished catalyst product 8# is obtained.

[0103] Example 9

[0104] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0105] Fe 2 O 3 : 30%,Al 2 O 3 : 29.0%, ZrO 2 : 19.8%, ZnO: 20%, additives: 1.2%.

[0106] The specific preparation process is:

[0107] 1. According to the proportion of each component in the dechlorination purifier, weigh 303.76g Fe(NO 3 ) 3 9H 2 O, 137.97gZr(NO 3 ) 4 ·5H 2 O, 426.6 g Al(NO 3 ) 3 9H 2 O, 146.22 g Zn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 70 °C and set aside.

[0108] 2. Prepare a 10% concentration of ammonia solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, maintain the precipitation temperature at 72°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 8.5. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 380°C to obtain the precursor.

[0109] 3. Weigh 3.28 g of phosphoric acid and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then diammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 380°C for 5 hours to obtain a semi-finished product.

[0110] 4. The calcined semi-finished product material in step 3 is crushed to above 200 meshes, 4% of graphite and 3% of deionized water are added thereto, mixed evenly and pressed into shape.

[0111] The finished catalyst product 9# is obtained.

[0112] Example 10

[0113] In this embodiment, the mass percentage of the components of the ultra-high precision conversion absorption type dechlorination purifier is required to be:

[0114] CuO: 4%, Al 2 O 3 :40.0%,ZrO 2 : 34.8%, ZnO: 20%, additives: 1.2%.

[0115] The specific preparation process is:

[0116] 1. According to the ratio of each component in the dechlorination purifier, 24.31gCu(NO 3 ) 2 ·3H 2 O, 242.3gZr(NO 3 ) 4 ·5H 2 O, 588.43 g Al(NO 3 ) 3 9H 2 O, 146.22 g Zn(NO 3 ) 2 6H 2 Prepare the mixed solution with 1 L of deionized water at 70 °C and set aside.

[0117] 2. Prepare a 10% concentration of ammonia solution, and then precipitate it with the mixed solution obtained in step 1. Stir rapidly during the precipitation process, maintain the precipitation temperature at 72°C, pH ≈ 8.0 during the precipitation process, and the end point pH is 8.5. Aging for 1h, filter and wash it to neutrality, then dry the filter cake at 120°C, and calcine at 380°C to obtain the precursor.

[0118] 3. Weigh 3.28 g of phosphoric acid and dissolve it in 60 g of deionized water to prepare a solution. The precursor obtained in step 2 is first crushed to more than 200 mesh by a crusher, and then diammonium dihydrogen phosphate is impregnated into the precursor by equal volume impregnation. The precursor is then dried at 120°C and calcined at 380°C for 5 hours to obtain a semi-finished product.

[0119] 4. The calcined semi-finished product material in step 3 is crushed to above 200 meshes, 4% of graphite and 3% of deionized water are added thereto, mixed evenly and pressed into shape.

[0120] That is, the finished catalyst product 10# is obtained.

[0121] Embodiment 11

[0122] This example is an activity evaluation experiment of the finished dechlorination purifiers (1#, 2#, 3#, 4#, 5#, 6#, 7#, 8#, 9#, 10#) prepared in the above examples 1 to 10. The evaluation of the dechlorination purifiers was performed using a fixed bed reactor.

[0123] Selected analytical instruments: Gas chromatograph: American Agilent GC-8890, ECD detector, mainly used to measure the chloride content in the reactor outlet gas.

[0124] Composition of raw gas for dechlorination agent activity determination: 9.0% CO 2 , 0.9% C 2 H 6 , 44% N 2 , 5.3% CH 4 , 15% CO, 25% H 2 , 0.8% C 3 H 8 , ethyl chloride 50ppm, methyl chloride 50ppm.

[0125] Activity determination: First, the dechlorination purifier was reduced with hydrogen. Reduction conditions: The reducing gas was H 2 and N 2 Mixed gas, temperature 450℃, pressure 0.5Mpa, air velocity 1000~2000h -1 After the catalyst reduction is completed, the temperature is lowered to 350°C at a rate of 30-50°C per hour, and then the raw gas is introduced, and the pressure is set to 1.0MPa. After the system is stable, the reactor outlet data is recorded and analyzed. The measurement results of 1#, 2#, 3#, 4#, 5#, 6#, 7#, 8#, 9#, and 10# dechlorination purifiers are shown in Table 1.

[0126] Table 1 Activity assay analysis data table

[0127]

[0128] As can be seen from the above table, the 1#, 2#, 3#, 4#, and 5# dechlorination purifiers developed by the present invention have a high removal accuracy for organic chlorine at a reaction temperature of 350°C, and the penetration chlorine capacity of organic chlorine under the condition of 8000 space velocity is greater than 5.0% (wt%), and the penetration chlorine capacity of organic chlorine under the condition of 4000 space velocity is greater than 4.5% (wt%). Increasing the space velocity has a certain effect on the penetration chlorine capacity of the desulfurizer, but the dechlorination purifier in the present invention still has a high penetration chlorine capacity and extremely high dechlorination accuracy at high space velocity.

[0129] In addition, the chlorine capacity of 6# decreased by 46.2% compared with 5#, because 6# purifier did not add alumina and did not form Al 2 O 3 / ZrO 2 Composite carrier. The chlorine capacity of 7# decreased by 29.3% compared with 5#, because 7# purifier did not add zirconium oxide, and could not form Al 2 O 3 / ZrO 2 Composite carrier. The chlorine capacity of 7# decreased by 29.3% compared with 5#, because 7# purifier did not add zirconium oxide, and could not form Al 2 O 3 / ZrO 2 Composite carrier. Compared with 5#, the chlorine capacity of 8# decreased by 11.7%, because 8# purifier was not impregnated with phosphate and no phosphide was formed. Compared with 5#, the chlorine capacity of 9# decreased by 20%, because 9# purifier did not add copper oxide, indicating that copper oxide has a greater impact on the entire purifier system. Compared with 5#, the chlorine capacity of 10# decreased by 59.5%, because 10# purifier did not add iron oxide, indicating that iron oxide has a huge impact on the entire purifier system. Through a series of comparative experiments, it can be seen that in this scheme, Al 2 O 3 / ZrO 2 The formation of the composite carrier, the combined use of iron oxide and copper oxide active components, and the introduction of phosphates have a significant impact on the dechlorination performance of this purifier.

[0130] The dechlorination purifier prepared by the present invention has the advantages of high chlorine penetration capacity, high dechlorination accuracy and adaptability to high air velocity, and can be applied to the deep purification process of organic chlorine in raw gas such as raw coal gas, coke oven gas, natural gas and gaseous hydrocarbons, and has great industrial promotion and application value.

[0131] The above-mentioned embodiments only express the specific implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the protection scope of the present application. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the technical solution concept of the present application, and these all belong to the protection scope of the present application.

[0132] This background section is provided to generally present the context of the invention, and the work of the presently named inventors, the work to the extent described in this background section, and aspects of this section that did not constitute prior art at the time of application are neither explicitly nor implicitly admitted to be prior art to the present invention.

Claims

1. An ultra-high precision conversion absorption type dechlorination purifier, characterized in that The invention comprises the following components in percentage by mass: Fe2O3: 5%-30%, CuO: 1%-10%, ZrO2: 10%-30%, Al2O3: 20%-40%, ZnO: 10-20%, and auxiliary agent: 0.5%-2%, and the total percentage by mass is 100%.

2. The ultra-high precision conversion absorption type dechlorination purifier according to claim 1, characterized in that The invention comprises the following components in percentage by mass: Fe2O3: 10%-30%, CuO: 4%-10%, ZrO2: 15%-30%, Al2O3: 25%-40%, ZnO: 10-20%, and auxiliary agent: 0.5%-2%, and the total percentage by mass is 100%.

3. The method for preparing an ultra-high precision conversion absorption type dechlorination purifier according to claim 1 or 2, characterized in that The main steps include: a) Weigh the corresponding iron salt, copper salt, zirconium salt, aluminum salt and zinc salt of each component in proportion, dissolve them in deionized water at 80-100° C. to prepare a mixed solution for standby use; b) preparing an alkali solution with a concentration of 10 to 15 wt %, and then co-precipitating with the mixed solution in a), stirring rapidly during the precipitation process, aging after precipitation, filtering, washing, drying, and calcining to obtain a precursor; c) crushing the precursor obtained in b), then impregnating it with equal volume / excessive volume of diammonium phosphate or phosphoric acid, and then drying and calcining the precursor to obtain a semi-finished product; d) Add a small amount of graphite and deionized water to the semi-finished product in c), mix well, and press into a φ5×5mm column or a 2-8mm diameter strip to obtain the dechlorination purifier.

4. The method for preparing an ultra-high precision conversion absorption type dechlorination purifier according to claim 3, characterized in that: The iron salt, copper salt, zirconium salt, aluminum salt and zinc salt in step a) are Fe(NO3)3·9H2O, Cu(NO3)2·3H2O, Zr(NO3)4·5H2O, Al(NO3)·9H2O and Zn(NO3)2·6H2O respectively.

5. The method for preparing an ultra-high precision conversion absorption type dechlorinating agent catalyst according to claim 3 or 4, characterized in that: The alkaline solution in step b) is an aqueous solution containing one or two of K2CO3, ammonium bicarbonate, ammonia water, sodium hydroxide, potassium hydroxide or Na2CO3.

6. The method for preparing an ultra-high precision conversion absorption type dechlorination purifier according to claim 5, characterized in that: In the step b), the precipitation temperature is maintained at 50-100° C., the pH value during the precipitation process is 7.5-9.0, and the end point pH value is 7.5-9.5; the aging time is 1-8 hours; the product is filtered and washed to neutrality, and then dried at 80-120° C.; and the product is calcined at 350-500° C. for 3-5 hours to obtain a precursor.

7. A method for preparing an ultra-high precision conversion absorption type dechlorination purifier according to claim 3, 4 or 6, characterized in that: In step c), the precursor is crushed to a size of 200 mesh or more; the precursor is dried at 80-200° C. and calcined at 350-500° C. for 3-5 hours.

8. The method for preparing an ultra-high precision conversion absorption type dechlorination purifier according to claim 7, characterized in that: The auxiliary agent in step c) is diammonium phosphate or phosphoric acid.

9. Use of the ultra-high precision conversion absorption type dechlorination purifier prepared according to the method of claim 3, 4, 6 or 8 in deep removal of large amounts of organic chlorine and inorganic chlorine in waste gas, coke oven gas, natural gas or gaseous hydrocarbon raw gas.

10. The use according to claim 9, characterized in that: The dechlorination purifier can deeply remove a large amount of chlorides at 220-350°C and can remove chlorides in the raw gas to below 0.01ppm.

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