CN1026556C - Reclaiming and reusing of waste hydrocarbon steam inversion catalyst - Google Patents

Abstract

The present invention relates to a method for recovering a waste nickel catalyst of hydrocarbon steam conversion, which is characterized in that nickel is not recovered by the conventional electrical solution method or the conventional chemical method, but the catalyst is prepared by a total reuse method without waste slag discharge. The method simplifies technical processes, reduces a calcination temperature and reduces the catalyst cost by one half to one third. A raw catalyst prepared from a waste catalyst recovered by the method of the present invention has physicochemical performance and activity corresponding to those of a catalyst with pure alpha-Al2O3 as carrier raw materials and has improved active stability.

Description

Reclaiming and reusing of waste hydrocarbon steam inversion catalyst

The invention belongs to a kind of Preparation of catalysts method, this catalyst is applied to the steam-reforming of the hydrocarbon raw material in the petrochemical industry production, also belongs to the recovery and utilization technology of spent catalyst.

Technical background:

In hydrogen manufacturing, synthetic ammonia and methanol industry, a kind of catalyst that hydrocarbon raw material is carried out pyrolytic conversion by steam of extensive use, the active constituent of this catalyst is nickel, carrier adopts Al mostly ₂O ₃This catalyst cost height, the catalyst that just need to more renew when catalysqt deactivation owing to contain precious metal nickel in the spent catalyst of unloading down, need to be reclaimed existing waste and old NiO/Al ₂O ₃Or NiO/CaO-Al ₂O ₃The recovery method of type catalyst described in " Shandong petrochemical industry " 87 years No2, generally is to adopt electric smelting method and chemical recovering method NiO ₃, its starting point all is placed on and reclaims on the nickel, technical sophistication, and expense is big, energy consumption height, and the nickel that reclaims, its purity often can not satisfy the requirement of controlling catalyst, and can only reclaim 80% NiO, remainder NiO and the Al that still has higher using value ₂O ₃Recrement just can only abandon, and causes the residue contamination environment, perhaps only has a small amount of waste residue to be used for paving the way or making cement, and these use the recycling that all belongs to low value.

The purpose of invention:

The present invention has realized a kind of catalyst recovery method of higher-value, and spent catalyst is recycled and reused, and still makes this catalyst, and not only complete to the recovery of NiO precious metal, also to carrier A l ₂O ₃Recycled, eliminated like this environmental pollution of waste residue, and effectively be used to high value, use be a kind of new recovery method, make cheaply catalyst.

The general introduction of invention:

With the waste and old NiO/Al that retrieves ₂O ₃Or NiO/CaO-Al ₂O ₃Type nickel is that the diluted acid with 1～15% cleaned, and can use H after steam reforming catalysts was removed the impurity such as stone ₂SO ₄, HCL, HNO ₃, best cleaning fluid adds rare HNO ₃(for the old catalyst of the contaminating impurities such as no iron rust, for example: the catalyst that unloads out from device reformer tube bottom also can be without pickling) again with these old catalyst oven dry and pulverize, wears into certain fineness (all by 300 mesh sieves).This powder just can be by a certain percentage and fresh raw material α-Al ₂O ₃Powder or other powder mixes, adopt the method for conventional Kaolinite Preparation of Catalyst carrier to carry out the machine-shaping of carrier is again made the conversion catalyst agent carrier.The proportioning of old powder and new powder can be mixed by arbitrary proportion between 0～100%, and the carrier for preparing like this is reprocessed into catalyst, and the catalyst that its active and fresh feed are made is identical, and activity stability can also improve.

The effect of invention:

It is significant using method of the present invention to reclaim its effect of old catalyst, has realized purpose of the present invention: reduced cost, simplified technology, eliminated the pollution of discharging waste residue, effectively utilized all the components of old catalyst.This method can make the cost 20～60% of Kaolinite Preparation of Catalyst carrier, makes the cost 20～40% of catalyst, because saved the amount 20～40% of the precious metal nickel of the required dipping of preparation raw catelyst, has also saved α-Al ₂O ₃Use amount 0～100%, can also reduce by 40～100 ℃ of sintering temperatures, reduced energy consumption.As press α-Al ₂O ₃: the batch mixing of spent catalyst=1: 1 is made base substrate A, and its sintering temperature can reduce by 60 ℃, can make fuel cost reduce about 100 yuan/tons.

With the catalyst of this method preparation, all with not reclaim old catalyst raw material suitable, activity and activity stability be to some extent raising also for its physical and chemical performance.Small investment does not need complex device, only need set up an edge mill.This method be because being uniformly dispersed of nickel can be oversimplified technology, and each reduces once with the dipping of original Kaolinite Preparation of Catalyst, oven dry, decomposition technique process.Use the inventive method that the activity stability of catalyst is improved, with the catalyst that above-mentioned carrier A is made, after the burin-in process, its retentive activity obviously is better than industrial NiO/Al commonly used under the same conditions ₂O ₃Catalyst.Such as the catalyst made from carrier A, after 800 ℃ of hydrothermal treatment consists, its activity is equivalent to pure α-Al ₂O ₃110% of the similar catalyst of making.The present invention is to Al ₂O ₃Recovery can reach 100%, can reach 99% to the rate of recovery of Ni.

The present invention is applicable to prefabricated carrier earlier, the preparation process of soaking the immersion-type hydrocarbon steam conversion catalyst of nickel subsequently.

Embodiment:

1. with waste and old NiO/Al ₂O ₃Or NiO/CaO-Al ₂O ₃The type hydrocarbon steam conversion catalyst is broken or levigate extremely all by 300 mesh sieves.Then with 5: 95 ratio and α-Al ₂O ₃The powder mixing adds a certain amount of binding agent again, and solid agent is taked the extrustion process moulding, and is then dry, cutting, and roasting namely gets carrier B, and a certain amount of nickel on the B dipping namely be can be made into new hydrocarbon steam conversion catalyst.

2. press the identical method of embodiment 1, with spent catalyst: α-Al ₂O ₃The ratio of powder=1: 1 is made carrier, and the nickel oxide of dipping 9wt% can make performance and similar brand-new NiO/Al ₂O ₃The raw catelyst that catalyst is suitable.

3. press the identical method of embodiment 1, with spent catalyst: α-Al ₂O ₃Powder is that 80: 20 ratio is made carrier, and the nickel oxide of dipping 6wt% can make performance and similar brand-new NiO/Al ₂O ₃The raw catelyst that catalyst is suitable.

Claims (3)

1, a kind of recovery multiplexing method of dip type nickel series hydrocarbon steam conversion catalyst is characterized in that:

A. with waste and old NiO/Al ₂O ₃Or NiO/CaO-Al ₂O ₃, the type catalyst needs levigate:

B. with waste and old catalyst and pure α Al ₂O ₃Mix by the arbitrary proportion between the 0-100%, routinely method Kaolinite Preparation of Catalyst carrier further floods active component nickel again, produces catalyst.

2, by the described method of claim 1, it is characterized in that the spent catalyst of regaining that contains NiO removed impurity such as stone after, again through the inorganic acid pickling of 1-15%.

3, by the described method of claim 2, it is characterized in that described acid is nitric acid.