CN105363444A - Composition for reducing emission of CO and NOx of FCC regeneration flue gas and preparation method of composition - Google Patents

Composition for reducing emission of CO and NOx of FCC regeneration flue gas and preparation method of composition Download PDF

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CN105363444A
CN105363444A CN 201410437782 CN201410437782A CN105363444A CN 105363444 A CN105363444 A CN 105363444A CN 201410437782 CN201410437782 CN 201410437782 CN 201410437782 A CN201410437782 A CN 201410437782A CN 105363444 A CN105363444 A CN 105363444A
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noble metal
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宋海涛
田辉平
朱玉霞
蒋文斌
陆友保
陈蓓艳
黄志青
沈宁元
郑学国
达志坚
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Abstract

The invention discloses a composition for reducing emission of CO and NOx of FCC regeneration flue gas and a preparation method of the composition. The composition is prepared from 0.5-30 wt% of rare earth elements, 0.01-0.15 wt% of precious metal elements and the balance inorganic oxide carriers basically containing no alkali metal or alkaline-earth metal according to oxide. In the preparation method, the composition where precious metal is introduced is processed by an alkaline solution before being dried and/or calcinated. The composition is used for fluid catalytic cracking, post-combustion caused by too high regeneration flue gas CO concentration can be effectively avoided, the emission concentration of CO and NOx in regeneration flue gas can be effectively controlled, and emission of smoke NOx is remarkably reduced, and basically no adverse influences are caused to distribution of FCC products.

Description

用于降低FCC再生烟气CO和N0<排放的组合物及其制备方法 FCC regenerator flue gas for reducing CO and N0 <compositions and preparation method emissions

技术领域 FIELD

[0001] 本发明涉及用一种用于降低催化裂化再生烟气CO和NOy排放的含贵金属组合物及其制备方法。 [0001] The present invention relates to compositions and method for preparing a noble metal-containing FCC regenerator flue gas emissions of CO and NOy used for reducing.

背景技术 Background technique

[0002] 在流化催化裂化(FCC)过程中,原料油与再生催化剂在提升管中快速接触进行催化裂化反应,反应生成的焦炭沉积到催化剂上造成其失活,生焦失活的催化剂经汽提后进入再生器进行烧焦再生。 [0002] In the fluidized catalytic cracking (FCC) process, the feedstock and regenerated catalyst in the riser quick contacting catalytic cracking reaction, the resultant reaction caused by the deposition of coke on the catalyst to its inactivation, coke deactivated catalyst was after stripping entering the regenerator for burning regeneration. 再生过程中,焦炭及焦炭中的含氮化合物在再生空气的作用下会产生CO和NOy等污染物,随着环保法规对CO和NOy等污染物控制指标的日益严格,降低FCC 再生烟气污染CO和NOx排放受到越来越普遍的关注。 Regeneration process, coke, and coke nitrogen-containing compounds and CO generated NOy other pollutants under the effect of regeneration air, as environmental regulations on CO and increasingly stringent pollution control NOy other indicators, reduced the FCC regenerator flue gas pollution CO and NOx emissions by more widespread concern.

[0003] 降低FCC装置再生烟气污染物排放的主要技术措施包括;原料油加氨预处理、再生器改造、使用助剂和烟气后处理等,其中助剂技术因具有操作灵活简便、不需装置改造及无二次污染等优点而得到普遍的关注和应用。 [0003] FCC regenerators reduce smoke emissions main technical measures include; feedstock oil plus ammonia pretreatment, the transformation of the regenerator, the flue gas treatment and the use of adjuvants and the like, which aid technology by having flexible operations, not alteration and need no secondary pollution and universal attention and application.

[0004] 贵金属助剂(贵金属CO助燃剂)已被广泛用于降低再生烟气CO排放,然而,现有CO贵金属助燃剂的使用通常会造成烟气NOy排放大幅增加。 [0004] The noble metal aids (CO Combustion noble metal) has been widely used to reduce CO emissions from the flue gas regeneration, however, the use of conventional noble metal CO Combustion usually results in a substantial increase in smoke emissions NOy.

[0005]CN1151878C公布了一种含铜铅一饰铅复合氧化物和氧化铅载体的非贵金属一氧化碳燃烧催化剂及其制备方法,该催化剂含有依次负载在氧化铅上的饰铅复合氧化物和铜铅复合氧化物,且二者的负载重量比例Ce-A^O/Al2〇3为0. 02 - 0. 10,W及化-A^O/Al2〇3 为0. 05 - 0. 15,所述铜铅复合氧化物W团簇状态均匀分散在其表面W高分散的饰铅复合氧化物纳米微晶覆盖的氧化铅载体上。 [0005] CN1151878C discloses a copper lead a non-noble metal combustion catalyst decorated and preparation of lead oxide and lead oxide composite support carbon monoxide, the catalyst comprising lead oxide supported on sequentially decorative composite oxide of lead and copper lead composite oxide, and both the load weight ratio Ce-a ^ O / Al2〇3 is 0. 02 - 0. 10, W and of -A ^ O / Al2〇3 0. 05 - 0.15, the said copper-lead complex oxide clusters W uniformly dispersed state in which the lead oxide support surface W finely dispersed nanocrystalline composite oxide of lead decorative covering.

[0006]CN1688508A公布了一种降低流化催化裂化烟道气NOy和CO排放的组合物及其应用,所述组合物包括铜和/或钻和载体,所述载体选自水滑石类化合物、尖晶石、氧化铅、铁酸锋、铅酸锋、铁酸锋/铅酸锋。 [0006] CN1688508A discloses a fluid catalytic cracking reduction compositions and the use of flue gas NOy and CO emissions, the composition comprises copper and / or cobalt and a carrier selected from a hydrotalcite compound, spinel, lead oxide, ferrite front, front lead-acid, ferrite front / front lead-acid.

[0007]W02005040311A1公开了降低FCC再生过程NOy排放的组合物,该组合物包括;含有Mg和Al的阴离子型粘±或固溶体、稀±金属氧化物、氧化铅和/或氧化娃一氧化铅W及Y 型沸石,该组合物还可W含有过渡金属化。 [0007] W02005040311A1 discloses a reduced FCC regeneration process NOy composition discharged, the composition comprising; lead anionic sticky ± or a solid solution containing Mg and Al, dilute ± metal oxide, lead oxide and / or oxide baby monoxide W and Y-type zeolite, the composition may also contain a transition metal of W.

[0008]CN102371165A公开了一种用于降低FCC再生烟气CO和NOx排放的低堆比组合物, 该组合物含有稀±元素及一种或几种非贵金属元素,优选将非贵金属负载于Y型沸石上。 [0008] CN102371165A discloses a low bulk composition ratio of the FCC regenerator flue gas for reducing NOx and CO emissions, the composition contains dilute ± elements and one or more non-noble metal element, preferably a non-noble metal is supported on Y the zeolite.

[0009]W上现有技术中,使用非贵金属,但由于不采用贵金属元素活性组分,其CO氧化活性偏低,所用非贵金属元素组分的含量较高,助剂组合物在主催化剂中的加入量通常较商。 [0009] W on the prior art, the use of non-noble metal, the noble metal element is not used but the active ingredient, its low CO oxidation activity, with a higher content of the non-noble metal element component, adjuvant composition in procatalyst the amount usually more providers.

[0010] US6165933公开了一种减少催化裂化过程NOx排放的CO助燃组合物(助剂)。 [0010] US6165933 discloses a composition of CO combustion in a catalytic cracking process NOx emissions (aid) reduction. 所述组合物包含;(i)基本上不含沸石的酸性金属氧化物;(ii)碱金属、碱±金属或是它们的混合物;(iii)储氧组分和(iv)铅。 Said composition comprising; (I) substantially free of zeolite acidic metal oxide; (ii) an alkali metal, an alkali metal or mixtures thereof ±; oxygen (iii) storage component and (iv) lead. 所述酸性氧化物载体优选氧化娃一氧化铅,所述储氧过渡金属氧化物优选为氧化饰。 The acidic oxide support preferably baby oxide lead oxide, transition metal oxide of the oxygen storage oxide is preferably decorated.

[0011]US7045056B2公开了一种用于同时降低催化裂化过程烟气CO和NOy排放的组合物,所述组合物含有:(i) 一种酸性氧化物载体;(ii)饰的氧化物;(iii) 一种除饰W外的铜系氧化物,其中(ii)与(iii)的重量比至少为1. 66:1 ;(iv)可选地一种IB和IIB族过渡金属氧化物,W及(V)至少一种贵金属元素。 [0011] US7045056B2 discloses a composition for catalytic cracking process while reducing flue gas emissions of CO and NOy, said composition comprising: (i) an acidic oxide support; (ii) an oxide decorated; ( iii) one other copper oxide decorated outside W, wherein (ii) weight (iii) ratio of at least 1. 66: 1; (iv) optionally one IB and IIB transition metal oxides, and W (V) at least one noble metal element.

[0012] W上使用贵金属的现有助剂中,所述含碱金属、碱±金属和不稳定过渡金属元素的助剂组合物在使用过程中会对裂化催化剂的裂化活性和选择性产生不利影响;此外,所述助剂组合物的CO助燃性能及降低NOy排放性仍需提高,助剂的水热稳定性需进一步改善。 [0012] W noble metal prior auxiliaries, the cracking activity of the alkali metal, alkali metal and ± labile transition metal element adjuvant composition during use and selectivity of the cracking catalyst will adversely Effect; in addition, combustion of CO and the adjuvant composition of reducing emissions NOy still need to improve hydrothermal stability need further improvement aid.

发明内容 SUMMARY

[0013] 本发明要解决的技术问题是在现有技术基础上提供一种含贵金属的降低催化裂化再生烟气CO和NOy排放的组合物,其具有更好的降低催化裂化再生烟气CO和NOy排放效果;本发明要解决的另外一个技术问题是提供上述组合物的制备和应用方法。 [0013] The present invention is to solve the technical problem of providing a noble metal-containing reducing cracking regeneration flue gas emissions of CO and NOy compositions on the basis of the prior art, having a better regeneration flue gas CO and reduce cracking NOy discharge effect; the present invention is to solve another technical problem is to provide the above composition preparation and application methods.

[0014] 本发明提供一种用于降低催化裂化再生烟气CO和NOy排放的组合物,W所述组合物的重量为基准,含有W氧化物计;(1)0. 5 - 30重量%的稀±元素,(2)0.Ol- 0. 15重量%的贵金属元素,和(3)平衡量的基本不含碱金属和碱±金属的无机氧化物载体,所述组合物的制备方法中,所述的贵金属元素引入到所述组合物中后,在干燥和/或赔烧前经碱性溶液处理。 [0014] The present invention provides a method for reducing the FCC regenerator flue gas composition and NOy CO emissions, the weight W of the composition as a reference, the W-containing oxides;. (1) 05--30 wt% dilute ± elements, (2) 0.Ol- 0. 15 wt% of the noble metal element, and (3) the balance being substantially free of alkali and ± alkali metal inorganic oxide support, preparation of the composition after, the noble metal element is introduced into the composition, drying and / or pre-treated with an alkaline solution to lose burning. 所述贵金属元素优选采用浸溃的方法负载于氧化物载体上,且负载贵金属后的组合物在干燥和/或赔烧前经碱性溶液处理。 The noble metal element is preferably impregnated using the method supported on the oxide carrier and a noble metal supported in the composition after drying and / or pre-treated with an alkaline solution to lose burning.

[0015] 本发明所提供的组合物还可含有W氧化物计不超过5重量%的选自IB~VIIB族非稀±元素中的一种或几种的金属添加剂组分。 [0015] The present invention provides a composition may further contain one or more metal oxides W additive component not more than 5% by weight of the non-selected Group IB ~ VIIB dilute ± elements.

[0016] 本发明还提供一种所述用于降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,包括制备含稀±元素组分和无机氧化物载体组分的浆液和喷雾干燥、赔烧,浸溃贵金属元素,采用碱性溶液处理和干燥和/或赔烧的步骤。 [0016] The present invention also provides a method for preparing FCC regenerator flue gas emissions of CO and NOy said composition for reducing, comprising the slurry and a dilute spray prepared containing elemental components ± inorganic oxide support component and dried Compensating burning, dipping noble metal element, an alkaline solution treatment, and drying and / or burning step lost.

[0017] 本发明进一步提供一种流化催化裂化方法,包括将姪油与催化剂接触反应和再生的步骤,W所述催化剂的总重量为基准,所述催化剂中含有0. 05 - 5重量%本发明所提供的用于降低催化裂化再生烟气CO和NOy排放的组合物。 [0017] The present invention further provides a fluid catalytic cracking process, comprising the step of contacting the oil nephew reaction and regeneration of the catalyst, the total weight W of the catalyst as a reference, the catalyst contains 0.05 - 5 wt% the present invention provides for reducing the FCC regenerator flue gas emissions of CO and NOy composition.

[0018] 本发明提供的降低催化裂化(FCC)再生烟气CO和NOy排放组合物,采用经稀±元素改性的氧化物载体,并在负载贵金属组分后采用碱性溶液处理,作为催化裂化助剂,可W 在再生器水热环境中保持较高的水热稳定性,具有较高的降低再生烟气NOy排放活性和较高的CO助燃活性;并且,本发明提供的组合物作为流化催化裂化降低CO和NOy排放助剂,焦炭和干气产率较低。 [0018] The present invention provides reduced cracking (FCC) regeneration flue gas emissions of CO and NOy compositions using dilute ± oxide support modified by the elements, and the alkaline solution treatment after a noble metal component as catalyst cracking additives, W can be kept high hydrothermal stability hydrothermal environments in the regenerator, the regenerator flue gas has a high reducing activity and higher emissions NOy CO combustion activity; and, the present invention provides a composition as Fluid catalytic cracking and reduced CO emissions aid NOy, lower coke and dry gas yields. 本发明提供的流化催化裂化方法,通过对降低CO和NOy排放助剂的化学组成进行调变和稳定化处理,可W使助剂具有更高的活性和稳定性,与使用现有降低CO 和NO,排放助剂的FCC方法相比,不仅助剂用量较低,而且降低CO和NO,排放活性更高。 Fluid catalytic cracking process of the present invention to provide, by chemical reduction of the CO emissions and aid NOy composition of modulation and stabilization treatment, so that W has a higher adjuvant activity and stability with the use of conventional reducing CO and NO, FCC emissions aid as compared to the method, not only lower amounts aid, but also reduces the CO and NO, emissions higher activity. 例女口,本发明所提供的Ce〇2含量10质量%、化2〇3含量0. 5质量%、PdO含量0. 06质量%且在浸溃贵金属Pd后采用氨水溶液处理的助剂组合物,按占催化剂总藏量0. 6重量%的比例与FCC主催化剂(商品牌号G0R-II)渗混均匀后,经80(TC、100%水蒸汽气氛下老化12小时后进行催化裂化反应一再生评价,与现有技术采用活性组分饱和浸溃方法制备的Ce化含量12%、PdO含量0. 06%但在浸溃贵金属后不采用氨水处理的对比组合物在对比组合物占催化剂总藏量0.9重量%、其它操作条件相同的情况下进行反应一再生评价的结果相比较, 本发明提供的助剂组合物再生烟气中NOy的排放浓度为10化pm,对比组合物再生烟气NOy的排放浓度为128ppm,烟气CO排放浓度也由对比组合物的0. 51体积%进一步降低到0. 42 体积%。 Example female population, the present invention provides Ce〇2 content 10% by mass, 2〇3 content of 0.5% by mass, of PdO content of 0.06% by mass solution of ammonia and the use of the impregnated precious metal Pd after the adjuvant composition composition, according to the ratio of the total catalyst inventory of 0.6 wt% and the main FCC catalyst (trade designation G0R-II) uniformly mixing the retentate, by 80 (TC, 100% steam cracking reaction was carried out after 12 hours of aging in an atmosphere a regeneration evaluation, the prior art was prepared using Ce content of active ingredient saturated dipping method 12%, PdO content of 0.06% after dipping but does not use the noble metal treated comparative composition accounted ammonia catalyst in Comparative composition total reserves carried out at 0.9 wt%, the same as other operating conditions are the reaction of a comparison result of the evaluation regeneration, the present invention provides an adjuvant composition NOy regeneration flue gas emission concentration of PM is 10, reproduction smoke comparative compositions NOy gas emission concentration is 128ppm, smoke and CO concentration is further reduced from 0.51% by volume of the composition to Comparative 0.42% by volume.

具体实施方式 detailed description

[0019] 本发明所提供的用于降低催化裂化再生烟气CO和NOy排放的组合物,采用经稀± 改性的氧化物载体,并在负载贵金属组分后采用碱性溶液处理。 [0019] The present invention provides for reducing the FCC regenerator flue gas emissions of CO and NOy composition by using dilute ± modified oxide support, and an alkaline solution treatment after a noble metal component. W所述组合物的重量为基准,含有W氧化物计;(1)0. 5 - 30重量%的稀±元素,(2)0.Ol- 0. 15重量%的贵金属元素,和(3)余量的基本不含碱金属和碱±金属的无机氧化物载体。 W is the weight of the composition as a reference, the W-containing oxides;. (1) 05--30 wt% of lean ± elements, (2) 0.Ol- 0. 15 wt% of the noble metal element, and (3 ) the balance substantially an alkali metal and an inorganic oxide support ± alkali metal. 所述组合物优选含有: (1) W氧化物计2 - 29. 99重量%例如2 - 20重量%的稀±元素,(2)W单质计0.Ol-0. 1重量%的贵金属元素,和(3)W氧化物计70 - 97. 99重量%例如70 - 95重量%的基本不含碱金属和碱±金属的无机氧化物载体;更优选含有:(1) 5 - 15重量%的稀±元素, (2) 0. 03 - 0. 08重量%的贵金属元素,和(3)84. 2 - 94. 97重量%例如80 - 90重量%的基本不含碱金属和碱±金属的无机氧化物载体。 The composition preferably comprises:. (1) W oxides 2 - 29.99 wt%, for example, 2 - 20% by weight of the dilute ± elements, (2) W elemental basis 0.Ol-0 1 wt% of the noble metal element and (3) W oxides 70-- 97.99 wt% e.g. 70--95% by weight of alkali metal base and an inorganic oxide support ± alkali metal; more preferably comprises: (1) 5 - 15 wt% dilute ± elements, (2) 0. 03 - 0.08 wt% of the noble metal element, and (3) 84 2 - 94.97 wt% e.g. 80--90% by weight of the basic alkali metal and an alkali metal ± the inorganic oxide support. 所述基本不含碱金属和碱±金属指无机氧化物载体中W氧化物计碱金属和碱±金属的总含量不超过1重量%,优选不超过0. 5重量%。 The substantially free of alkali metals and alkali metal ± refers to the total content of the inorganic oxide support W oxides of alkali and alkali metal is not more than ± 1% by weight, preferably not more than 0.5 wt%.

[0020] 本发明所提供的用于降低催化裂化再生烟气CO和NOy排放的组合物中,所述稀± 元素选自铜系元素中的一种或几种,优选为Ce、La和Pr中的一种或几种或包含Ce、La和Pr中的至少一种的混合稀±,更优选为Ce。 [0020] The present invention provides for reducing the FCC regenerator flue gas emissions of CO and NOy composition, said lean ± element selected from copper-based one or several elements, preferably Ce, La and Pr of one or more or comprising Ce, La and Pr at least one mixing dilute ±, more preferably Ce.

[002。 [002. 本发明所提供的组用于降低催化裂化再生烟气CO和NO,排放的合物中,所述贵金属元素为Pd、Ir、化中的一种或几种,优选为Pd。 Set of the present invention provides compositions for reducing the FCC regenerator flue gas CO and NO, emissions of the noble metal element is one or more of Pd, Ir, of the, preferably Pd.

[0022] 本发明所提供的用于降低催化裂化再生烟气CO和NOy排放的组合物中,所述无机氧化物载体选自氧化铅、沸石、尖晶石、高岭±、娃藻±、珍珠岩中的一种或几种,优选为氧化铅。 [0022] The compositions of the invention for reducing the FCC regenerator flue gas provided NOy and CO emissions, the inorganic oxide support is selected from lead oxide, zeolite, spinel, kaolin ±, baby ± algae, one or more of perlite, preferably lead oxide. 所述氧化铅选自拟薄水铅石、大孔活性氧化铅、铅溶胶中的一种或几种,优选为拟薄水铅石。 The lead oxide is selected from pseudoboehmite stone lead, lead oxide active macropores lead sol one or more, preferably pseudoboehmite plumbite.

[002引本发明所提供的用于降低催化裂化再生烟气CO和NOy排放的组合物还可含有W氧化物计不超过5重量%例如0. 1~5重量%的选自IB~VIIB族非稀±元素中的一种或几种的金属添加剂组分,通常所述的金属添加剂组分含量不超过2重量%,所述金属优选为1'1、2'、¥、化、10、胖和胞中的一种或几种,更优选所述金属添加剂组分为化的他合物,^ 所述组合物的重量为基准,W氧化物计,化的含量不超过2重量%例如为0. 2~2重量%。 [002 primer provided by the present invention for reducing the FCC regenerator flue gas emissions of CO and NOy W oxide compositions may also contain not more than 5 wt%, for example 0.1 to 5 wt% of at least a Group IB ~ VIIB non-dilute ± elements of one or several metal additive component is generally the metal content of the additive component not more than 2 wt%, the metal is preferably 1'1,2 ', ¥, of, 10, and fat cells of one or more, and more preferably the metal additive component of his compounds, ^ the weight of the composition as a reference, W oxide basis, of not more than 2 wt%, e.g. It is 0.2 to 2 wt%. 一种实施方式,所述用于降低催化裂化再生烟气CO和NOy排放的组合物,由W氧化物计: (1)0. 5 - 30重量%的稀±元素,(2)0.Ol- 0. 15重量%的贵金属元素,(3)0~5重量%的所述金属添加剂组分和(4)余量的基本不含碱金属和碱±金属的无机氧化物载体组成,进一步所述组合物由(1)W氧化物计2 - 29. 99重量%例如2 - 20重量%的稀±元素,(2) W单质计0.Ol- 0. 1重量%的贵金属元素,(3)W氧化物计70 - 97. 99重量%例如70 -95重量%的所述基本不含碱金属和碱±金属的无机氧化物载体和0~2重量%所述金属添加剂组分组成;更优选由;(1)5 - 15重量%的稀±元素,(2)0. 03 - 0. 08重量%的贵金属兀素,和(3)84. 2 - 94. 97重量%例如80 - 90重量%所述基本不含碱金属和碱±金属的无机氧化物载体和O~2重量%所述金属添加剂组分组成。 One embodiment, the FCC regenerator flue gas for reducing the emissions of CO and NOy composition, oxides of W: (1) 05--30 wt% of lean ± elements, (2) 0.Ol - 0.15% by weight of the noble metal element, (3) 0 to 5 wt% of the additive metal component and (4) the balance being substantially free of alkali and ± alkali metal inorganic oxide carrier composition, as further the composition of said meter (1) W oxide 2 - 29.99 wt%, for example, 2 - 20% by weight of the dilute ± elements, (2) W elemental basis 0.Ol- 0. 1 wt% of the noble metal element, (3 ) W oxides 70-- 97.99 wt% e.g. 70-95% by weight of the inorganic oxide support substantially free of alkali metals and alkali metals and 0 to ± 2% by weight of the metal additive constituents; more preferably the;. (1) 5 - 15% by weight of the dilute ± elements (2) 003-- 0.08 wt% Wu noble metal element, and (3) 842-- 94.97 wt% e.g. 80--90 % by weight of said alkali metal base and an alkali metal ± inorganic oxide support and said O ~ 2 wt% metal additive component.

[0024] 本发明提供的用于降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,所述稀±元素组分为铜系元素化合物的一种或几种,优选为Ce、La和Pr的化合物中的一种或几种,或是包括Ce、La和Pr中的一种或几种的化合物的混合稀±,更优选为Ce的化合物。 [0024] The present invention provides a method for preparing FCC regenerator flue gas emissions of CO and NOy composition decreases, the component element ± dilute copper compound one or several elements, preferably Ce, La Pr, and one or more compounds, comprising one or Ce, La and Pr or a mixture of several compounds of ± dilute, and more preferably is Ce compounds. 所述稀±元素优选通过在喷雾干燥前将稀±元素组分与氧化物载体组分混合成胶的方法负载于载体上。 The elements are preferably by ± diluted prior to spray drying and dilute ± elemental constituents mixed oxide support component synthetic methods supported on the carrier. 所述稀±元素组分可W通过含稀±元素化合物的固体或溶液方式与氧化物载体组分混合成胶,优选为化合物的溶液方式。 The component may dilute ± W mixed synthetic gums element by element-containing compound ± dilute solid solution or manner oxide support component, preferably a solution of compounds of.

[0025] 本发明提供的用于降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,所述的无机氧化物载体组分为所述的无机氧化物或无机氧化物前体。 [0025] A method for reducing the FCC regenerator flue gas emissions of CO and NOy compositions provided by the present invention, an oxide precursor of the inorganic oxide support component of the inorganic oxide or inorganic. 所述的无机氧化物例如氧化铅、尖晶石、高岭±、娃藻±、珍珠岩及其它常用粘±材料中的一种或几种,优选为氧化铅、高岭±、娃藻±、珍珠岩中的一种或几种,更优选为氧化铅。 The inorganic oxides such as lead oxide, spinel, kaolin ±, baby ± algae, perlite and other conventional adhesive materials ± one or more, preferably lead oxide, kaolin ±, baby alginate ± , one or more of perlite, more preferably lead oxide. 所述的无机氧化物前体为氧化铅前体中的一种或多种,所述氧化铅前体优选包括拟薄水铅石、大孔活性氧化铅中的一种或多种,或还包括铅溶胶,更优选,所述氧化铅前体为拟薄水铅石。 Inorganic oxide precursor prior to said one or more precursors of lead oxide, the lead oxide precursor preferably comprises pseudoboehmite plumbite, lead oxide active macropores one or more, or further sol including lead, and more preferably, the lead oxide precursor is pseudoboehmite plumbite. 所述拟薄水铅石优选在与稀±元素组分混合前进行酸化胶溶处理,酸化胶溶处理的方法为现有方法,例如可W 是将拟薄水铅石与水打浆形成氧化铅含量为5~45重量%的浆液,然后加入浓度为15~ 40重量%的无机酸水溶液,所述无机酸例如盐酸、硝酸、硫酸中之一种或多种,酸铅比(摩尔比)为0. 05~0. 5:1,优选为0. 08~0. 2:1。 The pseudoboehmite plumbite acidified peptization is preferably treated before mixing with the elemental constituents ± dilute, acidified peptization treatment method is a conventional method, for example W is a pseudoboehmite plumbite oxide with water to form lead beaten content of 5 to 45% by weight of the slurry, and then added at a concentration of 15 to 40% by weight of an aqueous solution of a mineral acid, a mineral acid such as hydrochloric acid, nitric acid, sulfuric acid or more of, lead acid ratio (molar ratio) 0.05 ~ 05: 1, preferably 0.08 ~ 02: 1.

[0026] 本发明提供的降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,所述金属添加剂组分为选自IB~VIIB族非稀±元素中的一种或几种的金属元素,W所述组合物的重量为基准,W氧化物计,所述金属添加剂组分的含量不超过5重量%。 [0026] A method to reduce FCC regenerator flue gas emissions of CO and NOy compositions provided by the present invention, the additive component is one metal selected from Group IB ~ VIIB elements ± non-thinned or more metal weight elements, W of the composition as a reference, W oxides, the metal content of the additive component is not more than 5 wt%. 所述金属添加剂组分优选为Ti、Zr、V、化、Mo、W和Mn中的一种或几种,更优选所述金属添加剂组分为化, W所述组合物的重量为基准,W氧化物计,化的含量不超过2重量%。 The metal additive component is preferably Ti, Zr, V, of, one or more of Mo, W and Mn, and more preferably the metal additive component of the weight W of the composition as a reference, the content of W oxide basis, of not more than 2 wt%. 当所述的组合物中含有金属添加剂组分时,所述金属添加剂可W采用浸溃法负载于喷雾成型的载体颗粒上, 也可采用在喷雾干燥前与载体组分混合成胶的方法负载。 When the additive composition contains a metal component, the metal additive may load W method impregnation method supported on the carrier particle spray molding, may be employed with a carrier prior to spray drying the synthetic rubber component blended . 优选在所述金属添加剂组分贵金属之前引入到载体上;更优选,所述金属添加剂组分在喷雾干燥前与载体组分混合形成浆液或胶体然后喷雾干燥;更更优选在稀±元素组分加入后加入所述的金属添加剂组分与载体组分混合成胶,例如先将稀±元素组分与载体组分混合成胶,然后加入所述的金属添加剂组分然后喷雾干燥。 Preferably before the metal additive is introduced into a noble metal component on the support; more preferably, the additive metal component and the carrier component to form a slurry before spray-drying or colloidal then spray dried; still more preferably ± dilute element component was added after the addition of the metal additive component with the carrier component mixed synthetic gums, e.g. ± first dilute component to the carrier component elements blended synthetic gums, followed by addition of the additive metal component and then spray dried.

[0027] 本发明所提供的用于降低催化裂化再生烟气CO和NOy排放的组合物制备方法中, 所述贵金属元素为Pt Ir、化中的一种或几种,优选为PcL所述贵金属元素优选通过含贵金属组分的可溶性盐溶液负载于氧化物载体上。 [0027] preparing a composition NOy FCC regenerator flue gas emissions of CO and the present invention is provided for reducing in the noble metal element is Pt Ir, of one or several, preferably the noble metal is PcL element is preferably supported on the oxide carrier solution containing a soluble salt of the precious metal component. 所述含贵金属组分的可溶性盐溶液可W在喷雾干燥前加入到氧化物载体组分中,也可在氧化物载体经喷雾干燥成型一赔烧后采用浸溃的方法负载。 Soluble salt solution containing the noble metal component may be added to the W oxide support component prior to spray drying, can also be supported on an oxide support formed by spray drying the impregnated using a compensation method for burning. 优选将含贵金属组分的可溶性盐溶液采用浸溃的方法负载于经喷雾干燥成型一赔烧后氧化物载体上。 Soluble salt solution containing the precious metal component is preferably impregnated using the method of spray-dried supported compensates burning after forming the oxide carrier. 所述浸溃的方法可W是饱和浸溃,也可W是过量浸溃,优选为过量浸溃。 The dipping method may be saturated dipping W, W may be impregnated in excess, preferably an excess of impregnated. 优选,浸溃时,所述贵金属溶液的体积为载体孔体积的1. 5 - 15倍,例如所述贵金属溶液的体积为载体孔体积的5 - 10倍。 Preferably, when the dipping, the volume of the solution of noble metal pore volume 1.5 - A 15 times, for example, the volume of the noble metal solution pore volume is 5 - A 10-fold.

[002引本发明提供的用于降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,所述氧化物载体负载贵金属元素后采用碱性溶液进行处理。 [002 primers of the present invention provides a method for preparing FCC regenerator flue gas emissions of CO and NOy composition decreases the oxide carrier supporting the noble metal element is processed using an alkaline solution. 所述碱性溶液优选非金属元素碱性溶液。 The alkaline solution is an alkaline solution is preferably non-metallic elements. 所述非金属元素碱性溶液优选为氨水和碱性倭盐溶液,所述碱性倭盐例如碳酸倭、 碳酸氨倭、磯酸氨二倭。 The non-metal element and the alkaline solution is preferably an aqueous ammonia solution of basic Japanese salts, e.g. salts of the basic Japanese Japanese carbonate, ammonium carbonate, Japanese, Japanese Rocky iminodiacetic acid. 所述非贵金属元素碱性溶液更优选为氨水。 The non-noble metal element of the alkaline solution is more preferably aqueous ammonia. 所述碱性溶液处理方法可W将负载贵金属元素后的组合物在碱性溶液中打浆接触,或者采用碱性溶液淋洗负载贵金属元素后的组合物。 The alkaline solution treatment may load W after beating noble metal element composition in contact with an alkaline solution or alkaline solution composition after rinsing supported noble metal element. 所述碱性溶液处理后的组合物经过滤、干燥和/或赔烧处理。 After the alkaline solution treatment composition was filtered, dried and / or burning treatment to lose. 所述碱性溶液的体积为组合物孔体积的1 - 10倍,优选为1. 5 - 5倍。 Volume of the alkaline solution composition of the pore volume of 1 - A 10-fold, preferably to 1. 5 - 5 times. 所述碱性溶液的浓度(指碱性溶液中非贵金属元素化合物的浓度,例如为氨水时是指氨的浓度,为碱性倭盐溶液时, 是指碱性倭盐的浓度)为0.Ol-lOmol/l,优选0. 05 - 5mol/l,更优选为0. 5 - 2mol/L0 所述处理的为将负载贵金属的组合物与碱性溶液接触,接触时间为《60min例如2~59分钟,优选为5 - 20min,温度没有特殊要求,例如可W为0~IOCTC,通常室温(15~4(TC) 下操作即可。 The concentration of the alkaline solution (the concentration refers to the noble metal element compound Africa alkaline solution, for example, when ammonia is the concentration of ammonia, Japanese salt solution is alkaline, alkaline Japanese refers to the concentration of salt) is 0. Ol-lOmol / l, preferably 0. 05 - 5mol / l, more preferably 0. 5 - 2mol / L0 of the process of the noble metal composition is contacted with an alkaline solution, a contact time of "60min ~ 2 e.g. 59 minutes, preferably 5 - 20min, temperature no special requirements, for example, W is 0 ~ IOCTC, usually operating at room temperature to (15 ~ 4 (TC).

[0029] 本发明提供的降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,所述的喷雾干燥可采用现有方法,其中喷雾干燥得到的颗粒的粒度分布与现有催化裂化催化剂相比没有特殊要求。 [0029] A method to reduce FCC regenerator flue gas emissions of CO and NOy compositions provided by the invention, the conventional spray drying method may be employed, wherein the particle size of the granules obtained by spray drying with the conventional catalytic cracking catalyst distribution no special requirements compared. 通常其平均粒径为60 - 75微米,粒径分布范围主要在20 - 149微米, 其中粒径为40 - 80微米的一般占50%W上。 Typically an average particle size 60--75 microns, a particle size distribution mainly in the range of 20--149 microns, wherein particle diameters of 40 - General account the 50% W 80 microns.

[0030] 本发明提供的用于降低催化裂化再生烟气CO和NOy排放的组合物的制备方法,一种优选的施方式,包括如下步骤: [0030] The present invention provides a method for preparing FCC regenerator flue gas emissions of CO and NOy composition is reduced, a preferred embodiment is applied, comprising the steps of:

[0031] (1)将拟薄水铅石与水打浆,加酸酸化,加入稀±化合物溶液,任选加入金属添加组分;其中酸化的酸铅比(摩尔比)为0.05~0.5:1,优选为0.08~0.2:1; [0031] (1) The lead pseudoboehmite beating stone and water, add a sprig, ± diluted compound solution was added, optionally adding a metal component is added; Lead acidified wherein ratio (molar ratio) of 0.05 to 0.5: 1 , preferably 0.08 to 0.2: 1;

[0032] (2)将步骤(1)得到的浆液喷雾干燥;得到载体颗粒; [0032] (2) The step (1) to give the spray-drying a slurry; to give support particles;

[003引做步骤似得到的载体颗粒浸溃贵金属化合物浪溃时间优选5 - 20min; [003 carrier particles do primers obtained in step-like wave of precious metal compound crushed dipping time is preferably 5 - 20min;

[0034] (4)步骤(3)得到的浸溃贵金属化合物后的颗粒与氨水接触进行处理,干燥、赔烧。 Obtained [0034] (4) Step (3) the particles are impregnated with ammonia noble metal compound after contacting treatment, drying, burning lost.

[0035] 本发明提供的流化催化裂化方法,包括将姪油与催化剂接触反应和再生的步骤, 其中,W所述催化剂的总重量为基准,所述催化剂中本发明提供的降低催化裂化再生烟气CO和NOx排放组合物的含量为0. 05 - 5重量%,优选为0. 1 - 1. 5重量%。 [0035] The fluid catalytic cracking process provided by the present invention, comprising the step of contacting the oil and the catalyst nephew reaction and regeneration, wherein the total weight W of the catalyst as a reference, the present invention provides a catalyst FCC regenerator reduced CO and NOx emissions content of the flue gas composition 0. 05--5% by weight, preferably 0. 1-- 1.5 wt%. 所述本发明提供的降低催化裂化再生烟气CO和NOy排放组合物可W是一种独立的颗粒或是作为裂化催化剂颗粒整体的一部分,优选为一种独立的颗粒。 The present invention provides a reduction in FCC regenerator flue gas emissions of CO and NOy W is a composition may be individual particles or as integral part of the cracking catalyst particles, is preferably an independent particle. 即本发明所述催化剂中含有本发明提供的降低催化裂化再生烟气CO和NOy排放组合物和裂化活性组分,本发明提供的降低催化裂化再生烟气CO和NOy排放组合物和裂化活性组分可W处于相同的颗粒中也可W处于不同的颗粒中。 I.e., the catalyst of the present invention contains the present invention provides a FCC regenerator flue gas to reduce emissions of CO and NOy cracking compositions and the active ingredient, the present invention provides a reduction in FCC regenerator flue gas emissions of CO and NOy cracking compositions and the active ingredient W may be divided in the same particles may also be in different W particles. 优选,本发明提供的降低催化裂化再生烟气CO和NOy排放组合物和裂化活性组分处于不同的颗粒中,即本发明所述催化剂中包括所述的降低催化裂化再生烟气CO和NOy 排放组合物颗粒和催化裂化催化剂颗粒,所述的催化裂化催化剂为现有催化裂化催化剂中的一种或几种,可W商购或者按照现有方法制备。 Preferably, the present invention provides a reduction in FCC regenerator flue gas emissions of CO and NOy cracking compositions and the active ingredient in different particles, i.e. the catalyst according to the present invention include reducing FCC regenerator flue gas emissions of CO and NOy composition particles and FCC catalyst particles, the conventional catalytic cracking catalyst is a catalytic cracking catalyst in one or more of, W may be commercially available or prepared according to a conventional method.

[0036] 本发明所述流化催化裂化方法中,所述催化剂再生的方法与现有再生方法相比没有特殊要求,包括部分再生、不完全再生和完全再生操作模式。 The [0036] fluid catalytic cracking process of the present invention, the regenerated catalyst compared with the conventional method is not required special reproducing method, comprising a partial regeneration, and complete regeneration incomplete regeneration operation mode. 所述再生方法可参见陈俊武主编,中国石化出版社2005年出版的《催化裂化工艺与工程》第1234页一1343页。 The regeneration method can be found in Chen Junwu editor of China Petrochemical Press in 2005 published "catalytic cracking technology and engineering" on page 1234 a 1343. 优选再生温度为65(TC- 73(TC。所述姪油为流化催化裂化常用的姪油,例如减压瓦斯油、常压渣油、减压渣油、脱渐青油、焦化蜡油或加氨处理油。 The regeneration temperature is preferably 65 (TC- 73 (TC. The oil is a nephew conventional fluidized catalytic cracking nephew oils, such as vacuum gas oils, atmospheric residues, vacuum residues, cyan gradually de-oil, coker gas oil ammonia or process oil.

[0037] 下面的实施例将对本发明予W进一步的说明,但并不因此而限制本发明。 [0037] The following examples of the present invention will be further described W, but does not thereby limit the present invention. 实施例和对比例中所用原料;硝酸饰[Ce(N03)3• 6&0]为分析纯,国药集团化学试剂有限公司生产;氯化铅(PdCLz)为分析纯,Pd含量> 59. 5% (含量单位未说明的,均为重量百分含量), 有研亿金新材料股份有限公司生产;硝酸館[化(N03)3,9H20]为分析纯,北京益利精细化学品有限公司生产;碳酸钢为分析纯,北京益利精细化学品有限公司生产;Y-Alz化微球粒径范围20 - 120微米,孔体积0. 36毫升/克(120°C烘干后孔体积0. 50毫升/克),不计水分氧化铅含量99. 5% (固含量95. 5% ),山东铅业公司生产;拟薄水铅石为工业级产品,氧化铅含量61重量%,孔体积为0. 31毫升/克,山东铅业公司生产;盐酸,浓度为36. 5重量%, 分析纯,北京化工厂生产;氨水,浓度为25 - 28%,分析纯,北京化工厂生产,稀释后使用; 催化裂化催化剂工业产品(商品牌号GOR-II,本发明中记为Cat-A) Examples and comparative materials used; decorative nitrate [Ce (N03) 3 • 6 & 0] AR grade, Sinopharm Chemical Reagent Co., Ltd.; lead chloride (PdCLz) of analytically pure, Pd content> 59.5% ( content per unit unspecified, are weight percent), there is research Billion in new material Co. production; Hall nitrate [of (N03) 3,9H20] were of analytical grade, Beijing Yili fine chemical Co., Ltd.; carbonate, analytical grade steel, Beijing Yili fine Chemicals Co., Ltd.; Y-Alz microsphere diameter range 20 - 120 microns, pore volume 0.36 ml / g (pore volume after baking 120 ° C 0.50 ml / g), excluding moisture lead oxide content of 99.5% (solids content 95.5%), produced by Shandong lead industry; pseudoboehmite plumbite for industrial products, lead oxide content of 61 wt%, a pore volume of 0 31 ml / g, produced by Shandong lead industry; hydrochloric acid at a concentration of 36.5 wt%, analytically pure, Beijing chemical Plant; ammonia concentration of 25--28%, analytically pure, Beijing chemical Plant, after dilution ; catalytic cracking catalysts of industrial products (trade designation GOR-II, the present invention is referred to as Cat-A) 胞2〇含量0.24%, RE2O3含量3.2%,Al2〇3含量48.0%,平均粒径67微米,中国石化催化剂有限公司生产。 2〇 cell content of 0.24%, RE2O3 content of 3.2%, Al2〇3 content of 48.0%, an average particle size of 67 microns, China Petrochemical Co catalyst.

[0038] 实施例1 [0038] Example 1

[0039] 本实施例说明本发明所述用于降低FCC再生烟气CO和NOy排放组合物Sl的制备。 [0039] This example illustrates the preparation of the FCC regenerator flue gas emissions of CO and NOy Sl composition of the present invention for reducing.

[0040] 称取4kg拟薄水铅石,加入到16kg去离子水中打浆分散,加入250血盐酸酸化20min后,加入WCe〇2计质量含量为240g/L的硝酸饰溶液1136血打浆分散,随后加入W 化2〇3计质量含量为57g/L的硝酸館溶液239mL继续打浆,喷雾干燥,60(TC赔烧比,得到组合物载体Ml。称取100g(按干基重量计)载体Ml,加入到400血水中,加入WPdO计质量含量为12. 5g/L的PdClz溶液4.SmU揽拌20min,过滤得到浸溃贵金属后的组合物滤饼,用浓度为2mol/L的氨水溶液SOmL淋洗滤饼,干燥,得到本发明所述组合物,记为Sl(其中Ce化含量10%质量,化2化含量0. 5%质量,PdO含量0. 06%质量)。 [0040] 4kg weighed after pseudoboehmite plumbite, added to 16kg of deionized water and dispersed beating, blood acidified with hydrochloric acid was added 250 20min, counted added WCe〇2 mass content of 240g / L nitric acid solution 1136 ornaments blood beating dispersion, followed by was added W content of 2〇3 count mass 57g / L 239mL museum nitrate solution continued beating, spray-drying, 60 (TC lose than burning, to give a carrier composition Ml. weighed 100g (dry weight basis) of Ml carriers, 400 was added to the blood, the amount of mass added WPdO meter 12. 5g / L solution of PdClz 4.SmU embrace stirred 20min, filtered to obtain a composition cake after dipping the noble metal, at a concentration of 2mol / L aqueous solution of ammonia leaching SOmL the filter cake was washed and dried to obtain the composition of the invention, referred to as Sl is (where Ce content of 10% by mass, of the content of 0.06% 2 0.5% by mass, the content by mass of PdO).

[00川实施例2 [Example 2 00 Chuan

[0042] 本实施例说明本发明所述降低FCC再生烟气CO和NO,排放组合物S2的制备。 [0042] This example illustrates the preparation of the present invention is to reduce the flue gas CO and NO, emissions S2 composition of the FCC regenerator.

[0043] 称取4kg拟薄水铅石,加入到16kg去离子水中打浆分散,加入250血盐酸酸化20min后,加入质量含量(WCe化计)为240g/L的硝酸饰溶液1386mL打浆分散,喷雾干燥,60(TC赔烧比,得到组合物载体M2。称取100g(按干基重量计)载体M2,加入到500血水中,加入质量含量(WPdO计)为12. 5g/L的PdClz溶液4.8血,揽拌20min,过滤得到浸溃贵金属后的组合物滤饼,用浓度为2mol/L的氨水溶液IOOmL淋洗滤饼,滤饼经40(TC赔烧2h,得到本发明所述组合物S2(其中Ce〇2含量12质量% ,PdO含量0.06质量% )。 [0043] Weigh 4kg after pseudoboehmite plumbite, added to 16kg of deionized beating dispersed in water, was added 250 blood acidified with HCl 20min, added mass content (WCE of count) of 240g / L decorative nitrate solution 1386mL beating dispersed spray dried, 60 (TC lose than burning, to give a carrier composition M2. weighed 100g (dry weight basis) vector M2, blood was added to 500 added mass content (WPdO basis) was 12. 5g / L solution of PdClz 4.8 blood, embrace stirred 20min, filtered to obtain a composition cake after dipping the noble metal, at a concentration of 2mol / L aqueous solution of ammonia IOOmL rinsed filter cake was 40 (TC lose burning 2h, to obtain the composition of the present invention were S2 (wherein the content of 12 mass% Ce〇2, PdO content of 0.06% by mass).

[0044] 实施例3 [0044] Example 3

[0045] 本实施例说明本发明所述降低FCC再生烟气CO和NO,排放组合物S3的制备。 [0045] This example illustrates the preparation of the present invention, the FCC regenerator flue gas CO and NO, emissions of the reduced composition S3.

[0046] 称取4kg拟薄水铅石,加入到16kg去离子水中打浆分散,加入250血盐酸酸化20min后,加入Ce〇2质量含量为240g/L的硝酸饰溶液1815mL打浆分散,喷雾干燥,60(TC赔烧比,得到组合物载体M3。称取100g(按干基重量计)载体M3,加入到350血水中,加入PdO质量含量为12. 5g/L的PdClz溶液4mL,揽拌20min,过滤得到浸溃贵金属后的组合物滤饼,用浓度为2mol/L的氨水溶液IOOmL淋洗滤饼,滤饼经40(TC赔烧化,得到本发明所述组合物S3 (其中Ce〇2含量15质量% ,PdO含量0.05质量% )。 [0046] 4kg weighed pseudoboehmite plumbite, was added to the deionized water dispersion 16kg beating, blood acidified by adding hydrochloric acid 250 20min, added Ce〇2 mass content of 240g / L of nitric acid solution of 1815mL decorative beating dispersion, spray-drying, 60 (TC lose than burning, to give a carrier composition M3. weighed 100g (dry weight basis) vector M3, blood was added to 350, the mass content of PdO was added 12. 5g / L solution of PdClz 4 mL, mix embrace 20min the composition of the filter cake obtained after dipping the noble metal, at a concentration of 2mol / L aqueous solution of ammonia IOOmL rinsed filter cake was 40 (TC compensation burnt, to obtain the composition of the present invention S3 (wherein Ce〇2 content of 15 mass%, PdO content of 0.05% by mass).

[0047] 实施例4 [0047] Example 4

[0048] 本实施例说明本发明所述降低FCC再生烟气CO和NO,排放组合物S4的制备。 [0048] This example illustrates the preparation of the present invention is to reduce the flue gas CO and NO, emissions S4 composition of the FCC regenerator.

[0049] 称取4kg拟薄水铅石,加入到16kg去离子水中打浆分散,加入250血盐酸酸化20min后,加入Ce〇2质量含量为240g/L的硝酸饰溶液894血打浆分散,随后加入化2〇3质量含量为57g/L的硝酸館溶液470mL继续打浆,喷雾干燥,60(TC赔烧比,得到组合物载体M4。称取100g(按干基重量计)载体M4,加入到400血水中,加入PdO质量含量为12. 5g/L的PdClz溶液5. 揽拌20min,过滤得到浸溃贵金属后的组合物滤饼,用浓度为2mol/ L的氨水溶液120mL淋洗滤饼,干燥,得到本发明所述组合物S4 (其中Ce化含量8质量%, 化2〇3含量1质量%,PdO含量0. 065质量% )。 [0049] 4kg weighed after pseudoboehmite plumbite, added to 16kg of deionized water and dispersed beating, blood acidified with hydrochloric acid was added 250 20min, added Ce〇2 mass content of 240g / L of nitric acid solution of 894 blood beating decorative dispersed, followed by addition of 2〇3 mass content of 57g / L 470mL museum nitrate solution continued beating, spray-drying, 60 (TC lose than burning, to give a carrier composition M4. weighed 100g (dry weight basis) vector M4, was added to 400 blood was added mass PdO content of 12. 5g / L solution of PdClz 5. embrace stirred 20min, filtered to obtain a composition cake after dipping the noble metal, at a concentration of 2mol / L aqueous ammonia solution 120mL cake was rinsed, dried to give the composition of the present invention, S4 (wherein the Ce content of 8% by mass, the content of 2〇3 1% by mass, of PdO content of 0.065% by mass).

[0050] 对比例1 [0050] Comparative Example 1

[0051] 本实施例说明本发明所述对比组合物CSl的制备。 [0051] The present embodiment of the present invention were prepared comparative compositions CSl FIG.

[0052] 参照实施例2方法制备对比组合物,只是浸溃贵金属后不采用氨水处理。 [0052] Referring to Comparative Example 2 process for preparing a composition embodiment, except not using a noble metal impregnated ammonia treatment. 称取4kg 拟薄水铅石,加入到16kg去离子水中打浆分散,加入250mL盐酸酸化20min后,加入质量含量(WCe化计)为240g/L的硝酸饰溶液1386血打浆分散,喷雾干燥,60(TC赔烧比,得到组合物载体CMl。称取100g(按干基重量计)载体CMl,加入到500血水中,加入质量含量(WPdO计)为12. 5g/L的PdClz溶液4.SmU揽拌20min,过滤得到浸溃贵金属后的组合物滤饼,滤饼经40(TC赔烧化,得到本发明所述组合物CSl(其中Ce〇2含量12质量%,PdO含量0.06质量% )。 After weighing 4kg pseudoboehmite plumbite, added to 16kg of deionized beating dispersed in water, was added 250mL of hydrochloric acid was acidified 20min, added mass content (WCE of count) of 240g / L of nitrate ornaments solution 1386 blood beating dispersion, spray-drying, 60 (TC lose than burning, to give a carrier composition CMl. weighed 100g (dry weight basis) vector CMl, 500 blood was added to added mass content (WPdO basis) was 12. 5g / L solution of PdClz 4.SmU embrace stirred 20min, filtered to obtain the composition after dipping noble metal cake, filter cake 40 (TC compensation burnt, to obtain the composition CSl the present invention (wherein the content of 12 mass% Ce〇2, of PdO content of 0.06% by mass).

[00閲对比例2 [00 reading Comparative Example 2

[0054] 本实施例说明本发明所述对比组合物CS2的制备。 The preparation of the present invention, the comparative composition CS2 [0054] This example illustrates.

[00巧]采用活性组分浸溃Y-AI2O3微球的方法制备对比组合物(稀±元素通过浸溃的方法负载于微球载体上),组合物中不加入金属添加剂组分化,且浸溃贵金属后不采用氨水处理。 [00 Qiao] The active ingredient impregnated Y-AI2O3 microsphere method of preparing a comparative composition (dilute ± impregnated elements by means of a load on a microsphere carrier) in the composition group metal additive was not added differentiation, and dip ammonia treatment without using a noble metal collapse. 称取Y-Al2〇3微球样品92.地烘干,量取Ce〇2质量含量为240g/L的硝酸饰溶液50mL 加入到烘干的Y-AI2O3微球样品中,揽拌均匀后,烘干,60(TC赔烧比,得到对比组合物载体CM2。取PdO质量含量为12. 5g/L的PdClz溶液4. 8血,用水稀释到总体积为48血后加入到载体CM2中,揽拌均匀后,烘干,得到本发明所述对比组合物CS2 (其中Ce化含量12%,PdO 含量0. 06% )。 Y-weighed sample of microspheres 92. Al2〇3 to dry, weighed Ce〇2 mass content of 240g / L of nitric acid was added to a 50mL solution decorative dried Y-AI2O3 microsphere sample, mix uniformly embrace, drying, after 60 (TC compensation than burning to obtain comparative composition carrier CM2. take PdO content of mass 12. 5g / L of a solution of 4.8 PdClz blood, diluted with water to a total volume of blood added to the support 48 in the CM2, after embrace mix evenly, drying to obtain a comparative composition according to the present invention CS2 (wherein the Ce content of 12%, PdO content of 0.06%).

[005引对比例3 [Comparative Example 3 005 primer

[0057] 按照现有技术制备对比组合物CS3,活性组分配比同对比例1,不同的是组合物制备过程中还引入的碱金属化。 [0057] was prepared according to the prior art comparative composition CS3, the distribution ratio of the active ingredient with Comparative Example 1, except that the preparation of the alkali metal composition during further introduced.

[005引称取4kg拟薄水铅石,加入到16kg去离子水中打浆分散,加入250血盐酸酸化20min后,加入质量含量(WCe化计)为240g/L的硝酸饰溶液1410血打浆分散,再加入72. 3g碳酸钢打浆分散,喷雾干燥,60(TC赔烧比,得到组合物载体CM3。称取100g(按干基重量计)载体CM3,加入到500血水中,加入质量含量(WPdO计)为12. 5g/L的PdClz溶液4.SmU揽拌20min,过滤得到浸溃贵金属后的组合物滤饼,滤饼经40(TC赔烧化,得到本发明所述组合物CS3(其中Ce02含量12质量%,NazO含量1.5% ,PdO含量0.06质量% )。 [005 cited weighed 4kg pseudoboehmite plumbite, was added to the beating 16kg of deionized water dispersion, acidified by adding 250 blood hydrochloric after 20min, was added mass content (WCE of count) of 240g / L of nitrate ornaments solution 1410 blood beating dispersion, 72. 3g carbonate added steel beating dispersion, spray-drying, 60 (TC lose than burning, to give a carrier composition CM3. weighed 100g (dry weight basis) carrier CM3, 500 blood was added to added mass content (WPdO basis) of 12. 5g / L solution of PdClz 4.SmU embrace stirred 20min, filtered to obtain the composition after dipping noble metal cake, filter cake 40 (TC compensation burnt, to obtain the composition of the present invention CS3 (wherein Ce02 content of 12% by mass, nazO content of 1.5%, PdO content of 0.06% by mass).

[0059] 下面的实施例和对比例,说明本发明提供的组合物和对比组合物助剂,对再生烟气NOy、CO排放及FCC产品分布的影响。 [0059] The following examples and comparative examples illustrate the present invention provides compositions and comparative compositions affecting additives, regenerated flue NOy, CO emissions and FCC product distribution.

[0060] 将本发明提供的助剂组合物(或对比组合物)按一定比例(占催化剂总藏量的0. 6 - 0. 9重量% )加入到主催化剂(Cat-A)中,渗混均匀后,经80(TC、100%水蒸汽气氛下老化12小时后进行催化裂化反应一再生评价。 [0060] The present invention provides an adjuvant composition (or a comparative composition) by a certain percentage (the total storage amount of the catalyst 0.6 - 0. 9 wt%) was added to the main catalyst (Cat-A), retentate after uniformly mixed, dried 80 (TC, 100% steam cracking reaction was carried out 12 hours after the evaluation of a reproduction aging atmosphere.

[0061] 实施例5 - 8和对比例4 - 6中,均采用小型固定流化床装置进行反应一再生评价,催化剂总装量9g,反应温度为50(TC,剂/油比为5,原料油性质见表1。气体产物通过在线色谱分析得到裂化气体组成;液体产物进行离线色谱分析得到汽油、柴油和重油产率; 采用空气在线烧焦再生,根据C〇2红外分析仪积分计算焦炭产率,所有产物收率归一后得出FCC产品分布。反应后经成汽提lOmin,进行原位烧焦再生,再生空气流量为200mL/min,再生时间15min,再生初始温度同反应温度,最高温度685C。收集再生过程中的烟气,再生结束后采用Testo350Pro烟气分析仪测定烟气中NOx和CO的浓度。 [0061] Example 5 - 8 and Comparative Example 4--6, the means are used in a fixed fluidized bed reaction was carried out a regeneration evaluation, the amount of the catalyst assembly 9g, the reaction temperature was 50 (TC, catalyst / oil ratio of 5, the raw material Table 1. properties of the gas oil composition of the product obtained by chromatographic analysis of the cracked gas line; off-line liquid product was chromatographed to give gasoline, diesel oil and heavy oil yield; using air line burning regeneration, the coke yield is calculated according to the integral infrared analyzer C〇2 rate, all the products obtained after FCC yields a normalized product distribution. after the reaction was stripped to lOmin, in-situ burning regeneration, the regeneration air flow rate of 200mL / min, regeneration time 15min, the reaction temperature regeneration with the initial temperature, maximum 685C temperature. collect the flue gas during the regeneration, the regeneration gas analyzer Testo350Pro end use concentration of NOx and CO in the flue gas was measured.

[0062] 实施例5 _ 8 [0062] Example 5 _ 8

[0063] 本组实施例说加入本发明提供的组合物Sl - S4对再生烟气N〇x、CO排放及FCC产品分布的影响。 [0063] Example embodiments of the present group of said added to the compositions of the present invention provides Sl - S4 Effect N〇x regeneration flue gas, CO emissions and FCC product distribution.

[0064] 其中,组合物Sl-S4占催化剂总藏量的比例分比为0. 6重量%、0. 8重量%、0. 8 重量%和0. 6重量%。 Ratio [0064] wherein the composition Sl-S4 of the total catalyst inventory of the division ratio is 0.6 wt%, 0.8 wt%, 0.8 wt% and 0.6 wt%.

[0065] 再生烟气中污染物排放检测结果及FCC产品分布列于表2。 [0065] The regeneration flue gas emissions and the detection result of FCC product distribution are listed in Table 2.

[0066] 对比例4 _ 6 [0066] Comparative Example 4 _ 6

[0067] 本对比例说明加入对比组合物CS1、CS2和CS3对再生烟气N〇x、CO排放及FCC产品分布的影响。 [0067] This comparative example illustrates a comparative composition added CS1, CS2 and CS3 impact N〇x regeneration flue gas, CO emissions and FCC product distribution.

[006引其中,对比组合物CS1、CS2和CS3占催化剂总藏量的比例均为0. 9重量% [Wherein lead 006, comparative compositions CS1, CS2, and the proportion of the total storage amount of the catalyst CS3 are accounted for 0.9 wt%

[0069] 再生烟气中污染物排放检测结果及FCC产品分布也列于表2。 [0069] The regeneration flue gas emissions and the detection result of FCC product distribution are also shown in Table 2.

[0070] 表1 [0070] TABLE 1

Figure CN105363444AD00111

[007引表2 [Table 2 Primer 007

Figure CN105363444AD00121

[0074] 由表2可见,本发明提供的降低CO和NOx排放助剂组合物,用于催化裂化过程,与现有技术制备的助剂(对比组合物)相比较,可W在用量更低的情况下,达到更高的CO助燃活性,同时对再生烟气中NOx催化转化活性有明显提高。 [0074] seen from Table 2, the present invention provides a reduced CO and NOx emissions aid composition for the catalytic cracking process, compared with the aid of prior art prepared (comparative composition), the amount of W can be less in the case where, to achieve higher CO combustion activity while regeneration flue gas NOx catalytic conversion activity has significantly increased.

Claims (24)

  1. 1. 一种用于催化裂化过程降低FCC再生烟气CO和NOx排放的助剂组合物,以所述组合物的重量为基准,含有以氧化物计:(1)0. 5 - 30重量%的稀土元素,(2)0. 01 - 0. 15重量%的贵金属元素,和(3)平衡量的基本不含碱金属和碱土金属的无机氧化物载体,所述组合物中引入贵金属元素后,在干燥和/或焙烧前经碱性溶液处理。 A catalytic cracking process for reducing the FCC regenerator flue gas composition comprising CO and aid NOx emissions, by weight of the composition as a reference, containing an oxide basis: (1) 05--30 wt% after the introduction of 0.15 wt% precious metal elements of noble metal elements, and (3) the balance being substantially free of alkali metals and alkaline earth metals of inorganic oxide support, the composition - a rare earth element, (2) 001. before drying and / or calcination treatment by an alkaline solution.
  2. 2. 按照权利要求1所述的组合物,其特征在于,所述贵金属元素采用浸渍的方法负载于氧化物载体上,且负载贵金属后的组合物在干燥和/或焙烧前经碱性溶液处理。 2. The composition according to claim 1, wherein said noble metal element after the impregnation method supported on the oxide carrier and a noble metal composition prior to drying and / or calcining the alkaline solution treatment .
  3. 3. 按照权利要求1所述的组合物,其特征在于,所述组合物含有以氧化物计:(1) 2 - 29. 99重量%的稀土元素,(2)0. 01 - 0. 1重量%的贵金属元素,和(3)70 - 97. 99重量% 的基本不含碱金属和碱土金属的无机氧化物载体。 3. The composition according to claim 1, wherein the composition contains an oxide basis: (1) 2 - 29.99 wt% of a rare earth element, (2) 001-- 0.1 wt% of the noble metal element, and (3) 70-- 97.99% by weight of inorganic oxide support substantially free of alkali metals and alkaline earth metals.
  4. 4. 按照权利要求3所述的组合物,其特征在于,所述组合物含有以氧化物计:(1)5 - 15重量%的稀土元素,(2) 0. 03 - 0. 08重量%的贵金属元素,和(3) 84. 92 - 94. 97重量% 的基本不含碱金属和碱土金属的无机氧化物载体。 4. The composition according to claim 3, wherein said composition contains an oxide basis: (1) 5 - 15 wt% of a rare earth element, (2) 0. 03 - 0.08 wt% noble metal element, and (3) 84. 92-- substantially 94.97% by weight of alkali metal and alkaline earth metal inorganic oxide support.
  5. 5. 按照权利要求1所述的组合物,其特征在于,所述稀土元素为Ce、La和Pr中的一种或几种或包含上述元素的至少一种。 5. The composition according to claim 1, wherein said rare earth element is Ce, La and Pr of one or more or comprising at least one of the above elements.
  6. 6. 按照权利要求1所述的组合物,其特征在于,所述贵金属元素为Pd、Ir、Rh中的一种或几种。 6. The composition according to claim 1, wherein said noble metal element is Pd, Ir, Rh one or several.
  7. 7. 按照权利要求1所述的组合物,其特征在于,所述无机氧化物载体选自氧化铝、沸石、尖晶石、高岭土、硅藻土、珍珠岩中的一种或几种。 7. The composition according to claim 1, wherein said inorganic oxide support selected from alumina, one or more of zeolite, spinel, kaolin, diatomaceous earth, perlite.
  8. 8. 按照权利要求1~7任一所述的组合物,其特征在于,所述组合物还含有以氧化物计不超过5重量%的选自IB~VIIB族非稀土元素中的一种或几种的金属添加剂组分。 8. The composition of claim any one of claims 1 to 7, characterized in that said composition further contains not more than one kind of oxides selected from 5% by weight of a Group IB ~ VIIB or non-rare-earth elements several metal additive component.
  9. 9. 按照权利要求8所述的组合物,其特征在于,所述金属添加剂组分为Cr;以所述组合物的重量为基准,以氧化物计,Cr的含量不超过2重量%。 9. The composition according to claim 8, wherein said additive metal component of Cr; the weight of the composition as a reference, in terms of oxide, Cr content of not more than 2 wt%.
  10. 10. 按照权利要求2所述的组合物,其特征在于,所述组合物的制备方法包括将所述基本不含碱金属和碱土金属的无机氧化物载体组分和稀土元素组分形成浆液、喷雾干燥、焙烧,浸渍贵金属元素、采用碱性溶液处理及干燥和/或焙烧的步骤。 10. The composition according to claim 2, wherein said composition comprises a method for preparing the inorganic oxide support substantially free of alkali component and a rare earth element and alkaline earth metal component slurry is formed, spray dried, calcined, impregnated with a noble metal element, an alkaline solution treatment and the step of drying and / or firing employed.
  11. 11. 按照权利要求1或2所述的组合物,其特征在于,所述基本不含碱金属和碱土金属的无机氧化物载体组分为氧化铝组分,所述氧化铝组分与稀土元素组分混合前经过酸化胶溶处理。 11. The composition of claim 1 or claim 2, wherein said inorganic oxide support substantially free of alkali metal and alkaline earth group metal into alumina component, alumina component and the rare earth element after acidified peptization treatment before mixing the components.
  12. 12. 按照权利要求11所述的组合物,其特征在于,所述无机氧化物载体组分为拟薄水铝石。 12. The composition of claim 11, wherein said inorganic oxide support component quasi boehmite.
  13. 13. 按照权利要求2所述的组合物,其特征在于,所述贵金属元素采用过量浸渍方法负载于载体上,浸渍时所述贵金属溶液的体积为载体孔体积的1. 5 - 15倍。 13. The composition according to claim 2, characterized in that, with an excess of the noble metal element supported on the carrier impregnation method, the noble metal impregnation solution by volume of pore volume 1.5 - A 15 times.
  14. 14. 按照权利要求13所述的组合物,其特征在于,所述贵金属溶液的体积为载体孔体积的5 - 10倍。 14. The composition of claim 13, wherein said noble metal volume of the solution is the pore volume of the carrier 5 - A 10-fold.
  15. 15. 按照权利要求1所述的组合物,其特征在于,所述碱性溶液为非金属元素碱性溶液。 15. The composition according to claim 1, wherein said alkaline solution is an alkaline solution non-metallic elements.
  16. 16. 按照权利要求15所述的组合物,其特征在于,所述非金属元素碱性溶液为氨水或碱性铵盐溶液。 16. The composition of claim 15, wherein the non-metallic element the alkaline solution is ammonia or a basic salt solution.
  17. 17. 按照权利要求1所述的组合物,其特征在于,所述引入贵金属后的组合物用碱性溶液处理时,所述碱性溶液的体积为组合物孔体积的1 一10倍。 17. The composition according to claim 1, wherein said composition after introduction of the noble metal is treated with an alkaline solution, the volume of the basic solution is a composition of 1 to 10 times the pore volume.
  18. 18. 按照权利要求17所述的组合物,其特征在于,所述碱性溶液的体积为组合物孔体积的1. 5 - 5倍。 18. The composition according to claim 17, wherein the volume of the alkaline solution is a 1.5 pore volume of the composition of 5 - fold.
  19. 19. 按照权利要求1、2、16、17或18所述的组合物,其特征在于,所述碱性溶液的浓度为0. 01 - 10mol/L。 19. The composition of claim 1,2,16,17 or 18, wherein the concentration of the alkaline solution is 0. 01 - 10mol / L.
  20. 20. 按照权利要求19所述的组合物,其特征在于,所述碱性溶液的浓度为0. 05 - 5mol/L〇 20. The composition of claim 19, wherein the concentration of the alkaline solution is 0. 05 - 5mol / L〇
  21. 21. 按照权利要求20所述的组合物,其特征在于,所述碱性溶液的浓度为0. 5 - 2mol/ L〇 21. The composition according to claim 20, wherein the concentration of the alkaline solution of 0. 5 - 2mol / L〇
  22. 22. -种流化催化裂化方法,包括将烃油与催化剂接触反应和再生的步骤,其特征在于,所述催化剂中含有权利要求1 一21任一项所述组合物,且权利要求1 一21任一项所述组合物的含量为〇. 05 - 5重量%。 22. - Species fluidized catalytic cracking process, comprising the step of contacting a hydrocarbon oil with the catalyst in the reaction and regeneration, wherein the catalyst comprises a composition as claimed in any one of the claims 1 a 21, as claimed in claim 1 and a 21 the content of the composition is any one billion 05 -. 5% by weight.
  23. 23. 按照权利要求22所述的方法,其特征在于,所述催化剂中权利要求1 一21任一项所述组合物的含量为0. 1 - 1. 5重量%。 23. The method according to claim 22, wherein, in the catalyst according to any of claims 1 a 21 a content of the composition is 0. 1-- 1.5 wt%.
  24. 24. 按照权利要求22或23所述的方法,其特征在于,所述催化剂包括权利要求1 一21 任一项所述组合物和裂化活性组分,权利要求1 一21任一项所述组合物与裂化活性组分处于不同的颗粒中或者在同一催化剂颗粒中含有权利要求1 一21任一项所述组合物与裂化活性组分。 24. The method of claim 22 or claim 23, wherein the catalyst comprises a composition according to any of claims 1 a 21, and cracking of the active ingredient, the composition according to any one of claims 1 a 21 It was cracking with the active ingredient, or in different particles contained in the same catalyst particle as claimed in claim cracking activity with a composition according to any component 21 1 a.
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US20020092796A1 (en) * 1995-05-05 2002-07-18 Peters Alan W. Reduced NOx combustion promoter for use in FCC processes
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